International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

ICNBME-2011
INTERNATIONAL CONFERENCE
on Nanotechnologies
and Biomedical Engineering
GERMAN-MOLDOVAN WORKSHOP ON
Novel Nanomaterials for Electronic,
Photonic and Biomedical Applications
Chisinau, Moldova, July 7-8, 2011

PROCEEDINGS
Organized by
 Academy of Sciences of Moldova
 Technical University of Moldova
 State Medical and Pharmaceutical University "Nicolae
Testemitanu" of the Republic of Moldova
 Moldavian Society of Biomedical Engineering
In cooperation with
 Medical Imagistic Society of Moldova
 Moldavian Association of Medical Informatics
Under the auspices
 of the German Ambassador to Moldova
Supported by
 European Federation for Medical Informatics
 GE Healthcare
 Alexander von Humboldt Foundation (Workshop)
 Global Biomarketing Group-Moldova
 NITECH S.R.L.
 Intermed Company
 XEROX Moldova

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

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All rights reserved. No parts of this book may by reproduced in

any form or by any means without written permision from the
publisher.

Published by: Technical University of Moldova

Editors: Corr. member Ion Tiginyanu and Prof. Dr. Victor Sontea

Responsibil for edition: Dr. Serghei Railean

Cover designer: Dmitri Anghiloglu

ICNBME-2011. International conference on Nanotechnologies and

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Biomedical Engineering greman-moldovan workshop on Novel
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Nanomaterials for Electronic, Photonic and Biomedical Applications,
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Chisinau, July 7-8, 2011
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?resp. for ed. Serghei Railean. - Ch.: "Elan Inc" SRL,
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2011 (Tipogr. "Elan Poligraf" SRL) - 460 p.
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Antetit.: Acad. of Sciences of Moldova, Techn. Univ. of Moldova, State
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Medical and Pharmaceuitcal Univ. "Nicolae Testemitanu" of the Rep. of
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Moldova [et al.].
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-Texte: lb. rom., germ., engl. - Bibliogr. la sfarsitul art. - 150 ex.

Elan Poligraf ???????????????????????????????

ISBN 978-9975-66-239-0
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© Technical University of Moldova, 2011

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International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Honorary Chairmans oh the ICNBME – 2011

 Academician Ion Ababii, Rector of the State Medical and Pharmaceutical
University "Nicolae Testemitanu" of the Republic of Moldova
 Academician Ion Bostan, Rector of the Technical University of Moldova
 Academician Gheorghe Duca, President of the Academy of Sciences of
Moldova

International Advisory Committee

R. Adelung Germany O. Maiorov Ukraine
A. Andriesh Moldova F. J. Manjón Herrera Spain
E. Arushanov Moldova H. Mimura Japan
R. Boyd Canada R. Negoescu Romania
J.-C. Buisson France T. Pauporte France
L. Chow USA D. Pavlidis Germany
P. Cristea Romania V. Pershenkov Russia
D. Dascalu Romania P. Schmuki Germany
D. Dimova-Malinovska Bulgaria A. Schulte USA
R. Engelbrecht Germany C. Schwab France
H. Föll Germany A. Simashkevich Moldova
V. Fomin Germany B. Simionescu Romania
Gh.Gheorghe Romania R. Singh USA
Gh.Ghidirim Moldova T. Sisianu Moldova
S. Groppa Moldova V. Socolov Ukraine
H. Hartnagel Germany M. Stevens-Kalceff Australia
N. Jula Romania R. Strungaru Romania
V. Kantser Moldova H. Teodorescu Romania
D. Lincot France V. Ushenco Ukraine
V. Litovchenko Ukraine D. Zaharia Romania

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International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Program Committee
I. Tiginyanu Moldova Chairman S. Langa Germany
V. Prisacari Moldova Co-Chairman J. Lloyd-Hughes UK
V. Dorogan Moldova Co-Chairman A. Rotaru Moldova
S. Andronic Moldova E.Rusu Moldova
G. Arzumanyan Russia A. Salam Hamdy Germany
E. Badinter Moldova A. Sarua UK
I. Balmus Moldova A. Saulea Moldova
A. Casian Moldova A. Sidorenco Moldova
R. Ciorap Romania V. Skuratov Russia
S. Ciubotaru Germany M. Sleahtitchi Moldova
A. Cojocaru Germany P. Stratulat Moldova
Gh.Curocichin Moldova N. Syrbu Moldova
M. Dragoman Romania V. Trofim Moldova
P. Filip Moldova D. Tsiulyanu Moldova
C. Gaindric Moldova V. Ursaki Moldova
P. Gashin Moldova A. Usatîi Moldova
V. Harabagiu Romania R. Werlein Swiss
V. Iakovlev Swiss I. Zatusevski Moldova
L. Kulyuk Moldova

Organizing Committee
V. Sontea Moldova Chairman Iu. Nica Moldova
V. Vovc Moldova Co - Chairman I. Pocaznoi Moldova
S. Railean Moldova Secretary V. Popa Moldova
T. Ciaicovschii Moldova A. Rosca Moldova
V. Captari Moldova A. Rosioru Moldova
L. Ghimpu Moldova V. Scripnic Moldova
O. Lupan Moldova S. Sisianu Moldova

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

CONTENTS
German-Moldovan Workshop on Novel Nanomaterials for
Electronic, Photonic and Biomedical Applications
Monte-Carlo-Simulation of Crystallographical Pore Growth in III-V-Semiconductors ..................... 13
MALTE LEISNER, JÜRGEN CARSTENSEN, AND HELMUT FÖLL
Porous InP as Piezoelectric Matrix Material in 1-3 Magnetoelectric Composite Sensors................... 16
M.-D. GERNGROSS, M. LEISNER, J. CARSTENSEN AND H. FÖLL
The Collaborative Research Center ―Magnetoelectric Composites - Future Biomagnetic
Interfaces‖ at the Christian-Albrechts-University in Kiel ............................................................................. 20
H. FÖLL
Investigation of Mesoporous Structures for Thermoelectric Applications .............................................. 21
A. COJOCARU, J. CARSTENSEN, J. BOOR, V. SCHMIDT AND H. FÖLL
Ballistic Charge Carrier Devices for Terahertz Signal Generation............................................................ 24
H.L. HARTNAGEL
Two Simple Examples for the Micro-nano Integration of Nanowires as Electronic Device Elements
.......................................................................................................................................................................................... 25
RAINER ADELUNG
Strain-Tunable Quantum Dot Devices ................................................................................................................. 28
A. RASTELLI, R. TROTTA, E. ZALLO, P. ATKINSON, E. MAGERL, F. DING, J. D. PLUMHOF, S.
KUMAR, K. DÖRR, O.G. SCHMIDT
Zinc Oxide Nanostructures: New Properties for Advanced Applications ................................................ 29
OLEG LUPAN, LEE CHOW, THIERRY PAUPORTÉ
Surface Plasmon Enhanced Luminescence from Ag covered Anatase Titania Nanotubes ................. 33
Mihai ENACHI, Veaceslav URSAKI, Vladimir SERGENTU
Development of GaN-based Nanosensors using Surface Charge Lithography ....................................... 36
VEACESLAV POPA, TUDOR BRANISTE, OLESEA VOLCIUC, DIMITRIS PAVLIDIS, ANDREI SARUA,
PETER HEARD, MARTIN KUBALL
Development of Conductive Nanotemplates on ZnSe ..................................................................................... 39
EDUARD MONAICO, ION TIGINYANU, GLEB COLIBABA, D. D. NEDEOGLO, ALA COJOCARU,
HELMUT FÖLL
Perspectives of Single Cast Nanowires Technology ......................................................................................... 43
ANATOLII IOISHER, EFIM BADINTER, NICOLAE LEPORDA , VITALIE POSTOLACHE,
EDUARD MONAICO, ION TIGHINYANU

Section 1: Nanotechnologies and Nanomaterials

Smart Self-healing Eco-friendly Nano and Nano-composite Protective Coatings ................................. 48
ABDEL SALAM HAMDY MAKHLOUF
Nanowires of Silicon Carbide and 3D SiC/C Nanocomposites With Inverse Opal Structure ............ 49
G.A. EMELCHENKO, A.A. ZHOKHOV, V.M. MASALOV, E.A. KUDRENKO, A.N. TERESHENKO, E.A.
STEINMAN, I.I. KHODOS, V.I. ZINENKO, YU.A. AGAFONOV
ZnO Growth Technologies: Current Status and Perspectives ..................................................................... 53
OLEG LUPAN

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High-Pressure Study of YVO4 Nanoboxes .......................................................................................................... 59

F.J. MANJÓN, O. GOMIS, S. RAY, S. F. LEÓN-LUIS, U.R. RODRÍGUEZ-MENDOZA, V. LAVÍN, A.
SEGURA, D. MARTÍNEZ-GARCÍA, AND CH. FERRER-ROCA
Collective Elementary Excitations of 2D Magnetoexcitons Taking Into Account Excited Landau
levels. ............................................................................................................................................................................... 60
S.A.MOSKALENKO, M.A.LIBERMAN, E.V.DUMANOV, S.RUSU, F.CERBU
Influence of Adsorption of Organic Molecules on the PL Spectra of Porous Nanostructure and
Carbon Nanotubes, Covering the Surface of Silicon. ...................................................................................... 66
V.G. LITOVCHENKO, T.I. GORBANYUK
Photoelectric Converters: Current State Analysis and Prospects of Evolution ...................................... 67
Y.I. YAKIMENKO, G.M. MLADENOV, V.M. SPIVAK, A.V. BOGDAN, V.M.KOVAL
Synthesis and Characterization of Colloidal PbS Quantum Dots in Gelatin........................................... 72
ANATOLIE MITIOGLU, CORNEL GHERMAN, RENATA LASCOVA, ANATOLII CUHARUC,
ANATOLIE GAVRILUŢA, LEONID CULIUC
Synthesis of AAO Nanotemplate and Its Properties ........................................................................................ 75
NATALIA TSYNTARU, BERKAY KAVAS, JEAN-PIERRE CELIS
Analysis of the Behavior of PVDF Layers Deposited under Various Conditions .................................. 80
VICTOR COJOCARU, ALEXEI KATASHEV, HORIA-NICOLAI TEODORESCU
Exciton Luminescence in In0.3Ga0.7As/GaAs Quantum Well Heterostructures ...................................... 83
ELI KAPON, ALEXANDRU MEREUŢA, ANDREI DOROGAN, NICOLAE DRAGUTAN,
TATIANA VIERU,NICOLAE SYRBU
Effect of Harmful Gases on the A.C. Conductivity of Tellurium Thin Films .......................................... 86
D.TSIULYANU, O.MOCREAC
Optical Properties of Phase Change Memory Ge1Sb2Te4 Glasses............................................................... 90
M.S.IOVU, E.P.COLOMEICO, V.G.BENEA, A.M.ANDRIESH
Exchange Electron-Hole Interaction of Two-Dimensional Magnetoexcitons under the Influence of
the Rashba Spin-Orbit Coupling ........................................................................................................................... 94
S.A. MOSKALENKO, I.V. PODLESNY, B.V. NOVIKOV, E.S. KISELYOVA,
I.A. LELYAKOV, AND L. GHERCIU
Magnetotransport Properties of Ultrathin LaMnO3 Layers ........................................................................ 97
OLEG SHAPOVAL, ALEXANDER BELENCHUK, EFIM ZASAVITSKY, VALERIU KANTSER, VASILY
MOSHNYAGA
Nonlinear Transmission of Two Successive Ultrashort Laser Pulses by a Thin Semiconductor Film
under Two-Photon Generation of Biexcitons. Giant Oscillator Strength Model ................................. 101
IGOR BELOUSSOV, PETER KHSDZHI, TATIANA SHEMYAKOVA, AND SPIRIDON RUSU
Quantum Oscillations of Conductivity in Bismuth Wires ........................................................................... 104
ELENA CONDREA
Superposition of the luminescence spectra of free and bound excitons in ZnP2-D48 .......................... 108
ION STAMOV, LUCRETIA NEMERENCO, IURII IVANENCO, NICOLAE SYRBU
Exciton Spectra of AgAsS2 Crystals ................................................................................................................... 111
LUCRETSIA NEMERENCO, IURIE IVANENCO
Large Oscillator Strength Excitons in PbGa2S4 Crystals............................................................................. 114
PARVAN V., MIROVSCII V., MASNIC A.
Effect of Time on the Properties of Crystallization Agents: Ice-forming Aerosols ............................. 117
EFIM ZASAVITSKY, VALERII KANTSER, ANATOLII SIDORENKO, ION GARABA,
EVGHENII POTAPOV, NICOLAI KIM

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Detection in the Contacts With Bismuth-Antimony Alloy: Numerical Modeling of the Contact
Area Role ..................................................................................................................................................................... 121
IACOV KERNER
Optical Properties of Amorphous As-Se Thin Films ..................................................................................... 124
D.V.HAREA, M.S.IOVU, V.G.BENEA, E.P.COLOMEICO, I.A.COJOCARU
Morphology and Luminescence Properties of ZnO layers produced by Magnetron Spattering .... 128
EMIL RUSU, IRINA GHIŢU, VLADIMIR PRILEPOV, VICTOR ZALAMAI, VEACESLAV URSAKI
Effective Laser Luminescence of Nanocomposites Eu(TTA)2(Ph3PO)2NO3-Polyvinylpyrrolidone 133
V.I. VERLAN, M.S. IOVU, S.A. BUZURNIUC, YU.H. NISTOR, I. CULEAC, C.I. TURTA,
V.E. ZUBAREVA, L.A. MALAHOV
Nanoporous Zinc Oxide Films Prepared by Magnetron Sputtering ........................................................ 138
L. GHIMPU, O. LUPAN, L. POPESCU, I.M. TIGINYANU
Interband Optical Transitions in the Region of Excitonic Resonance in In0.3Ga0.7As/GaAs
Quantum Wells .......................................................................................................................................................... 142
ELI KAPON, ALEXANDRU MEREUŢA, ANDREI DOROGAN, NICOLAE DRAGUTAN,TATIANA VIERU,
NICOLAE SYRBU, VICTOR ZALAMAI

Section 2: Micro- and Nano-objects, Nanostrucured and higly

integrated systems, Biophysics
Multi-gated Field Emitters for a Micro-column ............................................................................................. 145
HIDENORI MIMURA, AKIFUMI KOIKE, TORU AOKI, YOICHIRO NEO, TOMOYA YOSHIDA, AND
MASAYOSHI NAGAO
Nano Metrology Aspects of Design, Simulation, Fabrication, Testing , Reliability and Failure
Analysis of Wafer Fused VCSEL ........................................................................................................................ 148
VLADIMIR IAKOVLEV
Fundamental Issues in the Manufacturing of Nanoelectromechanical (NEMS) and Related
Nanosystems ............................................................................................................................................................... 154
R. SINGH, G.F. ALAPATT, N. GUPTA, K.F. POOLE
Topological Insulator Materials and Nanostructures for Future Electronics, Spintronics and
Energy Conversion ................................................................................................................................................... 157
VALERIU.KANTSER
Functionalised AlGaN/GaN Heterostructures for Electronic Saccharide Sensing .............................. 161
A. SARUA, T. SCHULLER, M. KUBALL, S. FLOWER, T. D. JAMES,
J. FOSSEY, Jo DAS, S. DEGROOT, M. GERMAIN
More Efficient Nanostructured Material for Noncontact Body Temperature Measurement .......... 164
ANATOLIE CASIAN, ION BALMUS, VIOREL DUSCIAC, VEACESLAV NICIC
Single-Crystal Microwires Based on Doped Bi for Anisotropic Thermoelectric Devices .................. 168
L. KONOPKO, A. NIKOLAEVA, T. HUBER, A. TSURKAN
Superconducting Spin Switch Based on Superconductor-Ferromagnet Nanostructures for
Spintronics .................................................................................................................................................................. 172
JAN KEHRLE, VLADIMIR ZDRAVKOV, CLAUS MUELLER, GUENTER OBERMEIER, MATTHIAS
SCHRECK,STEFAN GSELL, SIEGFRIED HORN, REINHARD TIDECKS, ROMAN MORARI, ANDREI PREPELITSA,
EVGENII ANTROPOV, ALEXEI SOCROVISCIUC, EBERHARD NOLD, LENAR TAGIROV, ANATOLI SIDORENKO
High Resolution Position Inductive Transducers for Harsh Environmental Conditions .................. 175
NICOLAE JULA, TUDOR URSU, CRISTINA NICOLETA DIACONESCU, RADU OBREJA
Electrostatic Ion Shutter with Ejecting Electrode as a Part of a Ion Mobility Spectrometer .......... 180
ANATOLY V. GOLOVIN

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The Simulation of Pulsed Heater for a Sampling System for the Ion Mobility Spectrometer ......... 183
EVGENIY MALKIN
Periodic Signals From a Nanopore Coulter Counter .................................................................................... 186
Y. RUDZEVICH,Y. LIN, G. EVANS, A. ORDONEZ, O. LUPAN AND L. CHOW
About the Using of Polarization Methods in Investigating the Polarization Sensitive Nanosystems
........................................................................................................................................................................................ 190
C.YU. ZENKOVA, I.V. SOLTYS
Interferometric Method Application for Sub-micrometers Thickness Measurements of Spin-
coated PEPC and PETPC Polymer Films ......................................................................................................... 194
A.MESHALKIN, A.ANDRIES, E.ACHIMOVA, L.BETS, I.ANDRIES, S.DRAHNEA
Design of the Holographic Fiber-optic Electronic Speckle Pattern Interferometer for Optical
Constants of Glasses Measurements. .................................................................................................................. 198
O. IASENIUC, A. ANDRIESH, E. ACHIMOVA, V. ABASHKIN
Improvement of SiO2(Ge)SiO2/Si Nanostructures by Low Dose γ-radiation ....................................... 203
S.T. SHISHIYANU , T.S. SHISHIYANU, E. YILMAZ, R. TURAN, N.A.P. MOGADDAM
Nanoperforated Indium Phosphide for Terahertz Imaging Bio-applications ....................................... 207
D. ESINENCO, L. SIRBU, I. VODA, L. GHIMPU, R. MULLER, R. VOICU, M. DANILA, A. LECA, T.
DASCALU, I.M. TIGINYANU and V. URSAKI
Nanolamellar Structures of Oxide-AIIIBVI:Cd Semiconductors Type for use as Detectors of
Radiation in the UV Spectral Region ................................................................................................................. 211
L.DMITROGLO, D. UNTILA, P.CHETRUSH, I. EVTODIEV, Iu. CARAMAN, G. LAZAR, V. NEDEFF
Approximation of MOSFET Transistor Characteristics in Micro- and Nanoelectronics ............... 215
ALEXANDR PENIN, ANATOLI SIDORENKO
Electronic Hydrostatic Transducer with Digital Output ............................................................................. 218
V. SMYSLOV, V. YAKUNIN, I. BELOTSERKOVSKII, AND A. YAKUNIN
Wave Model as a Physical Basis of an Algebra of Bio- and Nano- structures....................................... 221
BETTIN MIRONOV
Two-Photon Coherent Fields and its Application in Communication .................................................... 227
MARINA ŢURCAN
Ignition Method of Corona Discharge with Modulation of the Field in Ion Source of Ion Mobility
spectrometer ............................................................................................................................................................... 231
EVGENIY GROMOV
Calibration Method for Ion Mobility Spectrometer ...................................................................................... 234
VALERY VASILIEV
The Fitting Parameters Extraction of Conversion Model of the Low Dose Rate Effect in Bipolar
Devices .......................................................................................................................................................................... 236
ALEXANDER BAKERENKOV
The Controlling of Nanoparticles by the Polarization Methods ............................................................... 239
V.ANGELSKY, C.Yu. ZENKOVA
Preparation and Characterization of N-doped TiO2 with Enhanced Photocatalytic Activity ......... 243
C. PĂSTRĂVANU, M. IGNAT, E. POPOVICI, I. CRETESCU
Activities in Nanomedicine in Romania ............................................................................................................. 247
DAN DASCALU

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Section 3: Biomedical Instrumentation and Devices

Health Technology Management ......................................................................................................................... 248
VICTOR ŞONTEA, PETRU STRATULAT, REINHOLD WERLEIN
Micro-Spectroscopy of Single Erythrocytes Infected with the Malaria Parasite ................................. 252
SILKI ARORA, SANG HOON PARK, JENNIFER MAUSER,
DEBOPAM CHAKRABARTI, ALFONS SCHULTE
Ultra Violet Radiation Regulates Wettability Property of Prosthetic PMMA...................................... 255
YURI DEKHTYAR, LINDA LANCERE, NATALIYA POLYAKA,
ALEXANDER SUDNIKOVICH, FYODOR TYULKIN
Optical Dosimetry for Controlling the Efficiency of Laser Phototherapy ............................................. 257
M.M. ASIMOV, R.M. ASIMOV, A.N. RUBINOV, A.I. GISBRECHT
Electro-acoustical and Electrophysiological Examinations in Diagnostics of Otitis Media in Infants
........................................................................................................................................................................................ 263
I. ABABII, S. DIACOVA, M. MANIUC, P. ABABII, L. DANILOV
Installation for Local Hyperthermia in Crossed Laser Fluxes ................................................................... 266
IURIE NICA, SERGHEI ZAVRAJNÎI, ANDREI GRITZCO, IURIE TIRON, DUMITRU ESHANU,
VLADIMIR MUSTEATZA, NDREI STALBE
The Role of Microscopic Techniques in Performing Tympanoplasty in Children .............................. 271
I. ABABII, L. DANILOV, M. MANIUC, P. ABABII, S. DIACOVA
Biomedical Physiotherapeutic Complex ............................................................................................................ 273
VALERIAN DOROGAN, VITALIE SECRIERU, TATIANA VIERU, STANISLAV VIERU, ANDREI
DOROGAN, EUGENIU MUNTEANU, ŞTEFAN BALICA
The Change of Peripheral Excitability Caused by Millimeter Waves ..................................................... 277
AUREL SAULEA, VICTORIA CHIHAI
The Implementation of Modern Digital Technology in X-ray Medical Diagnoses in Republic of
Moldova – a Stringent Necessity. ......................................................................................................................... 279
ANDREI ROSCA
Sensors of Ultraviolet Radiation for Medical Equipment............................................................................ 281
I. ABABII, E. ARAMA
Influence of Face Mask on Breathing During Hyperventilation Test ...................................................... 285
TUDOR BESLEAGA, PASCALE CALABRESE, VICTOR VOVC, PIERRE BACONNIER, ION
MOLDOVANU, ANDRE EBERHARD
Heart Rate Variability: the Involvement of Breathing Pattern (chest breathing, abdominal
breathing) and Anxiety. .......................................................................................................................................... 288
ANDREI GANENCO, VICTR VOVC, ION MOLDOVANU, SVETLANA LOZOVANU
Optical Power Control Module ........................................................................................................................... 290
ANDREI GRITZCO, SERGEY ZAVRAJNYI, ANDREI STALBE, IURIE NICA
Photon Irradiation Device for Antimicrobial Therapy ................................................................................ 294
IURIE NICA, LEONID POGORELSCHI, EUGEN MAXIMOV, VALERIU CEBOTARI,
CONSTANTINIAVORSCHI, VITALIE BOLOGA, VLADIMIR NAHABA, EMILIA ŢÎMBALARI
Temperature Monitoring System ........................................................................................................................ 297
SERGHEI ZAVRAJNYI, IURIE TIRON, ANDREI GRIŢCO, ANDREI STALBE, IURIE NICA
Device for Testing of Biological Material .......................................................................................................... 301
BELIC O., ARAMĂ E., ŞTEFANEŢ M., IAVORSCHI A., PÎRŢAC V., BABUCI A.
Advanced Potential of the Photolpetismograph PPG-2 in the Non-invasive Vascular Diagnosis ... 304
A.SLOBOZEANU, I.ZATUŞEVSKI, A.CREŢU, V. ŞONTEA

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Complex device for recording and signal processing of cardiac activity ................................................ 307
VICTOR ŞONTEA, ANATOLIE IAVORSCHI, VALERII PAHOMI, VALERIU PÎRŢAC,
DMITRI ANGHILOGLU,SERGHEI RAILEAN
New Investigation Technologies of the Cardiovascular System and of the Vegetative Nervous
System .......................................................................................................................................................................... 310
V.SCRIPNIC, V.ȘONTEA, I.ZATUȘEVSKI, A.SAULEA, E.ZEMȚOVSKI,
A.IAVORSCHI, V.PÂRȚAC, V.SOCOLOV, N.ALEXEEVA
Millimeter Wave Nonthermal Therapeutic Device Based on Parallel-Strip Technology .................. 313
SAINSUS IURIE, RAILEAN SERGIU, ROTARU ANATOL,
CONEV ALEXEI, RUSSEV IURIE, POSTORONCA SVEATOSLAV, SCERBII DENIS
Obstructive Sleep Apnea: Biomedical Devices for Treatment ................................................................... 317
Victor VOVC

Section 4: Biomaterials
Mid-term Results of Tissue Engineered Valvular Grafts for Pulmonary Valve Replacement in
Pediatric Patients and Young Adults. ................................................................................................................ 319
S. CEBOTARI, I. TUDORACHE, E. CHEPTANARU, S. BARNACIUC, A. CAZACU, O. MALIGA, O. REPIN,
L. MANIUC, T. BREYMANN, S. SARIKOUCH, D. BOETHIG, A. GOERLER, A. HAVERICH, A.
CIUBOTARU
Interaction of Bacteria With Nanostructured Zinc-oxide Thin Films ..................................................... 320
ILIANA A. IVANOVA, ORLIN ANGELOV, LIUDMILA KRASTEVA, TATIANA PESHKOVA, KAROLINA
PAPAZOVA, DORIANA DIMOVA-MALINOVSKA, CECO D. DUSHKIN
DLC biocompatible thin films for cardiovascular implants........................................................................ 325
S.T. SHISHIYANU , T.S. SHISHIYANU, P.S. STEFANOV, V.K. GUEORGUIEV
Antimicrobial Polymers: from Structure Design to Specific Properties and Applications ............... 328
MADALINA ZANOAGA, FULGA TANASA
Biocompatible and Resorbable Polymeric Materials for Surgical Sutures ............................................ 329
FULGA TANASĂ, MĂDĂLINA ZĂNOAGĂ
Network Macromolecular Structures. The Crosslinker Effect .................................................................. 335
LOREDANA E. NITA, MANUELA T. NISTOR, AURICA P. CHIRIAC, IORDANA NEAMTU
Identification and Analysis of Sources Relative to the Characteristics of Pharmaceutical
Innovation ................................................................................................................................................................... 340
MAIA IORDATII, ALAIN VENOT, CATHERINE DUCLOS
Silica Nanoparticles for Improving Efficiency of Virus-Like Particle Based Hepatitis B Vaccine 344
MARINA ROMANOVA, YURY DEKHTYAR, ANNA KACHANOVSKA, DACE SKRASTINA, REGINA
RENHOFA, PAUL PUMPENS, ALOIZIJS PATMALNIEKS
Collagen - Isolation and Perspectives of Application of Nature Nanomaterials ................................... 347
ELENA MOCAN, OLGA TAGADIUC, TATIANA REVENCU AND VIOREL NACU
Colloidal Nanosilver – a Product of Nanotechnology .................................................................................... 350
CORINA SCUTARI, VEACESLAV GONCIAR, IVAN CEKMAN, NADEJDA GORCEACOVA
Synthesis of CdSe Nanoparticles and Their Effect on the Antioxidant Activity of Spirulina
Platensis and Porphyridium Cruentum Cells .................................................................................................. 354
V. RUDIC, L. CEPOI, L. RUDI, T.CHIRIAC, A. NICORICI, A. TODOSICIUC, T.GUTSUL
Influence of Copper Coordination Compounds and Cyanobacterian Remedy BioR on Bone
Collagen and Hydroxyproline Concentrations (ontogenetic view) ........................................................... 357
OLGA TAGADIUC, AURELIAN GULEA, VALERIU RUDIC, VALENTIN GUDUMAC

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Comparative Study Of The Mechanical Characteristics Of Dental Implants Made From

Biomaterials Covered With DLC Depositions ................................................................................................. 362
STANCA COMŞA, ADRIAN PACIOGA, DOINA GHEORGHIU, STEFAN MARIA
Using Nonconventional Structures as Protective Colloids in the Dispersion Polymerization of 2 -
Hydroxyethyl Methacrylate with a Comonomer with Spiroacetal Moiety ............................................ 365
AURICA P. CHIRIAC, LOREDANA E. NITA, MANUELA T. NISTOR
Innovative Realizations in the Research of Dental Implants ...................................................................... 369
GHEORGHE GRANCIUC

Section 5: Medical Imaging, Image and Signal Processing

Advanced EEG Signal Processing ....................................................................................................................... 373
RODICA STRUNGARU, G. MIHAELA UNGUREANU
Polarization-Singular Processing of Biological Layers Laser Images in Order to Diagnose and
Classify their Optical Properties .......................................................................................................................... 377
ALEXANDER G. USHENKO, ALEXANDER V. DUBOLAZOV, ARTEM O. KARACHEVTSEV
An Optimized Compounding Approach to Ultrasound Imaging .............................................................. 381
YAIR KERNER AND MOSHE PORAT
Elastography - New Imagistic Method for Assessment of Liver Structure in Children .................... 387
MARGINEAN OANA, BRANZANIUC KLARA, MARGINEAN C., PITEA ANA MARIA, AZAMFIREI
LEONARD, LUDMILA BOLOGA, LUDMILA CEREMPEI, NINEL REVENCO
Fetal Survey via Abdominal Recorded Signals ............................................................................................... 391
DRAGOS TARALUNGA, WERNER WOLF, MIHAELA UNGUREANU AND RODICA STRUNGARU
Statistic and Fractal Processing of Human Biological Fluids Phase-Inhomogeneous Images ......... 395
YURIY USHENKO, OLGA TELENHA, VALENTINE BALANETSKA, MAKSIM SIDOR
Ultrasound Imaging: Correction of Geometric Distortions using Warping .......................................... 400
ARI LEV-OR AND MOSHE PORAT
Application of a Threshold Methods for Compression of Vocal Signals ................................................ 404
MAHJOUBIAN MASOUD, G.N. ROZORYNOV, FENDRI MOHAMED AYMEN

Computed Tomography Aspects of the Endoscoic Sinus Surgery in Children .................................... 406
MIHAIL MANIUC, POLINA ABABII
The Interconnection of Polarization Singular Structure and Mueller-matrix Images of Biological
Tissues in the Tasks of Cancer Changes Diagnostics .................................................................................... 409
ALEXANDER DUBOLAZOV, ARTEM KARACHEVTSEV, VLADIMIR USHENKO, VADIM ISTRATIY

Section 6: Information Technologies for Health Care,

Telemedicine and E-Health
Bioengineering the Mind: from Artificial Intelligence towards Artificial Consciousness ................. 414
RADU NEGOESCU
Cross-Sector-Communication and Continuity of Care: Using Standards for an Integrative Health
Environment ............................................................................................................................................................... 419
ROLF ENGELBRECHT, CLAUDIA HILDEBRAND, HANS DEMSKI
New Parameter for Describing and Analysis of Optical-anisotropic Properties of Biological Liquid
Crystals Nets............................................................................................................................................................... 424
YURIY A. USHENKO

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Better Information, etter Decisions, better Care– Introducing a Web-based Inventory System for
Medical Devices in Moldova .................................................................................................................................. 427
CLAUDIO ZAUGG
Formation of Economic-managerial Knowledge System within Training of Healthcare Workers 431
OLGA KUDELINA
Towards an Images Dataset Processing trough Supervised and Unsupervised Learning ................. 434
NICOLETA ROGOVSCHI, NISTOR GROZAVU
Use of Telemedicine in Pilot Centers within the Perinatal System ........................................................... 438
P. STRATULAT, TATIANA CARAUȘ, M. BLUNIER, ALA CURTEANU

SonaRes - Computer-Aided Approach for Advanced Ultrasound Medical Diagnostics ................... 441
LIUDMILA BURTSEVA, SVETLANA COJOCARU, CONSTANTIN GAINDRIC,
OLGA POPCOVA, IULIAN SECRIERU
Information System Analysis of Heart Rate Variability .............................................................................. 445
ANATOLIE IAVORSCHI, VALERII PAHOMI, VALERIU PIRTAC, DMITRII ANGHILOGLU, SERGHEI
RAILEAN, ANDREI BRAGARENCO, VITALIE SCRIPNIC
The Analysis of the Legal Framework in the eHealth Field in Moldova, in the Context of
European Integration .............................................................................................................................................. 448
ALEXANDRU ROŞIORU
The Intelligent Support System for Remission in Patients with Psychiatric Disorders in Epilepsy
........................................................................................................................................................................................ 452
MARIA BUTNARU, ANA CAPATANA, GHEORGHE CAPATANA,
OLEG COBILEANSCHI ALEXANDRU POPOV

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Monte-Carlo-Simulation of Crystallographical
Pore Growth in III-V-Semiconductors
Malte LEISNER, Jürgen CARSTENSEN, and Helmut FÖLL
Institute for Materials Science, Christian-Albrechts-University of Kiel, Kaiserstrasse 2, 24143 Kiel,
Germany
[email protected]
Abstract – The growth of crystallographical pores in III-V-semiconductors can be understood in the
framework of a simple model, which is based on the assumption that the branching of pores is proportional to
the current density at the pore tips. The stochastic nature of this model allows its implementation into a
three-dimensional Monte-Carlo-simulation of pore growth. The simulation is able to reproduce the
experimentally observed crysto pore structures in III-V-semiconductors in full quantitative detail. The
different branching probabilities for different semiconductors, as well as doping levels, can be deduced from
the specific passivation behavior of the semiconductor-electrolyte-interface at the pore tips.

Index Terms – III-V, crystallographical pores, electrochemical etching, Monte-Carlo-Simulation, InP.

I. INTRODUCTION
Crystallographical pores (crysto pores) owe their name to
their crystallographic growth direction, e.g. the <111>B-
direction in III-V-semiconductors, which are the most
prominent semiconductor family to feature crysto pores.
They have been successfully etched into n-type InP, GaAs,
and GaP [1, 2] and show crystallographically defined
tetrahedron-shaped pore tips and crystallographical pore
walls. Due to the appearance of crystos in several other
semiconductors [3, 4], as well as in different electrolytes, the
mode of crystallographical pore growth can be seen as a
meta feature of pore growth [5]. Therefore crysto pore
growth can serve as a model system for the development of a
meta model of pore growth. As a starting point, the pore
growth in III-V-semiconductors, especially InP, will be
considered.
II. EXPERIMENTAL
Samples consisted of (100)-oriented n-type InP and GaAs
with different doping levels. All experiments have been
carried out in the electrochemical double cell described in
[6] at T = 20 °C. As electrolyte, 5 wt.% HCl has been used.
Experiments have been performed in constant-current-mode
with a short 1 s high voltage pulse in the beginning to enable
a homogeneous nucleation of pore growth.
III. RESULTS
An example of the resulting crysto pore structures is
presented in Fig. 1 for three different etching times in InP
with the doping level of ND = 8 · 1017 cm-3 and for a constant
current density of j = 0.4 mA/cm2. The left hand side shows Fig. 1. Resulting crysto pore structures in a constant current experiment, j
= 0.4 mA/cm2, on InP with the doping level ND = 8 · 1017 cm-3, (11̄0)-
SEM images of the (11̄0)-plane of the pore structures, the plane. Different etching times are indicated. The left hand side shows
right hand side the corresponding simulation details, as will SEM images of the pore structure, the right hand side the corresponding
be discussed in the subsequential part of this manuscript. simulation result.
Crysto pores growing into the two downward pointing
Further data has been obtained in these experiments: the
<111>B-directions can be identified as lengthy tunnels,
pore density of upward and downward growing pores as
whereas pores growing into the two upward pointing
function of depth, the pore depth as function of time, as well
<111>B-directions are intersecting the plane of view and are
as the number of active pores are all facts which the
therefore visible as triangular intersection points.
simulation aims to reproduce. But first a short description of
the model which is implemented in the simulation follows.
IV. MODEL
The model basically consists of two assumptions:
i) The branching probability per area and time at the pore

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

tips ptips, resp. pore walls pwalls, is proportional to the current 0 5 10 15 20 25 30

density at the pore tips jtips. Since current density is just 9 9
30 min
charge per time and area, within the current burst model this 8 150 min 8
assumtion can easily be understood as an increased 7
360 min
7
branching probability for short times of interface 6 6

pore [µm ]
-2
passivation.
5 5
ii) The valence of dissolution is constant, i.e. a constant
amount of semiconductor material is etched per unit time. 4 4
3 3
V. MONTE-CARLO-SIMULATION
2 2
The stochastic nature of the above described model allows
1 1
for its implementation into a three-dimensional Monte-
Carlo-Simulation, which has been carried out in a three- 0 0
dimensional simulation-array, which is schematically 0 5 10 15 20 25 30
illustrated in Fig. 2. d [µm]
(a)
0 5 10 15 20 25 30
9 9
x 60 min
y 8 150 min 8
z 7 360 min 7
6 6

pore [µm ]
-2 5 5
(110) 4 4
3 3
2 2
1 1
(110) simulation-array 0 0
0 5 10 15 20 25 30
Fig. 2. Schematic illustration of the three-dimensional simulation-array d [µm]
used in the Monte-Carlo-Simulation. The black chains of voxels represent
the crysto pores growing into the two upward pointing <111>B-directions (b)
respective to the (100)-oriented surface, the blue chains of voxels the 0 50 100 150 200 250 300 350 400
crysto pores growing into the two downward pointing <111>B-directions. 35 35

30 30
The array usually consists of (1024)3 voxels, which can be
25 25
allocated with different numbers that represent pore walls or
tips, which can be active or inactive, and be growing in
dpore [µm]

20 20
upward or downward direction. In an initial nucleation
15 15
routine, pores are randomly distributed in the topmost layers
of the nucleation area. The simulation array will then be 10 10
transformed into a new state in each iteration step according
5 5
to fixed rules:
1) Each pore grows one more voxel into its growth direction. 0 0
2) Branching and growth can only occur into free space, i.e. 0 50 100 150 200 250 300 350 400
no other pores are in the trajectory of the growing pore in an
t [min]
adjustable distance called lfree.
(c)
3) Pores can branch at pore tips, the resulting pore will grow
into the same direction (upward resp. downward) as the Fig. 3. Comparison of experiment (dots) and simulation (lines). Pore
density ρpore as function of pore depth of a) upward growing pores and
initial pore. The branching probability per iteration ktips is b) downward growing pores for three etching times. c) Pore depth dpore
proportional to the current density at the pore tips jtips and the as function of etching time.
branching probability per area and time ptips.
4) Pores can branch out of pore walls, the resulting pore will
6) If branching has occurred at one voxel, no branching can
grow into the opposite direction (upward resp. downward) as
occur out of the neighboring voxels, which will be set to an
the initial pore. The branching probability per iteration kwalls
―inactive‖ pore wall state. The number of affected neighbor
is proportional to the current density at the pore tips jtips and
voxels can be adjusted by the parameter lpass.
the branching probability per area and time pwalls.
5) If two pore tips meet in one voxel, one tip will continue to As already mentioned, Fig. 1 shows the crysto pore
grow, whereas the other one will stop to grow. structures resulting from the Monte-Carlo-Simulation of
crysto pore growth on (100) n-type InP with a doping level
of level of ND = 8 · 1017 cm-3 and for a constant current
density of j = 0.4 mA/cm2. The (11̄0)-plane is shown for

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

three different etching times besides the respective SEM On the contrary, the increasing normalized branching
image of the electrochemically etched pore structure. The probability at the pore walls with increasing doping level can
similarity between experimental and simulation results is be understood by the fact that pore walls are well passivated,
already striking on first view for all shown examples. which results in the formation of a space-charge-region
Similar results have been obtained for the (110)- plane (not (SCR) in the semiconductor. A part of the available etching
shown here). A more quantitative comparison is given in potential can thus drop in the SCR, leaving a decreased
Fig. 3. In Fig. 3a) the pore density ρpore of upward growing etching potential which drops in the electrolyte and is thus
pores is shown as function of depth for three etching times, available for the electrochemical reaction. Since the potential
as evaluated from SEM images (triangles). The lines show drop in the SCR decreases with increasing doping level, the
the corresponding simulation results. Fig. 3b) shows the potential left in the electrolyte increases with increasing
respective result for downward growing pores. Fig. 3c) doping level, leading to increasing branching probabilities
shows a comparison of the pore depth as function of etching with increasing doping level.
time. All simulation results show a very good agreement
ACKNOWLEDGMENTS
with the experimental results.
This work was funded by the collaborative research center
VI. DISCUSSION 855 ―Magnetoelectric Composites – Future Biomagnetic
In the preceding part of this manuscript it has been Interfaces‖ by the DFG.
demonstrated, that crysto pore growth can be very well
REFERENCES
modeled by a simple stochastic model which assigns specific
[1] T. Takizawa, S. Arai, and M. Nakahara, "Fabrication of
probabilities to the branching of pores at pore tips, resp. out
vertical and uniform-size porous InP structure by
of pore walls. For different materials and different doping
electrochemical anodization", Japan J. Appl. Phys.
levels, the branching probabilities per area (Wtips, resp.
137(2, 5A), L643 (1994).
Wwalls) given in Table 1 have been obtained.
[2] H. Föll, S. Langa, J. Carstensen, S. Lölkes, M.
Christophersen, and I.M. Tiginyanu, "Review: Pores in
Parameter InP InP GaAs
III-V Semiconductors", Adv. Mater. 15(3), 183 (2003).
8 · 1017 cm-3 1 · 1017 cm-3 2.5 · 1017 cm-3
[3] V. Lehmann, Electrochemistry of Silicon, Wiley-VCH,
Wtips / mm-2 19 59 30 Weinheim (2002).
Wwalls / mm-2 190 22 30 [4] C. Fang, H. Föll, and J. Carstensen, "Electrochemical
pore etching in germanium", J. Electroanal. Chem. 589,
The physico-chemical nature of the branching 259 (2006).
probabilities can be understood in a simple meta model, [5] M. Leisner, H. Föll, and J. Carstensen, "A meta model
which links the branching probability to the passivation for electrochemical pore growth in semiconductors", in
behavior of the semiconductor-electrolyte-interface at the Nanostructured semiconductors: from basic research to
pore tips, resp. pore walls. Passivation in this context means applications, ed. P. Granitzer, Springer (2011).
the coverage of the surface by chemical species, which [6] S. Langa, I.M. Tiginyanu, J. Carstensen, M.
impedes current flow and thus electrochemical dissolution. Christophersen, and H. Föll, "Formation of porous
The rather similar values of the normalized branching layers with different morphologies during anodic
probabilities for the pore tips can be understood by the fact, etching of n-InP", Electrochem. Solid-State Lett. 3(11),
that the passivation at the pore tips is rather similar because 514 (2000).
it is nearly not present, i.e. the pore tips are not passivated.

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Porous InP as Piezoelectric Matrix Material in

1-3 Magnetoelectric Composite Sensors
M.-D. GERNGROSS*, M. LEISNER, J. CARSTENSEN and H. FÖLL
Institute for Materials Science, Christian-Albrechts-University of Kiel,
Kaiserstrasse 2, 24143 Kiel, Germany
*
[email protected]

Abstract – This work shows the results of the fabrication of semi-insulating piezoelectric porous InP
structures by electrochemical etching and subsequent purely chemical post–etching in an isotropic HF,
HNO3, EtOH and HAc containing electrolyte. The piezoelectric modulus d14 of porous InP is measured to
around |60| pm / V, which larger by a factor of 30 compared to bulk InP.

Index Terms – indium phosphide, porous, piezoelectricity, magnetoelectric sensor.

µm ± 10 µm. The sample size is A = 0.25 cm2.

I. INTRODUCTION
All electrochemical etching experiments have been
This paper focuses on the production of an effective and
performed in the electrochemical double-cell as described
cheap piezoelectric material for the application in elsewhere [4]. The electrochemical etching has been per-
magnetoelectric 1-3 composite sensors. The concept is to formed under potentiostatic conditions at a constant tem-
apply porous and piezoelectric InP as the matrix material. In perature of 20 °C. For the first second a voltage pulse of 15
the second step a multilayer stack consisting of NiFe / FeGa V is applied to the sample in order to obtain a homogenous
showing giant magnetostrictive behavior will be used as pore nucleation. It is followed by a constant etching potential
magnetostrictive filler. of 7 V for 70 min. Afterwards the samples are carefully
The 1-3 composite arrangement of piezoelectric and rinsed in deionized water and blown dry in nitrogen.
magnetostrictive materials is chosen, because it allows for The purely chemical post-etching is carried out in a plastic
very large contact areas, providing excellent mechanical beaker at room temperature. The post-etching electrolyte
coupling between both components, and thus high sensitivity consist of HF : HNO3 : EtOH : HAc ( 3 : 8 : 15 : 24 ). In this
to magnetic fields. etching solution, the hydrofluoric acid serves as an etching
The main characteristic of piezoelectric materials is the agent, nitric acid as an oxidizing agent, and ethanol and
lack of an inversion center. InP as a III-V compound acetic acid as wetting agents. The ethanol also serves as a
semiconductor belongs to the 4,¯3m cubic crystal system. passivating agent in order to decrease the etching speed.
This crystal class is non centro-symmetric and non-polar. The samples are purely chemical post-etched for various
Thus InP is piezoelectric, but not pyroelectric. Looking at times from 8 h to 48 h to investigate the etching properties of
the piezoelectric modulus tensor of InP reveals that the d14 the etchant. After the post-etching process the samples are
component is the only remaining component of the carefully rinsed in deionized water and blown dry in
piezoelectric modulus tensor [1]. The maximum nitrogen.
piezoelectric effect is calculated to be in the <100> direction. The etched porous InP nanostructures have been
The piezoelectric properties of bulk InP have only been investigated with a HELIOS D477 SEM. The piezoelectric
measured very rarely [2, 3]. Up to now InP has not been response to an applied voltage has been measured with a
used as piezoelectric material, because it is not possible to double beam laser interferometer (DBLI) from aixACCT.
produce intrinsic InP. Even highly pure InP contains a lot of III. RESULTS & DISCUSSION
impurities, which serve as doping centers, so that a large Figure 1 (a) presents the InP current-line pore structure
number of free charge carriers exist short-circuiting the after anodic electrochemical etching (U > 0 V) with adjacent
charges induced by the piezoelectric effect. mechanical polishing to remove the nucleation layer, which
To overcome this problem, our approach is to produce a was performed for imaging and comparing the resulting pore
self-organized, hexagonally closed packed array of so-called structures after different chemical treatments. This structure
current-line pores with completely overlapping space charge is the result of the anodic electrochemical etching process
regions (SCR). Inside the space charge regions hardly any optimized to produce hexagonally closed packed pore arrays
free charge carriers are present, so that the induced in a self-organized manner.
polarization by the piezoelectric effect will not be shortened During the anodic electrochemical etching process the
anymore. minimum distance between pore walls is assumed to be
II. EXPERIMENTAL twice the width of the space charge region. At the end of the
For the experiments only single crystalline, double-side electrochemical etching process, the externally applied
polished (100) InP wafers are used. The wafers are doped voltage by the potentiostat is to a value determined by the
with S with a carrier concentration of ND = 1.1 · 1017 cm-3. surface charges. Hence the width of the space charge region
The resistivity is 0.019 Ωcm. The wafer thickness is 500 shrinks and thus the remaining conductive areas, where no
space charge region is present, increase. These conductive

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

areas can only be reduced if the pore wall width is reduced Figure 2 (a) shows the pore-ratio as a function of the
to twice the length of the SCR at cell off conditions. This etching time in the post-etching electrolyte. The pore ratio is
can be achieved by performing a post-etching step. The post- the ratio of the longitudinal and the transverse side of the
etching electrolyte has to be isotropic over the complete pore rectangular resp. elliptical pores. It is a quantitative measure
length and should be self-limiting as soon as the space for the change in the shape of the rectangular pores as a
charge regions of neighboring pores overlap again. As post- result of the post-etching. Fig. 2 (a) shows an increasing
etching electrolyte an HF : HNO3 : EtOH : HAc ( 3 : 8 : 15 : pore-ratio in the range from 0 h to 28 h of post-etching from
24 ) containing electrolyte has been developed. The pore around 1.7 for the not post-etched sample to a level in the
structure resulting from post-etching in this electrolyte is range of 2.35, reached after approximately 28 h of post-
shown in Fig. 1 (b). etching. The pore-ratio of the samples, being etched for 8 h
and 16 h in the post-etchant respectively, deviates from the
red line. A possible explanation for this could be that the
etch rate is higher for the surface near part of the pores in the
beginning of the post-etching process, but drops to zero after
twice the width of the SCR is reached.

2.4

2.2
pore ratio
2.0

1.8

(a) 1.6
0 8 16 24 32 40 48
time / h
(a)

200

180
width / nm

160

140

120

100
0 8 16 24 32 40 48
etching time / h
(b)
(b)
Fig. 1 Top view of porous InP (a) after anodic electrochemical etching (
U > 0 V) and (b) after subsequent purely chemical post-etching ( U = 0 V) Fig. 2 (a) pore ratio as a function of the etching time in the post-etching
after 48 h. electrolyte and (b) mean width of the pore walls as a function of the post-
etching time in the post-etching electrolyte.
Comparing both pore structures, one observes that the
pores change their shape from rectangular / square-like after Fig. 2 (b) shows the average pore wall width as a function
the anodic electrochemical etching to elliptic /circular after of the etching time in the post-etching electrolyte.
subsequent post-etching for 48 h. This etching behavior is The mean pore wall width is decreasing from around
only possible for isotropic etchants. 190 nm of the not post-etched sample to a level in the range
Looking at the distances between the pores, one of 150 nm. Again the mean pore wall width for the samples
recognizes that the pore wall width of two neighboring being post-etched for 8 h and 16 h deviate from the red line,
square-like resp. circular pores is mostly the smallest possibly due to the same reason as given for the pore ratio,
measured in the SEM images shown, while for two because the mean pore wall width of these two samples fits
neighboring rectangular like resp. elliptical pores oriented to the mean pore wall width of samples being post-etched for
parallel to each other is the largest found in the majority of a much longer time.
the cases. The level of 150 nm is reached after approximately 32 h
of post-etching and does not change with increasing post-

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

etching time. This indicates the self-limiting behavior of the nanostructures in InP by electrochemical etching, where the
post-etching electrolyte. leakage currents do not completely short the induced
This result is consistent with the result obtained in the polarization by the piezoelectric effect. Although the
analysis of the pore-ratio of these samples, because an displacement/voltage curve is not completely linear over the
increased pore-ratio goes along with a smaller mean pore entire voltage range, the d14 component of the only
wall width. The saturation value of both quantities is reached electrochemically etched sample is already larger by a factor
approximately at the same time, as one can see from the of about 10 compared to the d14 component of bulk InP [5].
diagrams shown in Figure 2 (a) and 2 (b).
The characteristic change in the pore geometry can be
Hyste re sis Freq ue ncy [Hz]: 50 00
understood by considering the space charge region
0.8 Hyste re sis A mp litu de [V ]: 3
surrounding each pore, the resulting voltage drop across the d av [n m/V ]: 0.0 78
SCR and the crystal-orientation dependence of the

displacement / nm
electrochemical and chemical etching in InP. The pores are 0.6

expanding in all directions, until an overlap of SCR of

neighboring pores occurs, which allows no further 0.4
dissolution of the InP by the post-etchant.
Figure 3 (a) and (b) show the result of the DBLI
measurement of the only electrochemically etched and the 0.2

electrochemically etched sample with additional post-

etching. The DBLI measures the displacement of the InP 0.0
sample due to the piezoelectric effect as a function of the -3 -2 -1 0 1 2 3
voltage, which is externally applied in <100> direction of the voltage / V
sample via two micromanipulators.
(a)
As InP is not a ferroelectric material, one expects a linear 0.15
dependence of the applied voltage on the measured Hystere sis Freq ue ncy [Hz]: 1
Hystere sis A mp litu de [V] : 0. 5
displacement. The chemical post-etching of the 0.10 d av [nm /V ]: 0.2 42
electrochemically etched samples reduces the leakage
displacement / nm

currents to a level low enough to use the piezoelectric 0.05

properties. In general, the expected piezoelectric
performance of the sample is better, the lower the leakage 0.00
currents are.
For the only electrochemically etched sample the voltage -0.05
is linearly increased from 0 V to 3 V, then linearly decreased
to –3 V and finally increased to 0 V again. For the -0.10
electrochemically etched and additionally post-etched
sample the voltage is linearly increased from 0 V to 0.5 V, -0.15
- 0.4 -0.2 0.0 0.2 0.4
then linearly decreased to –0.5 V and finally increased to 0
voltage / V
V again. The resulting displacement of the InP sample is
(b)
measured.
Figure 3 (a) shows the piezoelectric performance of the Fig. 3 DBLI measurement of porous InP (a) after anodic electrochemical
only electrochemically etched sample. In the voltage range, etching ( U > 0 V) and (b) after subsequent purely chemical post-etching (
where the applied voltage increases from 0 V to 3 V, one U = 0 V) after 48 h. The slope of the linear fit is denoted as dav.
observes a linear behavior of the resulting displacement until
Figure 3 (b) shows the piezoelectric performance of the
a voltage of 2.5 V is reached. At this position the
electrochemically etched and subsequently post-etched
displacement strongly increases, although the applied
sample. One obtains a linear dependence of the applied
voltage remains constant. Decreasing the applied voltage to
voltage on the measured displacement. In contrast to the
1.65 V also causes an increase in the displacement, though
purely electrochemically etched sample the positive limit of
the displacement is expected to decline for a decreasing
the applied voltage is reached completely. But more eye-
voltage. In the voltage range from 1.65 V to -3 V the
catching is the wavy shape of the displacement/voltage curve
expected linear behavior is observed and again in the range
of the sample. The waviness of the curve is an artifact of
from -3 V to 0 V. That the ending displacement of the
specimen mounting.
displacement/voltage curve is not equal to the starting
The sample exhibits a significantly higher slope with dav
displacement of 0 nm is most probably due to dielectric
= 0.242 nm / V compared to the only electrochemical etched
losses, which increase with the frequency of the applied
sample. The linear dependence of the applied voltage on the
voltage. The slope dav of the linear fit of the displacement /
displacement has been measured severeal times with a
voltage curve is 0.078 nm / V. From the slope of the linear
variation in dav by a factor of 2 in maximum.
displacement vs. applied voltage curve, the d14 component of
It is found to be around |60| pm/V, about a factor of 30
the porous InP sample can be derived, resulting in a value of
larger than the values measured on bulk InP [5].
|19| pm / V.
As shown in figure 3 (a) it is now possible to fabricate

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

IV. CONCLUSION ACKNOWLEDGMENTS

The first steps on the way to a magnetoelectric 1-3 This work was funded by the collaborative research center
composite sensor consisting of a piezoelectric matrix and a 855 ―Magnetoelectric Composites – Future Biomagnetic
magnetostrictive filler have been made. Interfaces‖ by the DFG.
It has been demonstrated that it is possible to produce REFERENCES
semi-insulating piezoelectric InP by anodic electrochemical [1] J.F. Nye, Physical properties of crystals: their
etching and subsequent purely chemical post-etching in an representation by tensors and matrices, Oxford
HF, HNO3, EtOH, HAc containing electrolyte. This University Press, Oxford (1985).
electrolyte has been optimized to show an isotropic and self- [2] K. Rottner, R. Helbig, and G. Müller, Appl. Phys. Lett.
limiting etching behavior over the complete pore length. 62(4), 352 (1993).
The d14 component of post-etched macroporous InP is [3] G. Arlt and P. Quadflieg, Phys. Stat. Sol. 25, 323-330
found to be around |60| pm/V, which is about a factor of 30 (1968).
larger than the values reported for bulk InP [5]. [4] S. Langa, I.M. Tiginyanu, J. Carstensen, M.
Though InP is the most suitable candidate for this Christophersen, and H. Föll, Electrochem. Solid-State
approach, in principle a new class of semi-insulating porous Lett. 3(11), 514 (2000).
single-crystalline piezoelectric materials can be fabricated [5] T.P. Pearsall, Properties, processing and applications of
from III-V semiconductors by this concept of indium phosphide, IEEE, London (2000).
electrochemical and pure chemical post-etching.

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

The Collaborative Research Center

―Magnetoelectric Composites - Future
Biomagnetic Interfaces‖ at the Christian-
Albrechts-University in Kiel
H. FÖLL
Institute for Materials Science, Christian-Albrechts-University of Kiel
[email protected]

I. ABSTRACT
The project depends on the exploitation of
In Jan. 2010 the ―Deutsche Forschungsgemeinschaft―
magnetoelectric composites, meaning mechanically coupled
(DFG) established a so-called ―Sonderforschungsbereich‖
structures of magnetostrictive and piezoelectric materials.
(Collaborative Research Center) for Research into
The working principle is very simple. A magnetic field
magnetoelectric composites for future biomagnetic interfaces
causes dimensional changes of a magnetostrictive material.
at the Christian-Albrechts-University (CAU) in Kiel /
The mechanical coupling to a piezoelectric material then
Germany; the project is funded with more than then 10 Mio
puts elastic stress on the piezoelectric material, resulting in a
€. The Institute of Materials Science with it‘s background in
voltage that is a measure of the magnetic field strength. In
functional materials and nanotechnology background was
reality, magnetoelectric composites are rather complex
instrumental in writing the proposal and in getting together
systems. An input vector (magnetic field) produces an output
... primary researchers from Electrical Engineering, Physics,
scalar (voltage), and the coupling between the input and the
and Medicine besides almost all groups of Materials Science
output relies on several vector / tensor relations (stress /
and Engineering. The speaker is Prof. E. Quandt from
strain induced in the magnetostrictive material, transfer to
Materials Science.
the (tensor) piezomaterial, position of contacts). In addition,
The project is scheduled for 4 (+ another 4) years. Its
noise and time constants (e.g. for mechanical resonance and
primary goal is the development of extremely sensitive
damping) need to be considered since the sensors are to be
(vector) sensor for magnetic fields. These sensors are to be
used for low-frequency (< 100 Hz) signals.
used in dense arrays (about 1 sensor /cm2) primarily for
Advanced technologies, usually derived from micro- or
medical purposes. A sensor-studded ―cap‖, for example, put
nanotechnology including MEMS and implemented in the
around the head of patients suffering from various neural
―Kiel Nanolab‖, are used to make magnetoelectric
disorder syndromes, should be able to pick up the magnetic
composites. In addition, some novel concepts are pursued.
fields from neuronal firing deep in the brain and tallow to
For example, layered structures of alternating piezo- and
localize malfunctioning brain areas with far higher precision
magnetostrictive materials clamped a only on end (and thus
than present techniques; similar potential uses are seen in
able to oscillate in one direction) have already proved
cardiography. The necessary sensitivity for magnetic field
sensitivities able to measure magnetic fields smaller 1 nT. A
must rival those of SQUIDs; the project thus is fairly
novel approach that will be presented elsewhere in the
ambitious because present technology is many orders of
workshop intend to use porous III-V semiconductors, in
magnitude less sensitive than SQUIDs.
particular InP, as the piezoelectric component. The
The project has 4 major partial projects an a central
piezoelectric properties of III-V semiconductors are well
project: Partial Project A develops the magnetoelectric
known but useless so far since the charges produced by
composites and is thus the core project for the undertaking; it
mechanical stress are quickly short-circuited by the
will be discussed in some detail in the presentation. Partial
conductivity of the material. Porous membranes, however,
Project B investigates the detailed structural. magnetic and
can be made to be semi-insulating and thus can be used as a
electric properties of the interfaces between the
new single-crystalline piezoelectric materials, as will be
magnetostrictive and piezoelectric materials used. Partial
shown. Filling the pores with a magnetostrictive material
Project C develops the sensor systems including theory and
then will produce a sensor with properties that could be
simulation tools, and partial project D introduces the medical
advantageous for certain applications.
component. The central Project provides analytical services
The presentation will give a general overview of the
like electron microscopy or a room heavily shielded against
project but then will focus on the material aspects.
magnetic fields for sensitive measurement (including
patients).

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Investigation of Mesoporous Structures for

Thermoelectric Applications
A. COJOCARU1*, J. CARSTENSEN1, J. BOOR2, V. SCHMIDT2 and H. FÖLL1
1
Institute for Materials Science, Christian-Albrechts-University of Kiel.
Kaiserstr. 2, D-24143 Kiel, Germany.
2
Max-Planck-Institute of Microstructure Physics Weinberg 2, D-06120 Halle, Germany
*
[email protected]
Abstract — Mesoporous silicon is an attractive material for thermoelectric application. For pore wall
Abstract —
thicknesses Mesoporous
around <100nm,silicon is an
phonons can attractive material
not penetrate for thermoelectric
the porous application.
layer while electrons Fordue
still can, pore wall
to there
thicknesses around <100nm, phonons can not penetrate the porous layer while electrons still can,
smaller mean free path length. The resulting good electrical and bad thermal conductivity is a premise fordue to there
smaller
efficient mean free path length.
thermoelectric devices.The resulting
This paper good electrical
presents resultsand bad thermal
regarding conductivity
homogeneity, highis aporosity,
premise and
for
efficient thermoelectric devices. This paper presents results regarding
optimal pore wall thicknesses for porous silicon based thermoelectric devices. homogeneity, high porosity, and
optimal pore wall thicknesses for porous silicon based thermoelectric devices.
Index Terms — electrochemical etching, mesoporous silicon, thermoelectric

- The porous layer should be uniform with a small

I. INTRODUCTION
spread of pore dimensions.
Porous silicon (PSi) has found various applications, e.g. in
- The pore walls should be structurally as perfect as
photonic devices [1], sensor systems [2] or drug-delivery
possible (not containing side pores, for example) to
devices [3]. In this paper electrochemically etched porous Si
minimize scattering of carriers and thus the
layers suitable for thermoelectric devices are discussed.
resistivity.
Thermoelectric devices need a high electrical conductivity
and low thermal conductivity. While in most materials
electrical and thermal conductivity are coupled by the
Wiedemann-Franz law, in porous material the big difference dpw
in mean free path lengths between electrons (110nm) and
phonons (300nm) [4] allows for a decoupling of both
conductivities.
In contrast to bulk silicon mesoporous silicon is well
known to show a very low thermal conductivity as soon as
the distance between pores becomes smaller than the mean
free path length of the phonons, while the electrical Pore
front
conductivity stays high. Several papers describe efforts to
enlarge the figure of merit ZT for thermoelectric application Fig. 1. SEM pictures of a cross section for pores. Electrochemically etched,
5 s, into n-type Si at 2 V for (0.02 –0.05) cm resistivity.
by optimizing porous materials [5 - 7]. This paper focuses on
producing porous Si layers [8, 9] with pore walls sizes in the
range of 20 - 100 nm. Since galvanostatically etched mesopores tend to show
diameter oscillation (cf., e.g., [11, 12]) all mesoporous layers
II. EXPERIMENTAL DATA presented here have been etched under potentiostatic
Low doped silicon allows for larger mobilities of the condition.
electrons, which would be beneficial for the thermoelectric A typical result of mesopores with an average pore wall
effect. Thus various electrolytes and etching conditions had thickness of dpw ≈ 100 nm when etching 5 sec and 15 sec, i.e.
been tested on low-doped material without getting just after finishing the pore nucleation, is shown respectively
reasonable porous layers. Thus in this paper we will only in Fig. 1 and Fig. 2a). The length of the pores is quite
focus on mesopores etched on (100)-oriented highly doped inhomogeneous, probably due to a small variation in the
n-type Si with resistivity of (0.02 – 0.05) cm. Etching has speed of pore nucleation at different position on the sample
been carried out in the electrochemical cell described in surface.
detail in [10] without illumination. As electrolyte of 48 wt. Etching for a longer time, e.g. for 30 min, the pore front
% HF dissolved in acetonitrile in a volume ratio of 1:2 has becomes straight as shown in Fig. 2b). This is a general
been used. aspect of mesopore growth. Probably due to diffusion
All experiments have been performed at a constant limitation increasing with pore length, the dissolution at the
temperature of T = 20 °C. pore tips slows down, leading to a self-stabilizing adjustment
of pore lengths.
III. RESULTS UND DISCUSSION
Just by etching pore walls less than 100 nm the thermal
conductivity is drastically reduced. In order to get a good
electrical conductivity the pore walls should fulfill several
properties:

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Acetonitril

Acetonitril + H2 O
Pore front
a) a)

dp
dpw

Pore front
b) b)
Fig. 2. SEM pictures of a cross section for pores in nucleation stage
electrochemically etched a) 15 s, 2V; b) 30 min, 2V into n-type Si for Fig. 4. SEM pictures of pores obtained with a ―differential‖ electrolyte.
(0.02 –0.05) cm resistivity. Start with acetonitril containing 48 wt.% HF in a ratio of (2:1), growth
with addition of water; a) overview (top region); b) pore tips.

but after further etching many side pores are found near the
dp << dSCR dpw dp << dSCR top. This feature does not become perfectly clear from Fig.
2a) and Fig. 2b) but at least the trend becomes visible.
The nucleation phase has a substantial influence on the
pore morphology. In the nucleation phase the pores are very
side thin and have a rather homogeneous pore density (Fig. 1).
pore
The pore wall thickness dpw is around 100 µm, which
pore tips too thin pore tips
a) b) corresponds to 2dSCR for the used resistivity, (dSCR –
thickness of the space charge region). As visible in Fig. 1
dp  dSCR dpw  2dSCR
and Fig. 2, the pore diameter dp is much smaller then the
pore wall thickness dpw. This geometry is illustrated in Fig. 3
no a). It is well known that optimal pore growth needs dp  dpw
side
pore  2dSCR (e.g. see [8]). For dp  2dSCR the electrical field
around the pore tips will be drastically increased. Since the
c) bigge r pore tip side pores have roughly the same diameter as the main
pores, the strong increase of the electrical field around any
Fig. 3. Schematic illustrations for a model of the pore nucleation phase. small "bump" in a pore wall may trigger the formation of
side pores, leading to pore morphologies as schematically
Since a straight pore front is essential for producing a shown in Fig. 3b), which correspond to the SEM images in
thermoelectric device, the mesoporous layers have typically Fig. 2b). So, to avoid side pore formation, a larger pore
been etched to a length of 100µm, which is a thicker layer diameter could be helpful, as illustrated in Fig. 3c).
than necessary for the device. As visible in Fig. 2 for longer As e.g. discussed in [8] diameters of mesopores etched
pores, the morphology changes from top to tip. Since a top with aqueous electrolytes are larger in comparison to pores
layer can be polished off, the relevant pore morphologies are etched with organic electrolytes. Therefore H2O was added
near the pore tips. to the electrolyte in a ratio acetonitril : H2O : HF = 2 : 1 : 1.
The main problem when increasing the etch time is the Indeed, larger pore diameters dp are found but the distance
formation of side pores. These side pores do not form between the pores dpw was larger as well, leading to the same
instantly near the pore tips but their density and length morphologies as shown schematically in Fig. 3, just on a
increases with etching time; e.g. at the beginning of all larger scale. Consequently side pores still occur.
experiments the pores have no side pores near the top, Fig. 4 shows the resulting pores when starting the etching
with pure organic electrolyte and adding water after roughly

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

5 seconds. As expected, a significant increase in pore The ―water-free‖ electrolytes are the best ones for
diameter was found as shown in Fig. 4a). Subsequently a mesopore structure formation. Much work remains to be
number of pores died out, leading finally to a pore done and further optimization of the etching process is
morphology as shown in Fig. 4b) where again the pore walls necessary.
are quite rough. ACKNOWLEDGMENTS
Dr. N. Abrosimov and Dr. H. Riemann from the IKZ
Berlin grew and wafered the Si-Ge crystals; their help is
greatly appreciated. This work has been supported by the
BMBF (Project PoSiTeM – 03X3539B).

REFERENCES
[1] F. Müller, A. Birner, U. Gösele, V. Lehmann, S. Ottow,
and H. Föll, J. Por. Mat. 2000, 7, 201.
[2] K.A. Kilian, T. Böcking, and J.J. Gooding, Chem.
Commun. 2009, Feature Article, 630.
[3] E.J. Anglin, L. Cheng, W.R. Freeman, and M.J. Sailor,
Adv. Drug Delivery Rev. 2008, 60(11), 1266.
[4] A.I. Hochbaum, R. Chen, R.D. Delgado, W. Liang, E.C.
Garnett, M. Najarian, A. Majumdar, and P. Yang,
Nature 2008, 451, 163.
[5] G. Joshi, H. Lee, Y. Lan, X. Wang, G. Zhu, D. Wang,
R.W. Gould, D.C. Cuff, M.Y. Tang, M.S. Dresselhaus,
G. Chen, and Z. Ren, Nano Letters 2008, 8(12), 4670.
[6] J. Lee, G.A. Galli, and J.C. Grossman, Nano Letters
Fig. 5. SEM pictures of a cross section of pores etched with electrolytes 2008, 8(11), 3750.
acetonitril:HF in ratio (4:1) under galvanostatic condition for constant [7] H.J. Goldsmid, Materials 2009, 2, 903.
applied etching current 50mA for 30 min. [8] V. Lehmann, Electrochemistry of Silicon, Wiley-VCH,
Weinheim (2002).
The water-free (as far as possible) electrolytes are the best [9] V. Kochergin and H. Föll, Porous semiconductors:
ones. While many other electrolytes have been tried too, Optical properties and applications, Springer, London
further improvements are still possible. Lowering the (2009).
temperature a few degrees or increasing the viscosity of the [10] H. Föll, M. Christophersen, J. Carstensen, and G. Hasse,
Mat. Sci. Eng. R 2002, 39(4), 93.
electrolyte has been shown to improve pore morphologies in
[11] S. Langa, J. Carstensen, I.M. Tiginyanu, M.
other cases, for example [13, 14] and need yet to be tried.
Christophersen, and H. Föll, Electrochem. Solid-State
Fig. 5 shows the best pore structures produced so far. The
Lett. 2001, 4(6), G50.
high growth rates of 3.3 µm/min for 100 µm could be [12] A. Cojocaru, J. Carstensen, J. Boor, D.S. Kim, V.
obtained. While not all goals are achieved yet, these pores Schmidt, and H. Föll, ECS Trans. 2011, 33(16), 193.
already show promising results. [13] E.K. Ossei-Wusu, A. Cojocaru, J. Carstensen, M.
IV. CONCLUSION Leisner, and H. Föll, ECS Trans. 2008, 16(3), 109.
The experimental results obtained permit to claim that [14] A. Cojocaru, J. Carstensen, E.K. Ossei-Wusu, M.
silicon with low resistivity is an attractive material for Leisner, O. Riemenschneider, and H. Föll, Phys. Stat.
thermoelectric application. Sol. (c) 2009, 206(7), 1571.

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Ballistic Charge Carrier Devices for Terahertz

Signal Generation.
H.L. HARTNAGEL
Technical University Darmstadt
Fachgruppe Mikrowellenelektronik
Darmstadt, Germany
www.mwe.tu-darmstadt.de
[email protected]

It is of great interest, to produce light-weight Terahertz Optimum conditions for this to occur are to be presented.
sources for the many appl ications such as security testing. Some time back, one of the doctoral candidates of the
By reducing the transit distance suitably, the charge carrier speaker manufactured and measured the first experimental
can be approximately ballistic, that is without any collision structure, thus verifying the initial theoretical results of
damping. Such structures have been fabricated by epitaxial Monte Carlo simulation by this author and his partner. This
technology. Another feature can be employed there, namely presentation describes a more detailed understanding of the
the loss-free reflection of carriers at a heterojunction barrier. charge bunching effects. An outlook is presented of further
Therefore the charge carriers can be made to resonate possible concepts such as structures made with graphene.
between two such barriers at a Terahertz frequency.

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Two Simple Examples for the Micro-nano

Integration of Nanowires as Electronic Device
Elements
Rainer ADELUNG
Functional Nanomaterials, Institute for Materials Science, University of Kiel, Kaiserstr.2, 24143, Kiel, Germany
[email protected]

Abstract – As a part of the conference talk about the mass fabrication and applications of nanostructures, the aim of
this paper is to review and compare two approaches for the simple fabrication and integration and of nanostructures
into Si-based microchips. The purpose of the integration is the utilization of the different and advanced electronic
properties of nanowires. The first method is based on a fracture approach, that integrates nanowires bound to a Si
substrate between micro electrodes. These are arrange in a horizontal manner, the second approach allows to
integrate free standing nanowires and even 3 dimensional nanowire networks in the chip. As an example for the
electronic properties of the nano-micro integrated structures the UV light sensitivity is sown here.

Index Terms – nanowires, nanostructures, Si-based nanochips

microstructure the photoresist. The main step for the

I. INTRODUCTION
nanowire template formation is the exposure of the samples
One dimensional (1D) metal and semiconductor structures
to thermal cycling down to cryogenic temperatures in order
have gained significant research interest due to their
to induce the stress in the photoresist thin film resulting in
different, partially advanced properties originating from
thin film cracks in the photoresist with nanoscopic openings
effects like a high surface to volume ratio or quantum
(~100 nm). By using the described pattern with parts of the
mechanical influenced properties dominating low
photoresist that are 200 µm long and 10 µm wide, the
dimensional materials, become the important components of
fracture pattern forms a highly reproducible well defined
micro and nanoelectronic devices [1]. In the past 15 years,
‗zig zag‘ pattern of cracks. The third step contains the
significant progress in synthesis and characterization of
deposition of metals or semiconductors by sputter deposition
nanostructures is done, applicability was typically
or another a PVD-process in high or ultra high vacuum. This
demonstrated by connecting nanowires with techniques like
deposition covers the whole wafer surface including the
EBL, FIB or direct connections with scanning probe tips
cracks. A deposition of material in the dimensions of about
revealing suitability of nanostructures in electronic and
50-100 nm nominal thickness with an adhesion promoter
optoelectronic devices [2].Various methods such as
underneath (thin layer of Ti or Cr) forms nanowires in a
templates [3,4,5], solution growths [6], vapor-liquid-solid
reliable manner in the crack. Too high amounts will lead to
(VLS) and its modified versions [7,8,9] as well as several
an overfilling, too small amounts in a dissentious chain of
others have been used to synthesize 1D structures. However,
clusters. Please note that the cracks have a relatively high
easy fabrication routes allowing the integration of nanowires
aspect ration of 5-7 which reduces the amount that will be
into standard lithography are not yet well established. An
deposited into the crack up to a factor of 10. In contrast, the
optimal integration route should add minimal additional
nominal thickness will be reached in the lithographically
fabrication steps and be compatible with the standard micro
formed openings that form the connectors to the nanowires.
processing.
The fifth final step is the lift off to separate the superfluous
II. NANOWIRE FORMATION AND INTEGRATION metal on top of the photoresist from the microstructured
APPROACHES contacts grown in the openings formed by lithography and
One approach called "fracture approach" is based on a the nanosized wires formed within the thin film cracks. This
thin film fracture approach [10,11,12], the other one is photoresist mask lift off was performed by first soaking the
based on a modified VLS process allowing a bridging of the sample in acetone for about 1 minute and then keeping it in
contacts through interpenetrating junctions [13], will be an ultrasonic bath for roughly 2 seconds. Keeping the sample
called here "penetration approach". for long time in an ultrasonic bath may destroy the
In general, the fabrication of the nanowire within the fracture nanowires.
approach microchips contains 5 steps, compare [14] and see Vapor-liquid-solid (VLS) or Vapor-Solid (VS) methods
figure 1. As first step, Shipley 1813 photoresist is spin are typically utilized to grow free standing nanostructures in
coated in a thickness of ~560 nm thickness on silicon a large variety like nano -rods, -wires, -sails, -etc. Usually
substrates of 76 mm-diameter with <100> orientation and a VLS growth processes can be performed in a horizontal tube
p-doping resulting in a resistivity of 1-10 Ωcm. Please note furnace equipped with a controlled gas flow control. The
that the 380 μm thick wafers are top terminated with a 100 needed recipes are the precursor material (typically metalls),
nm thick thermally grown insulating SiO2. In a second step, catalytic nanoparticles (e.g. gold) and the substrate on which
a mould for micro contact lines and the nanowires will be structures will be grown. Experimental variants are
formed. Conventional photolithography is used to

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Fig. 2. Growth of three dimensional nanostructures on the current lines of a

Si-chip. a) shows the principle, a gap between two current lines can be
bridges by growing free standing but interpenetrating nanostructures (arrow
point to the interpenetration area). b) Photograph of a 1 cm2 Si chip that is
exposed on the area occurring bright with the nanostructure growth
conditions. c) This are is shown under the electron microscope where free
standing ZnO structures are growing. d) The magnification from c shows
the gap between the current lines (darker contrast in the middle) which is
bridged by interpenetrating and free standing ZnO structures.

This allows to shape individual nanoscale connectors at

specific places on a circuit. A precondition for the
integration is the possibility to keep the synthesis temperate
Fig.1. Fracture approach for the fabrication of nanowires with contacts on a on a level that will not destroy already structured electronics.
Si-chip. a) Photoresist on a Si-wafer is microstructured to form a mold for
the later contact lines and a prerequisit for the nanowire formation at the 10
This can be achieved by an active cooling of the silicon
µm wide bridge (magnified). b) The image shows a different view of the substrate or as in our case to lower the process temperature
bridge used for the nanowire formation. The magnification shows an on the chip by shielding all areas where no deposition will
optical microscopy image of the photoresist in the bridge area after take place.
exposing it to thermal cycling that effects the fracture of the thin film. The
higer magnification shows the regularity of the crack pattern. c) Schematic III. EXAMPLES FOR THE ELECTRONIC PROPERTIES:
overview over the process that is described in the text, resulting in
The above described Nanostructures are already used as
nanowires, represented in d) AFM image of nanowires formed in the 10 µm
wide area between the micro contacts. The magnification shows that the gas sensors or field effect transistors, depending on the used
wires consist of a chain of clusters. metals or semiconductors. It turns out that the nanostructure
sensors are advanced in terms of responding pressure and
time. A remarkable feature was shown by Penner et al. [18]
temperature, gas flow rate and relative source and substrate
that is a change in mechanism of a hydrogen sensor. While
distances. The growth contains the following 3 steps: (i)
usually the conductivity decreases with increased hydrogen
During heating in the furnace above the melting temperature
concentration, the conductivity increases in a Pd-nanowire if
of the eutectic, the precursor mixture (ZnO + graphite)
they are exposed to hydrogen. This phenomenon could be
transforms into vapor phase and is transported to substrates
observed also for gold nanowires integrated by the above
by carrier gas. (ii) The deposited precursor atoms or
described approach [14]. Figure 3 shows the respones of
molecules form liquid-droplet eutectic alloy with catalytic
ZnO nanowires formed by the above described methods on
particles. (iii) Caused by supersaturation, the precursor
chips. In Figure 3a, the fracture approach was utilized and
material is deposited at the interface between the catalyst
nanowires were formed from sputter deposited ZnO. For
droplet and its surface. This enables to lift the droplet due to
comparison, the response shown in 3b originates from free
capillary forces and continue to grow nanowires. During
standing interpenetrating ZnO structures. The viewgraph
cooling the phase separation occurs resulting in formation of
shows a fast response in both cases, however, differences are
1D rods with catalytic particle on the top [15,16,17]. In
characteristic for both fabrication procedures. As a general
typical VLS process, temperature, amount of precursor
tendency, polycrystalline wires are faster and more sensitive.
material, size of catalytic particles and the gas flow rate are
The grain boundaries between the particles are important
the main controlling parameters for growth of 1type of the
sensitive elements that enlarge the effective surface of a
1D structure. The nanostructures grow in preferential crystal
nanowire.
directions faster than in others, causing the material to shape
in a crystalline manner. For the VLS process exists, the here IV. CONCLUSION
used process doesn't need a catalyst and a tube furnace. A The two briefly shown examples for micro nano
prime example for the nanostructure growth is ZnO. By integration demonstrate a feasibility of nanowire based
using the ability of ZnO to interpenetrate during crystal electronics, especially for sensor applications. In the
growth, gaps between current lines can be bridged above presentation, further examples for the application of
chips, see Figure 2. nanostructures will be given based on the large scale

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synthesis of nanoscale building blocks into macroscopically pp. 631-638, 2003.

expanded 3 D networks. [5] L. Shi, C. Pei, and Q. Li, ''Fabrication of ordered single
crystalline CuInSe2 nanowires arrays,'' Cryst. Eng.
Comm. vol. 12, pp. 3882-3885, 2010.
[6] J. D. Holmes, K. P. Johnston, R. C. Doty, and B. A.
Korgel, '' Control of Thickness and Orientation of
Solution-Grown Silicon Nanowires,'' Science, vol. 287,
pp. 1471, 2000.
[7] C. Y. Lee, T. Y. Tseng, S.Y Li and P. Lin, "Growth of
zinc oxide nanowires on silicon (100)," Tamkang J. Sci.
Eng., 6, no.2, pp. 127-132, 2003.
[8] H. J. Fan, P. Werner, and M. Zacharias, "Semiconductor
nanowires: from self-organization to patterned growth,",
Small 2, pp.700-717, no. 6, 2006.
[9] S. Jebril, H. Kuhlmann, S. Müller, C. Ronning, L.
Kienle, V. Duppel, Y. K. Mishra, and R. Adelung,
"Epitactically interpenetrated high quality ZnO
nanostructured junctions on microchips grown by the
vapor-liquid-solid method," Crystal Growth & Design,
vol. 10, pp.2842-2846, 2010.
[10] R. Adelung , O. C Aktas, J. Franc, A. Biswas, R. Kunz,
M. Elbahri, J. Kanzow, U. Schürmann, and F. Faupel.
"Strain-controlled growth of nanowires within thin-film
cracks,", Nat. Mater., vol. 3, pp. 375-379, 2004.
[11] M. Elbahri, S. K. Rudra, S. Wille, S. Jebril, M.
Scharnberg, D. Paretkar, R. Kunz, H. Rui, A. Biswas,
and R. Adelung, "Employing thin-film delamination for
the formation of shadow masks for nanostructure
Fabrication,", Adv. Mater., vol. 18, pp.1059–1062,
2006.
[12] B. E. Alaca, H. Sehitoglu, and T. Saif, "Guided self-
Fig. 3. Response to UV-light of integrated nanowires a) nanowires made assembly of metallic nanowires and channels," Appl.
by the fracture approach, b) free standing nanostructures formed by Phys. Lett., vol. 84, pp.4669-4671, 2004.
interpenetration during growth. [13] S. Jebril, H. Kuhlmann, S. Müller, C. Ronning, L.
Applications include flexible semiconductors and Kienle, V. Duppel, Y.K. Mishra, R. Adelung:
ceramics as well as applications of superhydrophilicity and Epitactically Interpenetrated High Quality ZnO
superhydrophobicity. Nanostructured Junctions on Microchips Grown by the
Vapor-Liquid-Solid Method, J. Cryst. Growth Des.
REFERENCES 10(7), pp. 2842-2846, 2010.
[1] C. M. Lieber, and Z. L. Wang, "Functional Nanowires," [14] S. Jebril, M. Elbahri, G. Titazu, K. Subbannajui, S.
MRS Bulletin, vol. 32, pp. 99-108, 2007. Essa, F. Niebelschutz, C.C. Rohling, V. Cimalla, O.
[2] J. T. Hu, T. W. Odom, and C. M. Lieber, ―Chemistry Ambacher, B. Schmidt, D. Kabiraj, D. Avasti, and R.
and Physics in One Dimension: Synthesis and Properties Adelung " Integration of thin film fracture based
of Nanowires and Nanotubes,‖ Acc. Chem. Res. vol. 32, nanowires into microchip fabrication", Small 4(12) pp.
pp. 435-445, 1999. 2214-2221, 2008.
[3] F. Schlottig, M. Textor, N. D. Spencer, K. Sekinger, and [15] R. S. Wagner and W. C. Ellis, "Vapor liquid solid
F. Ochanda, ''Characterization of nanoscale metal growth of mechanism of single crystal growth" Appl.
structures obtained by template synthesis'', Fresenius J. Phys. Lett, vol. 4, pp. 89, 1964.
Anal. Chem. vol. 361, pp. 684–686, 1998. [16] H. Huang, "Fabrication and mechanics of nanorods,"
[4] O. Rabin, P. R: Herz, Y. M. Lin, A. I. Akinwande, S. B. Rev. Adv. Mater. Sci., vol. 13, pp. 41, 2006.
Cronin, and M. S. Dresselhaus, ''Formation of thick [17] D. S. Kim, R. Scholz, U. Gösele, M. Zacharias, "Gold at
porous anodic alumina films and nanowire arrays on the root or at the tip of ZnO nanowires: A model,"
silicon wafers and glass,'' Adv. Funct. Mater. vol. 13, Small, vol. 4, pp.1615-1659, 2008.
[18] F. Favier, E. C. Walter, M. P. Zach, T. Benter, R. M.
Penner, Science, vol. 293, pp. 2227-2231, 2001.

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Strain-Tunable Quantum Dot Devices

A. RASTELLI, R. TROTTA, E. ZALLO, P. ATKINSON, E. MAGERL, F. DING, J. D. PLUMHOF,
S. KUMAR, K. DÖRR, O.G. SCHMIDT
Institute for Integrative Nanosciences, IFW Dresden, Helmholtzstr. 20, 01069 Dresden, Germany
[email protected]
Abstract – We introduce a new class of quantum dot-based devices, in which the semiconductor structures
are integrated on top of piezoelectric actuators. This combination allows on one hand to study in detail the
effects produced by variable strains (up to about 0.2%) on the excitonic emission of single quantum dots and
on the other to manipulate their electronic- and optical properties to achieve specific requirements. In fact,
by combining strain with electric fields we are able to obtain (i) independent control of emission energy and
charge-state of a QD, (ii) wavelength-tunable single-QD light-emitting diodes and (iii) frequency-stabilized
sources of single photons at predefined wavelengths. Possible future extensions and applications of this
technology will be discussed.

Index Terms – Epitaxial Quantum Dots, Single photon sources, Strained semiconductors, Tunable sources
of single photons.

epitaxial QDs compared to other solid state emitters. On the

I. INTRODUCTION other hand the structure designs for electrical pumping and
Optically active semiconductor quantum dots (QDs) can for exploiting the GSE are not compatible, making
be made as nanoinclusions of a low energy bandgap material additional ―tuning knobs‖ indispensible.
in a matrix with larger energy bandgap. One of the simplest II. RESULTS
ways to obtain QDs with excellent structural, electronic, and In this contribution we introduce a new class of QD-based
optical properties is represented by self-assembly of 3D devices, in which the semiconductor structures are integrated
nanoislands during lattice-mismatched heteroepitaxial on top of piezoelectric actuators. This combination allows us
growth. In this, so-called Stranski-Krastanow (SK) growth on one hand to study in detail the effects produced by
mode, elastic stress is one of the main driving forces leading variable strains (up to about 0.2%) on the excitonic emission
to the formation and evolution of QDs. The most prominent of single QDs and on the other to add a powerful ―tuning
example is represented by InGaAs QDs in GaAs matrix. A knob‖ to QDs.
large number of experiments have demonstrated that these We first discuss the effects of biaxial strain on the
QDs are excellent quantum emitters which can be used as emission of single QDs embedded in optical microcavities
sources of triggered single photons, indistinguishable [3]. Afterwards we show that strain does not only affect the
photons and polarization entangled photon pairs. On the emission energy of QDs but also the relative binding
other hand virtually strain-free GaAs/AlGaAs QDs can be energies of excitonic species confined in QDs [4] and the
made by using templates of self-assembled nanoholes on an fine structure splitting of neutral excitons[5].
AlGaAs surface. We then discuss a technological approach to combine
Whatever approach is used, QDs are affected by dot-to- strain with electric fields on the same device.
dot fluctuations. This makes it difficult to obtain QDs with
electronic and optical properties which meet (sometimes
very stringent) requirements for their use in advanced REFERENCES
quantum optics experiments, especially involving [1] R.B. Patel et al. Nature Photon. 4, 632 (2010)
independent sources. Post-growth techniques are therefore [2] A.J. Bennet et al Nature Phys. Nature Physics 6, 947
required to fine-tune the optical properties of QDs. Vertical (2010)
electric fields (applied along the growth direction) represent [3] T. Zander, A. Herklotz, S. Kiravittaya, M. Benyoucef,
the most powerful ―tuning knob‖ to date. By using the so F. Ding, P. Atkinson, S. Kumar, J. D. Plumhof, K. Dörr,
called ―giant Stark effect‖ (GSE) both the emission energy AR, O. G. Schmidt, Optics Express 17, 22452 (2009)
and the excitonic fine-structure splitting can be widely tuned [4] F. Ding et al PRL 104, 067405 (2010). D. Knuth, The
[1, 2]. The latter is important for generation of entangled Art of Programming. Addison-Wesley, 1973
photon pairs. Electric fields can also be used to electrically [5] J. D. Plumhof, V. Krapek, F. Ding, K. D. Jöns, R.
pump single QDs. This feature, which takes profit of mature Hafenbrak, P. Klenovsky, A. Herklotz, K. Dörr, P.
semiconductor technology, is one of the major advantages of Michler, AR, O. G. Schmidt, Phys. Rev. B (R) 83,
121302 (2011)

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Zinc Oxide Nanostructures:New Properties for

Advanced Applications
Oleg LUPAN, Lee CHOW, Thierry PAUPORTÉ
Technical University of Moldova
University of Central Florida, USA
Chimie-Paristech, LECIME, UMR7575, CNRS, France
[email protected]

Abstract – Zinc oxide is a material which exhibits a variety of new properties at nanometer dimensions.
Various synthesis techniques have been carried out to provide growth of nanowires, nanorods, nanorings,
nanosprings, and nanobelts of ZnO under various conditions. These nanostructures show that ZnO possesses
probably the richest family of nanoarchitectures among all materials, including their structures and
properties. Such nanoarchitectures are potential building blocks for novel applications in optoelectronics,
sensors, photovoltaic and nano-biomedical sciences. This work presents a review of various nano
architectures of ZnO grown by the electrochemical, hydrothermal and solid–vapor phase techniques and
their properties. The possible applications of ZnO nanowires as sensors, nano-DSSC, photodetectors and
nano-LEDs will be presented.

Index Terms – ZnO, nanowire, nanorod, nanosensor, nano-LED, nanophotodetector.

ZnO low-dimensional structures in novel nanodevices will

I. INTRODUCTION be discussed.
Low-dimensional ZnO materials have become the focus II. EXPERIMENTAL
of a lot of researches due to their performances in The fabrication method of nanosensors by using
electronics, optoelectronics, photonics and biomedical individual ZnO nanowire or nanorod released from an
applications. In the last decade, the growth of ZnO has been agglomeration of nanowires as-grown on initial substrate has
an active research field due to their applications as sensors been described in our previous works [5,6] and reviewed in
and catalysts. However, since the nanotechnology initiative [3,4]. Nanowires can be released from the initial substrate by
led by the USA, investigations of one-dimensional (1D) sonication in ethanol or it can be used a direct contact
materials, like nanowires and nanorods has become a leading technique can be used to transfer nanowires to a SiO 2-coated
edge for the nanotechnologies and for nanoscience. The Si substrate. These procedures can be found in our previous
reduction of material size induces new electrical, chemical, works [4,5]. Rigid contacts were fabricated with a single
optical and mechanical performances, which are believed to ZnO nanowire on the sensor substrate template (glass with
be the results of aspect-ratio impact, size and quantum Cr/Au as electrodes) by using FIB metal deposition. For the
confinement effects. 1D nanorods are ideal for investigating sensor characterization, the measuring apparatus consists of
the transport process in confined spaces. This can result in a closed quartz chamber connected to a gas flow system [4-
future understanding of new phenomena in low-dimensional 6]. The concentration of gases for test was measured using a
structures. It could be a forward step for developing new pre-calibrated mass flow controller. Gases and air were
generation of nanodevices with better performance [1-8]. introduced to a gas mixer via a two-way valve using separate
In this context zinc oxide is one of the key materials. It mass flow controllers. By monitoring the output voltage
combines strong piezoelectric and pyroelectric properties. across the nanorod based sensor, the resistance was
Also, ZnO posses a wide direct band-gap (3.36 eV), which is measured in dry air and in a test gas. A computer with
good for optoelectronic applications. The exciton binding suitable LabView interface allows all controls and
energy (60 meV) in ZnO crystal is higher that in GaN, which acquisition of data. A linear behavior of the current-voltage
can give excitonic emission at room temperature more curves was recorded, which is important for the sensing.
efficient than other materials. At the same time, ZnO is a ZnO nanowires have also been synthesized by
transparent material to visible light and could be doped electrodeposition, a soft deposition technique that is suitable
easily to obtain lower resistivity and/or bandgap for specific with plastic lightweight substrates [7].
applications. It is a strong candidate for high temperature
electronic devices that can reliably operate in space and III. RESULTS
other harsh environments [3]. A scanning electron microscope image of the connected
The topic of our presentation here is to review the low- ZnO nanowire is presented in Figure 1. Focused ion beam
dimensional structures that have been grown for ZnO by (FIB) instrument was used to pattern metal electrodes
electrochemical or hydrothermal deposition and contacting both ends of a single ZnO nanowire. The
corresponding mechanisms. The potential applications of separation of the electrodes was about 5 m. The fabricated

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

device based on a single wire of 100 nm in diameter shown at 393 nm for either as-prepared or annealed samples. The
in Figure 1a, was used in our studies. light emission turn-on voltage was 4.4 V and the UV-
Figure 1b shows the transient response of the 100 nm emission was very bright even at low applied forward bias
ZnO-nanowire gas sensor under exposure to 100 ppm of H2 6.4 V. Our data clearly state the remarkable quality of the
gas at room temperature. electrochemical ZnO material and ZnO-NWs/p-GaN
Ultraviolet (UV) photoconductive nanosensors based on interface as well as effectiveness of electrodeposited
an individual ZnO nanowire (100 nm in diameter) are epitaxial ZnO as an active layer in UV-LED structure
important for nanoscience. This nano-detector is prepared in [10,11]. By copper-doping the ZnO NWs, we have shown
a FIB set-up by using nanodeposition for metal electrodes that the emission wavelength of the LED structure could be
and studied as was reported before [8,9]. The photoresponse shifted towards the visible wavelength region [12]. ZnO
of the ultraviolet sensor demonstrated that the output signal NWs were also grown by electrodeposition on p-Si and LED
of the sensors is reproducible under UV irradiation. The structures, were made and discussed in Ref. [13]. Other
photoresponse and characteristics of the ZnO nanowire applications of electrodeposited zinc oxide low-dimensional
device demonstrates that focused ion beam process offers a structures also include dye-sensitized solar cells which were
way to fabricate novel nanodevices on a single ZnO reported in Ref.[14]. The ZnO wires ensure a fast electron
nanowire with diameters as small as 100 nm [6]. The transfer from the excited dye to the back contact of the
response and recovery times to UV light exposure are photoanode [14]. Photodetectors and other devices structures
relatively fast for a single ZnO nanowire photodetector were reported in other papers [15-17]. In Appendixes A-E,
compared to an individual zinc oxide nanorod grown by some morphological and structural properties of the ZnO
aqueous chemical deposition [9]. nanostructures and applications have been shown. More
detailed description for these low-dimensional structures and
their characteristics have been reported in our works [2-20].
IV. CONCLUSION
We report on zinc oxide nanostructures – properties and
possible applications in future devices. It has been shown a
single nanowire nanosensors made from ZnO nanowire can
be produced. Fabricated nanodevices showed a promising
sensitivity to H2 gas, which makes possible its further
applications in sensors. The presented single ZnO nanowire
sensor proves to be promising for application in various
processes [3,4]. Also, ZnO nanowires grown by
electrodeposition or hydrothermal techniques have been
integrated in LEDs and DSSC structures and have been
discussed here.
APPENDIX A

Fig. 1. (a) FESEM image of a single ZnO nanowire (NW) connected in a

nanosensor structure by FIB technique. (b) Gas response curves of the 100
nm zinc oxide nanowire–based gas sensor under exposure to 100 ppm of H2
gas at room temperature.

The epitaxial synthesis of ZnO nanowire arrays on a p-

type GaN (0001) single crystalline thin film on sapphire by
an electrochemical technique was demonstrated for the first
time in our works [10,11]. The nanowires were directly Fig. A. The UV response for a single ZnO nanowire-based UV
epitaxially grown onto the p-GaN films with an in-plane photoconductive detector.
relationship of ZnO[10-10] parallel to GaN[10-10]. By GA-
XRD experiments, the ZnO mosaicity was shown to be as
low as 1.18°. The n-ZnO NWs/p-GaN heterostructure was
integrated in a light emitting diode structure device [10,11].
The rectifying behavior was shown with a forward current
onset at 3V. The LEDs emitted a unique UV-light centered

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

APPENDIX B APPENDIX D

Fig. D. SEM image of epitaxial ZnO Nanowires electrodeposited on p-GaN

(0.10 mM ZnCl2) and (b) (0.25 mM ZnCl2). Inset shows cross-sectional
Fig. B. SEM image of the ZnO nanowires grown by an electrochemical view of the ZnO nanowires on p-GaN single crystal forming a
technique at 90 C from ZnCl2 and KCl solution. (a) pure ZnO grown for heterostructure used for nano-LED applications.
9000s; (b) Cd-ZnO grown on FTO substrate for 7200 s. These nanowires
were used as building nanoblocks for LED, DSSC solar cells and for APPENDIX E
nanosensors structures.

APPENDIX C
Front Back contact-
contact- p-GaN/In-
ITO Ga/Cu

Bulldog-clip

Fig. E. The inset shows an image of the blue- light emission spot under a dc
Fig. C. SEM image (tilted 65 ) of epitaxial ZnO Nanorods grown on p- bias of 8.5 V at room temperature from zinc oxide nanowires grown on p-
GaN by hydrothermal technique. It is forming a heterostructure (n-ZnO/p- GaN substrate.
GaN) used for low-dimensional-LED applications.
ACKNOWLEDGMENTS
This research was performed with the financial support of
the C-nano Ile-de-France program (nanoZnO-LED Project).

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Dr. O. Lupan acknowledges the CNRS for support as an [11] O. Lupan, Th. Pauporté, B. Viana, I. M. Tiginyanu, V.
invited scientist at the LECIME-ENSCP, France. Dr.L. V. Ursaki and R. Cortés, ―Epitaxial Electrodeposition of
Chow acknowledges partial financial support from US ZnO Nanowire Arrays on p-GaN for Efficient UV-
Department of Agriculture, award #58-3148-8-175. Light-Emitting Diode Fabrication,‖ ACS Appl. Mater.
Financial support by Supreme Council for Science and Interfaces, 2010, 2 (7), pp 2083–2090, July 2010.
Technological Development of the Academy of Sciences of [12] O. Lupan, T. Pauporté, B. Viana, P. Aschehoug,
Moldova are acknowledged. ―Electrodeposition of Cu-doped ZnO nanowire arrays
and heterojunction formation with p-GaN for color
REFERENCES
tunable light emitting diode applications, Electrochimica
[1] Z. L. Wang, ―Zinc oxide nanostructures: growth,
Acta, In Press, doi:10.1016/j.electacta.2011.02.004
properties and applications,‖ J. Phys.: Condens. Matter.,
online Feb. 2011.
vol. 16, pp. R829–R858, 2004.
[13] O. Lupan, T. Pauporté and B. Viana, ―Low-Temperature
[2] T. Pauporté, Design of solution-grown ZnO
Growth of ZnO Nanowire Arrays on p-Silicon (111) for
nanostructures. In: Z.M. Wang, Editor, Lecture Notes on
Visible-Light-Emitting Diode Fabrication,‖ J. Phys.
Nanoscale Science and Technology. Volume 5. Toward
Chem. C, 2010, 114 (35), pp 14781–14785, August
Functional Nanomaterials, Springer Books, New York,
2010.
pp. 77–125, 2009.
[14] O. Lupan, V.M. Guérin, I.M. Tiginyanu, V.V. Ursaki, L.
[3] I. M. Tiginyanu, O. Lupan, V. V. Ursaki, L. Chow, M.
Chow, H. Heinrich, T. Pauporté, ―Well-aligned arrays of
Enachi, ―Nanostructures of Metal Oxides.‖
vertically oriented ZnO nanowires electrodeposited on
Comprehensive Semiconductor Science & Technology,
ITO-coated glass and their integration in dye sensitized
Chapter 3.11, pp. 396-479, 2011.
solar cells‖, Journal of Photochemistry and
[4] G. Chai, O. Lupan, L. Chow, ―Focused ion beam
Photobiology A: Chemistry, vol. 211(1), pp. 65-73,
fabrication of carbon nanotube and ZnO nanodevices‖
March 2010.
in Nanofabrication Using Focused Ion and Electron
[15] L. Chow, O. Lupan, Guangyu Chai, ―FIB fabrication of
Beams Principles and Applications, Edited by Ivo Utke,
ZnO nanotetrapod and cross-sensor,‖ Physica Status
Stanislav Moshkalev and Phillip Russell ISBN13:
Solidi (b), vol. 247(7), pp. 1628–1632, July 2010.
9780199734214 ISBN10: 0199734216 752 pages, Nov
[16] O. Lupan, L. Chow, S. Shishiyanu, E. Monaico, T.
2011.
Shishiyanu, V. Şontea, B. Roldan Cuenya, A. Naitabdi,
[5] O. Lupan, G. Chai, L. Chow, ―Novel hydrogen gas
S. Park, and A. Schulte, ―Nanostructured zinc oxide
sensor based on single ZnO nanorod,‖ Microelectronics
films synthesized by successive chemical solution
Eng., vol. 85, pp. 2220-2226, 2008.
deposition for gas sensor applications,‖ Materials
[6] O. Lupan, V.V. Ursaki, G. Chai, L. Chow, G.A.
Research Bulletin, vol. 44, pp. 63-69, 2009.
Emelchenko, I.M. Tiginyanu, A.N. Gruzintsev, A.N.
[17] O. Lupan, G. Chai, L. Chow, G. A. Emelchenko, H.
Redkin, ―Selective hydrogen gas nanosensor using
Heinrich, V. V. Ursaki, A. N. Gruzintsev, I. M.
individual ZnO nanowire with fast response at room
Tiginyanu and A. N. Redkin, ―Ultraviolet
temperature,‖ Sensors and Actuators B: Chemical, vol.
photoconductive sensor based on single ZnO nanowire,‖
144(1), pp. 56-66, January 2010.
Physica Status Solidi (a), vol. 207(7), July 2010, Pages:
[7] Lupan O., Pauporté T., ―Hydrothermal treatment for the
1735–1740.
marked structural and optical quality improvement of
[18] O. Lupan, G. Chai, L. Chow, ―Fabrication of ZnO
ZnO nanowire arrays deposited on lightweight flexible
nanorod-based hydrogen gas nanosensor,‖
substrates.,‖ J. Cryst. Growth, vol. 312, pp. 2454-2458,
Microelectronics Journal, vol. 38, pp. 1211-1216,
2010.
December 2007.
[8] O. Lupan, G. Chai, L. Chow, ―Fabrication of ZnO
[19] V.V. Ursaki, O.I. Lupan, L. Chow, I.M. Tiginyanu,
nanorod-based hydrogen gas nanosensor,‖
V.V. Zalamai, ―Rapid thermal annealing induced
Microelectronics Journal, vol. 38, pp. 1211-1216,
change of the mechanism of multiphonon resonant
December 2007.
Raman scattering from ZnO nanorods,‖ Solid State
[9] O. Lupan, L. Chow, G. Chai, L. Chernyak, O. Lopatiuk-
Communications, vol. 143, pp. 437-441, 2007.
Tirpak, H. Heinrich, ―Focused-ion-beam fabrication of
[20] O. Lupan, G.A. Emelchenko, V.V. Ursaki, G. Chai,
ZnO nanorod-based UV photodetector using the in-situ
A.N. Redkin, A.N. Gruzintsev, I.M. Tiginyanu, L.
lift-out technique,‖ Physica Status Solidi (a), vol.
Chow, L.K. Ono, B. Roldan Cuenya, H. Heinrich, E.E.
205(11), pp. 2673–2678, Nov. 2008.
Yakimov, ―Synthesis and characterization of ZnO
[10] O. Lupan, Th. Pauporté, B. Viana, Low-Voltage UV-
nanowires for nanosensor applications,‖ Materials
Electroluminescence from ZnO-Nanowire Array/p-GaN
Research Bulletin, vol 45(8), pp. 1026-1032, August
Light-Emitting Diodes, Advanced Materials, vol.
2010.
22(30), pp. 3298–3302, August 2010.

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Surface Plasmon Enhanced Luminescence from

Ag covered Anatase Titania Nanotubes
Mihai ENACHI1, Veaceslav URSAKI2, Vladimir SERGENTU2
1
National Center for Materials Study and Testing, Technical University of Moldova, Stefan cel Mare
av. 168, Chisinau MD-2004, Republic of Moldova, e-mail: [email protected]
2
Institute of Applied Physics of the Academy of Sciences of Moldova, Academy str. 5, Chisinau MD-
2028, Moldova
[email protected]

Abstract – We show that coating of titania nanotubes by Ag layers with thickness of 5 – 20 nm leads to the
increase of the near-bandgap photoluminescence intensity by one order of magnitude, while the effect of Au
coatings is insignificant. Titania nanotibes with average outer diameter of 250 nm and wall thickness of 70
nm with anatase structure were produced by anodization of Ti foils in an ethylene glycol based electrolyte
containing a mixture of HF and H 3PO4 followed by annealing at 300 oC. The enhancement of the band-edge
emission is believed to be due to the effect of surface plasmons in Ag coatings. This suggestion is supported by
calculations of dispersion relations of surface plasmons at the Ag/TiO 2 interface and by the measurement of
the transmission spectra of uncoated and metal coated titania nanotubes.

Index Terms – luminescence, optical absorption, surface plasmons, titania nanotuves, dispersion relations.

systems such as Ag/ZnO films [7], Ag (or Al)/InGaN

I. INTRODUCTION quantum wells [8].
Titania (TiO2) is widely used as a pigment, in sensors, In this work, we demonstrate that the band-edge emission
electrocatalysis, and Graetzel-type solar cells (e.g. [1] and from titania nanotubes produced by electrochemical
references therein). Among titatia nanostructures, titania anodization of titanium can be enhanced by the deposition of
nanotubes (TiO2 NTs) have improved properties for Ag films. This enhancement is due to the excitation of
application in photocatalysis, sensing, photoelectrolysis, surface plasmons in Ag.
photovoltaics, lithium ion batteries, and biomedical II. SAMPLE PREPARATION AND EXPERIMENTAL
applications [2]. Recently, titania also gained interest as a DETAILS
material used in photonic band gap crystals for the visible Technological conditions for the preparation of porous
spectrum of light due to its high index of refraction and low TiO2 layers with controlled morphology and porosity on the
absorption [3]. basis of Ti foils (Aldrich) include rinsing and sonicating in
Titania nanotubes have been produced by a variety of isopropyl alcohol, drying and anodizing. The investigated
methods including deposition into a nanoporous alumina samples were anodized in a mixture of HF (1 ml) and H 3PO4
template, sol–gel transcription using organo-gelators as (11 ml) in ethylene glycol (120 ml) under 120 V during 2
templates, seeded growth, and hydrothermal processes [1,2]. hours. This treatment results in the fabrication of TiO2
However, among all methods, electrochemical anodization nanotubes with outer diameters around 250 nm and the wall
of titanium is a cost-effective approach for the growth of thickness of 70 nm, as illustrated in Fig. 1. The samples were
highly ordered TiO2 NTs [4]. annealed at 300 oC during one hour after anodization. Ag
Optical properties of TiO2 NTs, particularly and Au coatings were deposited onto titania nanotubes by
luminescence, are very important for photonic applications. means of a Cressington magnetron sputtering coater.
In a recent work, the spectral distribution of A VEGA TESCAN TS 5130 MM scanning electron
cathodoluminescence from a cluster of nanotubes clearly microscope (SEM) was used for morphological
demonstrated the formation of resonator modes [5]. Taking characterization of the samples.
into account the possibility of doping porous titania Photoluminescence (PL) was excited by 351 nm line of an
templates with rare earth and transition metal ions and the Ar+ SpectraPhysics laser and analyzed through a double
morphology controlled light scattering properties, one can spectrometer at low temperature (10 K). The resolution was
expect that luminescent materials prepared on porous TiO2 better than 0.5 meV. The samples were mounted on the cold
templates are prospective for random laser applications [6]. station of a LTS-22-C-330 cryostat.
The development of methods for enhancing the Raman spectra were measured at room temperature with a
luminescence efficiency from titania nanotubes is an Confocal MonoVista CRS spectrometer.
important task. Enhancement of the emission due to surface
plasmons was observed in some metal-semiconductor

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

active. The Raman shift for these phonons is 514 cm-1 for the
A1g mode, 399 cm-1 and 514 cm-1 for the B1g modes, and 144
cm-1, 197 cm-1 and 639 cm-1 for the Eg modes [9]. Therefore,
the A1g and one of the B1g modes overlap. The two E g modes
at 144 cm-1, 197 cm-1 are outside of the range of measured
Raman shifts.

Fig. 1. SEM image of TiO2 nanotubes produced by etching Ti foils in a

mixture of HF and H3PO4 in ethylene glycol.

III. RESULTS AND DISCUTIONS

Figure 2 presents the PL spectra of TiO2 nanotubes (with
the morphology illustrated in Fig.1) subjected to annealing at Fig. 3. Raman spectrum of TiO2 NTs measured at room temperature.
300 oC and covered with Ag films of different thicknesses.
The luminescence measured in the spectral range from 370 As concerns the nature of the observed PL bands,
to 500 nm is dominated by the near bandgap emission which previously two sharp lines peaking at 3.31 and 3.37 eV have
includes two narrow lines at 371 nm (3.34 eV) and 372 nm been observed in the near bandgap PL spectra of anatase
(3.33 eV) followed by several phonon replica with phonon titania [10]. These lines were interpreted as defect-trapped-
energy equal to 50 meV. exciton related although the free-exciton origin of the 3.31
eV peak was also argued. Apart from this possible nature of
the PL lines at 3.34 eV and 3.33 eV observed in our samples,
their relation to free-to-bound transitions can not be
excluded [11].
The data presented in Fig. 2 demonstrate that covering of
TiO2 NTs with Ag films with thickness of 5 to 20 nm leads
to increased near-bandgap luminescence intensity. The
thicker is the Ag film the stronger is luminescence.
However, the increase of the film thickness beyond 20 nm
results in a decrease of the luminescence intensity (not
shown in this graph). We believe that this decrease is due to
increased absorption in the metal film of both excitation and
emission light. As concerns the increase of the luminescence
intensity with Ag films up to 20 nm, it is suggested to be due
to the enhancement of both the excitation field and the
bandedge emission via surface plasmons in the Ag film, the
second effect being stronger, since the excitation wavelength
(351 nm) does not match very well the surface plasmon (SP)
resonance. Fig. 4 shows the dispersion relations of surface
Fig. 2. PL spectra of TiO2 NTs covered with Ag films with thickness of 5 plasmon polaritons (SPP) on Ag/TiO2 and Au/TiO2 surfaces
nm (1), 10 nm (2) and 20 nm (3) measured at 10 K.
calculated by the dielectric functions. For a single interface
between a metal and a dielectric the dispersion relation can
The luminescence comes from the anatase phase of titania be derived from Maxwell‘s equations and boundary
as demonstrated by the Raman spectrum presented in Fig. 3. conditions [12]:
Anatase is tetragonal, with two TiO2 formula units (six   d ( )   m ( )
atoms) per primitive cell. The space group is D4h19 (I4/amd). k SPP ( )  , (1)
The 18-dimensional reducible representation generated by c  d ( )   m ( )
the atomic displacements contains the zone-center (k=0) with m(ω) and d(ω) being the permittivity of the metal and
modes: 3 acoustic modes and 15 optical modes. The the dielectric, respectively (c is the speed of light).
irreducible representations corresponding to the 15 optical Therefore, the SP frequencies of Ag/TiO2 and Au/TiO2 are
modes are 1A1g + 1A2u + 2B1g + 1B2u + 3Eg +2Eu. Three calculated as ~3 eV and ~2.3 eV, respectively, and the
modes are infrared active, the A2u mode and the two Eu density states of the SP mode become dramatically larger
modes. The B2u mode is silent. The remaining six modes with approaching these frequencies.
corresponding to symmetries A1g + 2B1g + 3Eg are Raman

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

diameter of 250 nm and wall thickness of 70 nm is increased

by an order of magnitude by coating with an Ag film with
the thickness of 20 nm. The enhancement is due to the effect
of surface plasmons in Ag coatings.
ACKNOWLEDGMENTS
This work was supported by the Academy of Sciences of
Moldova under Contract No. 10.820.05.01/BF.
REFERENCES
[1] I. M. Tiginyanu, O. Lupan, V. V Ursaki, L. Chow, M.
Enachi, Nanostructures of Metal Oxides.
Comprehensive Semiconductor Science and
Fig. 4. Dispersion relations of the SPP at Ag/TiO2, and Au/TiO2 interfaces. Technology, Chapter 3.11, pp. 396-479,
2011.
One can see from Fig. 2 that the emission around 380 nm [2] C. Grimes and G. K. Mor, TiO2 Nanotube Arrays:
is enhanced by a factor of 2 with Ag coating, while the Synthesis, Properties, and Applications. Springer,
emission around 400 – 440 nm is enhanced by an order of Berlin, 2009.
magnitude, since the energy of this emission corresponds to [3] V. V. Sergentu, I. M. Tiginyanu, V. V. Ursaki, M.
the resonance energy of the surface plasmons. At the same Enachi, S. P. Albu, and P. Schmuki, ―Prediction of
time, one should note that the emission intensity from negative index material lenses based on metallo-
samples coated with Au films is not influenced with film dielectric nanotubes‖, Phys. Status Solidi (RRL), vol. 2,
thicknesses up to 20 nm, it being decreased by thicker films. pp. 242-244, 2008.
These data are corroborated by measurements of the optical [4] M. Enachi, I. Tiginyanu, V. Sprincean, V. Ursaki, ―Self-
transmission in Ag and Au coated TiO2 NTs (Fig. 5). organized nucleation layer for the formation of ordered
Absorption bands are observed around 420 nm and 630 nm arrays of double-walled TiO2 nanotubes with
in Ag and Au coated samples, respectively. One can expect temperature controlled inner diameter‖, Phys. Status
that the luminescence intensity in the range of 600 nm would Solidi (RRL), vol. 4, pp. 100–102, 2010.
be increased by Au coating. However, our samples do not [5] M. Enachi, M. Stevens-Kalceff, I. Tiginyanu, V.V.
exhibit any emission at these wavelengths. Ursaki, ―Cathodoluminescence of TiO2 nanotubes
prepared by low-temperature anodization of Ti foils‖,
Materials Letters, vol. 64, pp. 2155–2158, 2010.
[6] V. V. Ursaki, I. M. Tiginyanu, L. Sirbu, and M. Enachi,
―Luminescent materials based on semiconductor
compound templates for random laser applications‖,
Phys. Status Solidi C, Vol. 6, No. 5, 1097–1104, 2009.
[7] M. Liu, S. W. Qu, W. W. Yu, S. Y. Bao, C. Y. Ma, Q.
Y. Zhang, J. He, J. C. Jiang, E. I. Meletis, C. L. Chen,
―Photoluminescence and extinction enhancement from
ZnO films embedded with Ag nanoparticles‖, Appl.
Phys. Lett., vol. 97, pp. 231906, 2010.
[8] K. Okamoto, I. Niki, A. Shvartser, Y. Narukawa, T.
Mukai, and A. Scherer, ―Surface-plasmon-enhanced
light emitters based on InGaN quantum wells‖, Nature
Mater., vol. 3, 601-605, 2004.
[9] T. Ohsaka, F. Izumi, Y. Fujiki, ―Raman spectrum of
anatase TiO2‖, J. Raman Spectrosc, vol. 7, pp. 321-324
(1978).
Fig. 5. Transmission curves of Ag (20 nm) and Au (20 nm) coated TiO2
[10] A. Suisalu, J. Aarik, H. Mändar, I. Sildos,
NTs. The transmission of coated samples (Tcoat) is divided by the ―Spectroscopic study of nanocrystalline TiO2 thin films
transmission of uncoated ones (Tuncoat). grown by atomic layer deposition‖, Thin Solid Films,
vol. 336, pp. 295-298, 1998.
IV. CONCLUSION
[11] M. Enachi, V. Trofim, V. Coseac, I. M. Tiginyanu, V.
The results of this study demonstrate possibilities to
V. Ursaki, ―Structure and luminescence properties of
enhance the luminescence from titania nanotubes via coating
titania nanotubes‖, Mold. J. Phys. Sci., vol. 8, pp. 2014-
with metal films. The near-bandgap photoluminescence
220, 2009.
intensity from anatase titania nanotubes with average
[12] H. Raether, Surface Plasmons on Smooth and Rough
Surfaces and on Gratings. Springer, Berlin, 1988.

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Development of GaN-based Nanosensors using

Surface Charge Lithography
Veaceslav POPA,1 Tudor BRANISTE,1 Olesea VOLCIUC,1 Dimitris PAVLIDIS,2 Andrei SARUA,3 Peter
HEARD,4 Martin KUBALL3
1
National Center for Materials Study and Testing, Technical University of Moldova, Stefan cel Mare av.
168, Chisinau MD-2004, Republic of Moldova
2
Technical University Darmstadt, Darmstadt 23584, Germany
3
H.H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS81TL, United Kingdom
4
Interface Analysis Centre, Oldbury House, 121 St. Michael's Hill, Bristol BS28BS, United Kingdom
[email protected]

Abstract – Semiconductor nanotechnology is a fast developing branch of modern engineering that offers
perspectives for the development of electronic devices with superior parameters. A special and important
niche in nanotechnology is allocated to the fabrication of nanosensors which are expected to exhibit higher
sensitivity in comparison with classical microelectronic sensors. Various aspects of fabrication of GaN based
nanosensors using Surface Charge Lithography are discussed and preliminary tests for gas sensors
applications are presented.

Index Terms – GaN, nanostructuring, surface charge lithography, sensors.

I. INTRODUCTION
GaN and related ternary alloys became important
a)
materials for UV light emitting devices and for high-
temperature high-power electronics. MBE, MOCVD and
HVPE have been developed for the epitaxial growth of these
materials. A strong impetus to the development of device
structures based on GaN was given by the implementation of
AlGaN/GaN interface, leading to the fabrication of 2DEG
FETs capable to operate at GHz frequencies with low noise
and high gain parameters [1]. The development of GaN-
based bipolar transistors is unfortunately limited by poor p-
type doping, that is why Schottky and field effect devices
became the most intensive developed electronic elements on
this material [2].
An important and challenging property specific to III-
group nitrides is their chemical stability. In this connection
processing of the materials involved require usually high b)
energy particles, e.g. reactive ion etching techniques instead
of wet chemical treatment. This leads to the creation of
surface defects which diminish the performance of the
fabricated devices. An alternative technique, called Surface
Charge Lithography, for meso- and nanostructuring of GaN
was developed by our group over the last years [3-5]. This is
a maskless technique that offers the possibility to fabricate
GaN-based structures with dimensions less than 100 nm by
direct ‗writing‘ in a controlled fashion by the focused ion
beam with subsequent photoelectrochemical etching of the
sample. The role of ion beam treatment is to induce surface
negative charge that shields the material against
photoelectrochemical etching. The potential application of
the fabricated structures by this method is demonstrated for Fig.1 The general view of FETs (a) and GaN nanowalls
FETs and gas sensors. connecting source and drain (b).

II. TECHNOLOGICAL PART

GaN epilayers used in our experiments were grown by density was about 109 cm-2. Ohmic contacts were formed by
MOCVD on c-plane sapphire substrates. The free carrier evaporation of Ti/Au metals (50nm/150nm). Rapid thermal
concentration was about 1017 cm-3 whereas the dislocations annealing necessary to improve the quality of ohmic contacts
was excluded in order to avoid modifications of surface

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

properties. For the focused ion beam treatment the FEI Strata of the gates after lift-off process. An optical image of the
FIB 201 was used at the energy of 30 keV and dose of final structure is presented in Figure 2a, whereas its I-V
6.6*1012 cm-2 of Ga ions. The photoelectrochemical etching characteristics are presented in Figures 2b and 2c.
was performed in 0.1 M of KOH solution under focused UV It is important to note that the gate-source characterization
illumination provided by a 350 W Hg lamp. Figure 1 shows high leakage related to the highly defective gallium
presents the design of the future transistors after mesa- nitride nucleation layer which is also resistant to
structuring with surface charge lithography method. photoelectrochemical etching. This problem was partially
solved using RIE process during 2 minutes in Ar atmosphere
resulting in gate-source current decrease by almost 2 times.
a) As one can see from I-V characteristics illustrated in
Figure 2b, there is a high leakage between Ni gate and
source-drain channel related to poor Schottky contact quality
resulting from the high density of surface defects caused by
FIB treatment. Also the weak modulation of drain current by
gate-source potential is the result of highly shunting effect of
the thick channel in comparison with thin modulated space
charge region.

a)

b)

b)

c)

Fig.3. SEM image of the fabricated GaN-based nanowall (a) and its
gas response characteristics (b)

GaN material has the potential for applications in gas

Fig.2. Ni gate on top of GaN nanowalls (a), drain current
variation by gate potential (b) and gate-source I-V sensors, especially in harsh environments where other
characteristics (c). materials exhibit fast degradation. The SCL technique was
used for the fabrication of individual nanowires of GaN for
the gas sensor applications. The design of the GaN
In order to achieve modulation of the drain-source current, nanowire-based gas sensors is presented in Figure 3, along
we deposited Ni gate using RF-magnetron sputtering with with the gas response characteristics towards H2 and CO
the thickness of 500 nm after rapid thermal annealing (RTA) gases at the temperature of 280C.
process at 800C during 30 sec in nitrogen atmosphere. From the characteristics involved we found a linear
Thick layers are necessary in order to exclude discontinuity dependence between the sensitivity and operation

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temperature for both investigated gaseous species. In

addition, there are different threshold temperatures: 215C in
III. . CONCLUSION
case of 1000 ppm H2 and 110C for 2000 ppm of CO. The We demonstrated the possibility of the Surface Charge
transient characteristics are promising, in particular they Lithography for the fabrication of electronic devices based
reveal 5 sec response and recovery times for the case of CO, on GaN nanowalls and nanowires. There are still open
and 10 seconds response time and 15 sec recovery time for questions regarding buffer layer shortcutting effect and
H2. The possible gas response mechanism is discussed in one quality of interface between metal contacts and FIB treated
of our previous paper [4]. GaN surface.
In order to improve the sensitivity parameter of our
sensors we made use of cathalythic properties of Pt nano- ACKNOWLEDGMENTS
dots deposited by the DC-plasma sputtering method. The This work was supported by the Academy of Sciences of
effect can be easily seen from the dependences presented in Moldova under the State Programme on Nanotechnologies
Figure 4 where the sensitivity towards H2 increased 6 times and Nanomaterials. VP would like to thank the Alexander
after 20 sec deposition and 3 times for the case of CO. von Humboldt Foundation for the financial support. AS
would like to thank Great Western Research for funding.

REFERENCES
[1] S. Strite, ―GaN, AlN and InN: A Review‖ J. Vac. Sci.
no a) Technol. B 10, pp.1237 (1992).
[2] X.J.Wang, ―Electrical characteristics of high
performance Au/n-GaN Schottky diodes‖ Journal of
Electronic Materials V. 27, Number 11, pp.1272-1276
(1998).
[3] I. M. Tiginyanu, V. Popa, and O. Volciuc, ―Surface-
charge lithography for GaN microstructuring based on
photoelectrochemical etching techniques‖ Applied
Physics Letters, Vol. 86, pp. 174102 (2005).
[4] Veaceslav Popa, Ion Tiginyanu, Olesea Volciuc, Andrei
Sarua, Peter Heard, Martin Kuball, ―Fabrication of GaN
nanowalls and nanowires using surface charge
lithography‖ Materials Letters, V. 62, Issue 30, pp.
4576-4578 (2008).
[5] I. M. Tiginyanu, V. Popa, and M. A. Stevens-Kalceff,
―Membrane-assisted revelation of the spatial
nanoarchitecture of dislocation networks‖, Materials
Letters, Vol. 65, pp. 360-362 (2011).
no
b)

Fig.4. Improvement of sensitivity parameter towards CO

(a) and H2 (b) after Pt sputtering.

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Development of Conductive Nanotemplates on

ZnSe
Eduard MONAICO1, Ion TIGINYANU1,2, Gleb COLIBABA3, D. D. NEDEOGLO3,
Ala COJOCARU4, Helmut FÖLL4
1
National Center for Materials Study and Testing, Technical University of Moldova,
[email protected]
2
Laboratory of Nanotechnology, Institute of Electronic Engineering and Nanotechnology,
Academy of Sciences of Moldova, Chisinau 2028, Moldova
[email protected]
3
State University of Moldova, Chisinau 2009, Moldova
[email protected], [email protected]
4
Chair for General Materials Science and Microwave Laboratory,
Christian-Albrechts-University of Kiel, Kaiserstr. 2, Kiel 24143, Germany
[email protected], [email protected]

Abstract – We demonstrate the possibility to fabricate arrays of pores oriented perpendicular and parallel to
the top surface of the ZnSe nanotemplate. The control of material conductivity allows one to produce porous
ZnSe samples with the mean pore diameter and characteristic skeleton wall thickness from several hundreds
of nanometers to about 15 nm. In addition, electrochemical treatment of ZnSe single crystals using
photoresist masks allows one to prepare buried porous structures with pores directed parallel to the top
template surface, which is especially important for photonic applications.

Index Terms – electrochemical etching, porous ZnSe, in-plane approaches, wide-band-gap semiconductor
nanotemplates, morphology characterization.

crystalline substrates in a neutral electrolyte [7-9]. Besides,

I. INTRODUCTION
the feasibility of indium phosphide nanotemplates for
Nanotemplates are widely used in nanofabrication,
electrochemical deposition of arrays of platinum nanotubes
particularly in the production of large assembles of
with diameters both larger and smaller than 100 nm was
nanowires and nanotubes of various materials with defined
demonstrated [7].
diameters and lengths. For many concrete applications it is
The electronic band gaps of InP, GaAs and CdSe are 1.3;
necessary to integrate a large amount of nanowires in one
1.4 and 1.7 eV at 300 K respectively, which means that the
bundle or array to achieve required functionalities. Over the
nanotemplates based on these materials are opaque in the
last decade, different template-based nanofabrication
visible region of the spectrum. Among III–V and II–VI
approaches have been developed which offer the possibility
semiconductors one may consider the wide band gap
to produce large assembles of nanowires and nanotubes of
compounds GaN (Eg = 3.3 eV), ZnO (3.3 eV) and ZnSe (2.7
various materials with defined diameters and lengths. Two
eV) as good candidates for the fabrication of conductive
types of templates are widely used for nanofabrication
nanotemplates transparent in the visible region. We were
purposes, namely porous Al2O3 [1-4] and etched ion track
forced to exclude the first two materials from consideration
membranes based either on inorganic materials or on organic
since GaN crystalline substrates are not yet commercially
polymers [5,6]. Both, porous Al2O3 and etched ion track
available, while ZnO, according to our preliminary studies,
membranes, however, exhibit high resistivity and therefore
seems to be inappropriate for electrochemical pore growth. It
they often play a passive role in nanofabrication processes.
is difficult to obtain wide bandgap semiconductors, like
In particular, templated growth of nanowires via
ZnSe, with high electrical conductivity due to self-
electroplating is provided usually by the metal contact
compensation phenomena inherent to these materials [10].
deposited on the back side of the high-resistivity
In connection with this, over the last years special efforts
membranes, while electroplating of metal nanotubes requires
have been undertaken at the State University of Moldova
additional technological steps e.g. chemical modification of
which resulted in the development of an approach of co-
the inner surface of the pores prior to electrodeposition
doping ZnSe by Al and Zn impurities for the purpose of
which leads to the incorporation of spurious phases in the
controlling the material electrical conductivity necessary for
nanotube walls. In this connection an important
the application of the technology of electrochemical
technological task is the development of cost-effective
porosification [11].
semiconductor nanotemplates which properties could be
easily controlled by external illumination, applied electric II. PREPARATION OF ZNSE NANOTEMPLATES
fields etc. We have proposed a cost-effective technology for We used 1 mm thick n-ZnSe substrates with free electron
controlled fabrication of semiconductor nanotemplates with concentrations from 7 × 1016 cm–3 to 2 × 1018 cm–3. A
self-organized quasi-ordered distribution of nanochannels method based on doping the samples with Al from a Zn+Al
using anodic etching of III-V (GaAs, InP) and II-VI (CdSe) melt was used for controlling the conductivity of ZnSe

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crystals [11]. This doping procedure allows one to produce possibility to use a porous ZnSe matrix for the purpose of
suitable conductive samples for controlled nanostructuring electroplating arrays of metal nanotubes [14].
using electrochemical etching techniques.
Anodic etching of ZnSe was carried out in dark at room
temperature in K2Cr2O7:H2SO4:H2O electrolyte with the ratio
5:100:10. Anodization was performed in potentiostatic
regime in an electrochemical double cell as described
elsewhere [12], the sample being mounted between the cells.
The area of the sample exposed to the electrolyte was 0.25
cm2. The electrolyte was pumped through both cells in a
continuous mode. A four-electrode configuration was used
[12]: a Pt reference electrode in the electrolyte, a Pt sense
electrode on the sample, a Pt counter electrode, and a Pt
working electrode. The electrodes were connected to a
specially designed potentiostat. The applied voltage was
varied from +5 V to +30 V for ZnSe samples, depending on
the substrate conductivity. After growth of pores, the top
nucleation layer of samples was removed by isotropic wet
etching.
A TESCAN Scanning Electron Microscope (SEM)
equipped with an Oxford Instruments INCA Energy
Dispersive X-ray (EDX) system was used to study the
morphology and chemical composition of the samples.
III. MORPHOLOGY CHARACTERIZATION OF ZNSE
NANOTEMPLATES
The anodization of ZnSe substrates with electron
concentration of 7 x 1016 cm-3 at the applied voltage of 25 V
results in the formation of pores with the mean diameter of
around 400 nm (Fig. 1a), while pores with the mean
diameter of around 40 nm are produced in ZnSe substrates
with the electron concentration of 2 x 1018 cm-3 anodized at 8
V (Fig. 1b). The width of the porous skeleton walls
correlates with the diameter of pores, i.e. in
all porous samples the width of the skeleton
walls proves to be nearly equal to the pore
diameter. Note, that the minimum pore diameter obtained
by electrochemical etching of ZnSe until now is 40 nm [13].
According to our explorations, the higher is the electron
concentration, the lower should be the applied voltage
during anodization, and the smaller is the diameter of the
pores produced. We succeeded to reduce de pore diameter
down to 15 nm by anodization of ZnSe substrates with the
electron concentration of 2 x 1018 cm-3 at 5 V, but the
porous skeleton walls thickness in this case remain
around 40 nm. This can be explained by overlapping in the
pore wall of two regions representing depletion layers. Thus,
to reduce the wall thickness is necessary to further increase
the electron concentration in ZnSe substrates, which
unfortunately cannot be easily realized. But, for some
applications of nanotemplates it is not strictly necessary to
have small pore wall thickness. Due to reduction of pore
wall thickness the number of free electron concentration is
also reduced. At the same time it is clear that for uniform
electrochemical deposition of metal species on the inner Fig. 1. SEM images taken from ZnSe nanotemplate prepared on crystalline
surface of pores along the whole length, the substrates with free electron concentration of 8 x 10 16 cm-3 (a) and 2 x 1018
cm-3 (b,c) by anodization in a K2Cr2O7:H2SO4:H2O electrolyte with the ratio
semiconductor nanotemplates have to possess high of 5:100:10.
skeleton conductivity.
We explained for the first time the dynamics of pore The possibility to control the diameter of pores just by
growth in n-ZnSe by analyzing the development of the pore changing the applied potential during anodic etching enables
morphology as a function of depth and demonstrated the one to prepare multilayer porous structures in one
technological process. Thus, successive anodization of ZnSe

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substrates at varied applied voltage results in layer layer which remains intact during the electrochemical
porosification at different length scales [14]. treatment. The thickness of this surface layer is of the order
IV. IN-PLANE TECHNOLOGICAL APPROACHES OF of the surface depletion region, i. e. from several tens to
ZNSE NANOTEMPLATE FABRICATION several hundreds of nanometers, depending on the
Porous ZnSe structures with pores propagating in the conductivity of the anodized substrate. A three layer
direction parallel to the sample surface (Fig. 2a) are of structure is shown in Fig. 8a for a ZnSe sample, where a
especial interest for the fabrication of two-dimensional resist layer is reminiscent on a part of the sample. A surface
photonic crystals, including metallo-dielectric ones, since layer of the virgin ZnSe is seen under the resist layer, and
this geometry allows a wide implementation of structures the porous structure is buried under this surface layer.
which can be easily explored under different polarizations of
the incident electromagnetic radiation.

Fig. 2. (a) Schematic representation of the technology for the preparation of

nanotemplates with pores propagating in the direction parallel to the sample
surface (in-plane approach) and (b) after optimization of the etching
conditions.

Nanowires and nanotubes are generally grown in the

perpendicular direction to the substrate surface. Nanowires
grown in-plane with the substrate surface are more suitable
for conventional planar processing techniques. The first
approach was initially demonstrated using GaAs [15], but in-
plane growth from etched facets (such as sidewalls and V-
grooves) on the substrate surface has been more widely used
for Si [16-18]. On the Si (110) substrate, deep trenches with
(111) side walls can be easily formed by anisotropic etching. Fig. 3. Porous structures buried in ZnSe substrates.

While the design shown in Fig. 2a is more suitable for in-

plane porosification of epilayers, the approach shown in Fig. The developed ZnSe nanotemplates with pores parallel to
2b proves to be efficient for in-plane pore growth in bulk the crystal surface are suitable for the electrochemical
substrates. In the latter case the ohmic contact is deposited deposition of metals inside pores, similar to the
onto the opposite surface of the sample, and electrochemical nanotemplates with pores perpendicular to the surface of the
etching is performed through windows in the photoresist. sample.
The experiments demonstrated that the electrochemical V. CONCLUSION
etching starts at the interface between the open surface and The results of this study demonstrate the possibility to
the electrolyte. Consequently, due to the high conductivity of fabricate porous ZnSe nanotemplates with uniform
the sample, the pores propagate along the current lines in all distribution of pores and geometrical parameters controlled
directions, inclusively underneath the photoresist in a by the conductivity of the substrate and the technological
direction parallel to the sample surface, as illustrated in Fig. conditions applied by etching in a K2Cr2O7:H2SO4:H2O
3. Moreover, the photoresist can be easily dissolved in base electrolyte. Electrochemical treatment in these electrolytes
solution. using photoresist masks allows one to prepare buried porous
An interesting feature of porous structures obtained by structures with pores directed parallel to the template top
this method is the fabrication of buried porous layers, as surface, which is especially important for photonic
illustrated in Fig. 3. The pores grow under a thin surface applications.

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The high conductivity of the semiconductor nanotemplate envelope. Electrochem. Commun., vol. 10, pp. 731–734,
skeleton provides conditions for uniform electrochemical 2008.
deposition of metal species on the inner surface of pores. [8] I.M. Tiginyanu, V.V. Ursaki, E. Monaico, E. Foca, H.
Moreover, the high value of the refractive index of ZnSe and Föll, Pore Etching in III-V and II-VI Semiconductor
its transparency in the visible region suggest that metallo– Compounds in Neutral Electrolyte. Electrochemical and
semiconductor structures are promising for the elaboration Solid-State Letters, vol. 10, D127, 2007.
of negative refractive index metamaterials, in particular of [9] I.M. Tiginyanu, E. Monaico, S. Albu and V.V. Ursaki,
novel focusing elements and beam splitters for applications Environmentally friendly approach for nonlithographyc
in the visible region of the spectrum. nanostructuring of materials. Physica Status Solidi
(RRL), vol. 1, pp. 98-100, 2007.
ACKNOWLEDGMENTS
[10] Y. Marfaing, Self-Compensation in II-VI Compounds.
This work was supported by the Supreme Council for
Prog. Cryst. Growth Charact., vol. 4, pp. 317-343, 1981.
Research and Technological Development of the Academy
[11] G. N. Ivanova, D. D. Nedeoglo, N. D. Negeoglo, V. P.
of Sciences of Moldova under grant no 11.819.05.12A and
Sirkeli, I. M. Tiginyanu and V. V. Ursaki, Interaction of
by Alexander von Humboldt Foundation.
intrinsic defects with impurities in Al doped ZnSe single
REFERENCES crystals. J. Appl. Phys., vol. 101, 063543, 2007.
[1] M. V. Kamalakar and A. Raychaudhuri, A Novel [12] S. Langa, J. Carstensen, M. Christophersen, H. Foll and
Method of Synthesis of Dense Arrays of Aligned Single I. M. Tiginyanu, Observation of crossing pores in
Crystalline Copper Nanotubes Using Electrodeposition anodically-etched n-GaAs. J Appl. Phys. Lett., vol. 78
in the Presence of a Rotating Electric Field. Advanced pp. 1074–1076, 2001.
Materials, vol. 20, pp. 149–154, 2008. [13] E. Monaico, I. M. Tiginyanu, V.V. Ursaki, A. Sarua, M.
[2] Y. Piao, H. Kim, Fabrication of nanostructured Kuball, D.D. Nedeoglo and V.P. Sirkeli,
materials using porous alumina template and their Photoluminescence and vibrational properties of
applications for sensing and electrocatalysis. J. Nanosci. nanostructured ZnSe templates. Semicond. Sci.
Nanotechnol., vol. 9, pp. 2215-2233, 2009. Technol., vol. 22, pp. 1115–1121, 2007.
[3] S. Gaurav, M. V. Pishko and G. A. Craig, Fabrication of [14] E. Monaico, P. Tighineanu, S. Langa, H. L. Hartnagel
metallic nanowire arrays by electrodeposition into and I. M. Tiginyanu ZnSe-based conductive
nanoporous alumina membranes: effect of barrier layer. nanotemplates for nanofabrication. Phys. Stat. Sol.
Journal of Materials Science, vol. 42, pp. 4738-4744, (RRL), vol. 3, pp. 97-99, 2009.
2007. [15] K. Haraguchi, K. Hiruma, K. Hosomi, M. Shirai and T.
[4] A. Ghahremaninezhad and A. Dolati, A study on Katsuyama, Growth mechanism of planar-type GaAs
electrochemical growth behavior of the Co–Ni alloy nanowhiskers. J. Vac. Sci. Technol. B, vol. 15, pp.
nanowires in anodic aluminum oxide template. Journal 1685-1687, 1997.
of Alloys and Compounds, vol. 480, pp. 275-278, 2009. [16] R. He, D. Gao, R. Fan, A. I. Hochbaum, C. Carraro, R.
[5] T.W. Cornelius, B. Schiedt, D. Severin, G. Pépy, M. Maboudian and P. Yang, Si nanowires bridges in
Toulemonde, P.Y. Apel, P. Boesecke and C. Trautmann. microtrenches: integration of growth into device
Nanopore4s in track-etched polymer membranes fabrication. Adv. Mater., vol. 17, pp. 2098-2102, 2005.
characterized by small-angle x-ray scattering. [17] M. S. Islam, S. Sharma, T. I. Kamins and R. S.
Nanotechnology, vol. 21, 155702, 2010. Williams, A novel interconnection technique for
[6] J. Duan, J. Liu, D. Mo, H. Yao, K. Maaz, Y. Chen, Y. manufacturing nanowires devices. Appl. Phys. A, vol.
Sun et al., Controlled crystallinity and crystallographic 80, pp. 1133-1140, 2005.
orientation of Cu nanowires fabricated in ion-track [18] M. S. Islam, S. Sharma, T. I. Kamins and R. S.
templates. Nanotechnology, vol. 21, 365605, 2010. Williams, Ultrahigh-density silicon nanobridges formed
[7] Ion Tiginyanu, Elena Monaico, Eduard Monaico, between two vertical silicon surfaces. Nanotechnology,
Ordered arrays of metal nanotubes in semiconductor vol. 15, L5-L8, 2004.

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

Perspectives of Single Cast Nanowires

Technology
Anatolii IOISHER1, Efim BADINTER1, Nicolae LEPORDA2 ,
Vitalie POSTOLACHE1, Eduard MONAICO3, Ion TIGHINYANU2
1
Institite “ELIRI”(Chisinau), [email protected], [email protected],
2
Institute of Electronic Engineering and Nanotechnologies, Academy of Sciences of Moldova
[email protected], [email protected]
3
National Center for Materials Study and Testing, Technical University of Moldova,
[email protected]

Abstract – The paper is dedicated to production potential of glass-coated cast nanowire with metal-,
semimetal- and semiconductor-based cores by means of Taylor-Ulitovsky method. Criteria of melted core-
formative material penetration into a drawing capillary were analyzed. Theoretical preconditions of the
reduction of cast microwire diameter up to nano-dimensions of core are reviewed and an improved method of
cast nanowire manufacturing is proposed. Correctness of conclusions was experimentally proved and
laboratory samples of micro- and nano-wires with core diameter of about 200-300 nanometers were produced,
even in case of materials with poor adhesion.

Index Terms – nanowire, cast microwire, glass insulation, electromagnetic field.

solid-state physics, as a sample of quasi-one-dimensional

crystalline object. Quantum dimensional effects have been
I. INTRODUCTION
investigated on the basis of microwires with small core
Rapid development of nanotechnology, including
diameter and a number of interesting results have been
various aspects of application, has led to an increased
obtained [4, 5]. However, such microwires have not found
interest in production of glass-coated micro- and nanowires
practical application. Some components and devices made
with core diameter less than 300 nanometers [1]. Such
on the basis of super-thin metal- and metal alloy-based
micro- and nanowires can find application in the field of
microwires confined themselves to laboratory samples such
medicine and biology, e.g. for the development of miniature
as, for instance, radiation electrometer involving conductive
sensors and probes, including thermoelectric ones,
and mechanical properties of such microwires.
ecological small power engineering and electronics for
Due to the abrupt reduction of production and
binding nano- and micro-objects and other branches of
application of cast microwires in nineties, investigations on
science and engineering.
manufacturing methods of such microwires have been
The process of cast micro- and nanowire production
stopped. Though nowadays there is a revival of interest in
is known to include the following:
some types of such microwires, especially magnetic ones
 melting of a definite amount of conductive material [6], casting technology still remain insufficiently
(metal, semimetal, semiconductor) placed into a glass investigated. Potential of further reduction of microwire
tube in a suspended state at electromagnetic (EM) field diameter and estimation of prospects of cast nanowire
of a high-frequency inductor; production are reviewed in the present report.
 heating and softening of the glass pipe end owing to
II. RESULTS AND DISCUSIONS
thermal contact with a molten drop of conductive
Theoretical and experimental studies of glass-coated
material and forming a microbath in the form of
cast microwire production have demonstrated that core
softened glass which is flowing round this levitating
diameter as well as overall diameter significantly depend on
drop;
such physical parameters of applied materials, as dynamic
 pulling down of the lower end of that coating (for
instance by means of coiling onto a spool) into a viscosity  and surface tension σg of glass within the
capillary, which is later on filled in with the said temperature range investigated, interfacial tension on glass-
conductive material from the microbath that is a core- coreformative material border σmg within the area of
formative material; microwire formation, density of materials used for
 cooling of the pulled down filament, which after microwire casting, as well as on rate of microwire drawing
crystallization of core and glass forms the said glass- vs and some other technological parameters. Many of the
coated cast micro- or nanowire. abovementioned parameters depend on temperature Т of
Attempts of production of super-thin glass-coated cast casting process and in a complicated way on main
microwires (by means of Taylor-Ulitovsky method [2]) with technological parameters [2].
core diameter less than 1 micron have been undertaken since The mass of the drop of core-formative material M
early 70 of the past century, when nano-technology was not forming (along with covering softened glass-coating) the so-
so advanced [3]. Such microwires, especially semimetal- and called micro-bath is of great importance too. This drop is at a
semiconductor-based ones, were of interest from the view of suspended state because of ponderomotive forces of high-

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

frequency electromagnetic field (EF) of inductor and adhesion to glass only. Having selected samples with
pressure difference р under and over the micro-bath required diameter, such microwires (with core made of Bi
(owing to glass-tube rarefaction). The weight of the drop and Bi-based alloys with Sb, Pb and Sn) were used for
Мk, suspended only by EF, is called critical one. If М > Мk research of their physical properties (as quasi-one-
, the microwire core diameter is to a greater extent defined dimensional objects) [4, 5].
by thermophysical parameters of glass and rate of microwire It must be however emphasized that the mentioned
drawing [3, 7]. At that glass tube feeding rate vg, geometry formulas (1) and (2) are correct only for a definite range of
and rarefaction, density of core-formative material m and casting rate and some other technological parameters, such
configuration of intensity of electromagnetic field over and as glass tube feeding rate, its overall dimensions, microbath
below inductor is of a great importance for microwire temperature range and others. Thus, in the case of increase
geometry formation. of rate vdr , starting from 1,5 m/s, at other fixed parameters,
Over the time of broad application and research of cast some increase of core diameter with further stabilization at
microwires with resistive core, diminution of the core higher rates has been observed instead of decrease of the
diameter as much as possible has been considered mainly in said parameter. (Especially when weight of drop is over the
order to increase microwire linear resistance. In the critical value). This is indicative of the need in further
framework of Zotov‘s theoretical model [7], the dependence investigation of Taylor-Ulitovsky process in order to define
of microwire radius r (which is considered as a homogenous potential and requirements of production of long single cast
filament) on a number of physical parameters of glass and microwires on the basis of various materials.
microwire drawing rate (in case of not so great rates) has Currently there is no comprehensive theory
been deduced: unambiguously describing interconnection and
interdependency of different technological and physical
parameters affecting the process of microwire casting and
r = D/2 = 0,9 2/3 / (σg2/3 · vdr1/3 g ), (1) final properties of microwire (and, perhaps, there will be no
ever owing to its extremely complexity of the process).
where g – glass density. Here D should be considered as an Accordingly, there is an unsolved problem regarding
overall microwire diameter, though the authors regard it as ultimate potential of this manufacturing method and minimal
the core diameter. achievable core diameter. Thus, it would be expedient to
If the weight of drop of melted core-formative material divide description of microwire casting process by means of
in the micro-bath is less than the critical value, then the Ulitovsky method into separate partial problems which can
authors of the present work define semiempirical be solved easier regarding tasks put by later on.
dependence of core diameter d on a number of technological In order realize this let us formulate two main sub-tasks:
parameters, which have a direct impact on the geometry of 1) determination of the criteria of initial penetration of
forming micro- and nanowires and which may be regarded melted core-formative material into forming capillary and
as governing parameters of casting process [8]: extreme allowable diameters of such a capillary;
2) revealing of input values physicotechnological
d = kT g4/3 / (g g1/3vdr2/3), (2) parameters of casting process ensuring combined drawing of
glass capillary with minimal diameter and melted core-
formative material filling in this capillary with further
crystallization.
where vdr is capillary drawing rate; kT – nondimensional When melted core-formative material (let call it metal)
empirical coefficient dependent on a number of additional penetrates into capillary the main role is played by the
technological parameters (in case of our experiments kT  following: 1) capillary effect due to the surface tension of
110-6, all the values of physical parameters are expressed in metal; 2) inter-phase tension on a border glass-metal; 3)
SI units). The empirical formula (2) is close to theoretical pressure over a melted metal inside of a glass-tube of a
formula (1) in terms of structure, though its distinguishing micro-bath; 4) dimensions of drop of melted metal (to be
feature is stronger power dependence of diameter on glass more exact, height of drop of melted metal in a micro-bath
viscosity. Нm over the point of penetration point into a capillary),
As evident from both mentioned formulas, the lesser forces which carry metal, induced by downward movement
glass viscosity and greater casting rate the lesser microwire of walls of primary stretching cone and metal adhesion to
diameter becomes without limitations. Having ensured a glass. It is worth to be pointed out that in the upper part of
great rate of microwire coiling onto a spool and decreasing the primary stretching cone the speed of wall movement is
glass viscosity, for instance by means of increase of slow enough and it does not exceed (2…5) · vg , where vg
operating temperature of the micro-bath, cast nanowires with – the rate of glass tube feeding into inductor area.
core diameter less than 100 nanometers might be produced.
Correspondingly, carrying force F is also weak; it rises in its
As long ago as in eighties of the past century the authors of
bottom part and in the beginning of the secondary stretching
the present report have managed to produce microwires with
cone.
ultra-thin bismuth-based core with core diameter within the
It is especially worth to emphasize that the internal
range from 80 up to 300 nanometers by means of the said
method. But at that time the overall diameter of the produced diameter of forming capillary d = 2r is mostly defined by
microwire was over 30 - 40 microns. Its casting method was variable radius rc(x) of primary stretching cone, giving
unstable, the core diameter fluctuating within a broad range onion-like shape to drop of metal and microbath in a whole (
(up to 300 %), and such a super-thin microwire was able to x – is vertical axe). In the report of Yu. Chugaevsky [9] it
be made of two core-formative materials with perfect was obtained the theoretical relation describing the shape of

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

the mentioned primary cone: F1+F2+F3= F4, (4)

2
  where forces promoting penetration of metal into a
ln R0 / rc  , (3)
2H
r  R  x 
2 2
capillary are listed on the left, while forces preventing from
 1  2 ln rc /  
c 0
 that are listed on the right. Here:
F1 = (p0 - p)·r2 – force, caused by pressure difference
over and below drop of melted metal in a microbath;
where R0, Н – radius and height of molten drop,  - radius F2 =  m g H r2 – force of pressure of column of melted
of a conditional column of melt on which ponderomotive metal with height Н on its surface at entrance to a capillary
force of electromagnetic field does not operate,. (this height depends on diameter and shape of drop of melted
Derivation of the obtained formula assumes by default metal in a microbath);
that the weight of the drop is completely counterbalanced by F3 – carrying force related to movement of walls of the
ponderomotive forces of electromagnetic field of inductor primary stretching cone and adhesion of metal to glass.
excluding a thin cylindrical ―rod‖ with radius  along axis of Taking into account that this force must ensure acceleration
the drop. The weight of this rod P = mgH generates
2
of column of melted metal from close to zero speed up to
vertical pressure along axis of area of capillary formation speed vs of capillary pulling drawing, it is easy to show that
and it is along with pressure difference over the drop of
melted metal both inside of capillary and under it (p0 - p) F3=(/2)m vs2 r2;
one of the component forces, promoting penetration of metal
into the capillary. Here m – density of core-formative
material, g – acceleration of gravity, pа – atmosphere F4 = 2m r – forces of surface tension of metal on a
border metal-vacuum inside of glass capillary.
pressure, p – rarefaction inside a glass tube over a
microbath. With the help of the abovementioned formulas it can be
The said model does not take into account horizontal shown that the radius of capillary a core-formative material
component of metal pressure on glass coating of a primary can penetrate in is defined by the following equation:
stretching cone, which significantly impacts on the diameter
of the said cone and, in the end, on the diameter d of
stretching capillary in comparison with expected one in r = 4m / { [(p0 - p) + m g H + m vs2]}. (5)
accordance with calculation.
As is well known, the high-frequency field of inductor As it can be seen from (5) in case of reduction of surface
(both cup-like and multi-coil one) has a singularity along the tension of metal m and increase of capillary drawing rate vs
vertical axis where expulsive force equals to zero.
reduction of diameter of microwire to be obtained d = 2r
Correspondingly, in case of suspended melt of metal within
can be achieved without any limitations, that does not
the bottom part of incipient drop a special area is formed (a
contradict to equations (1) and (2). It is worth to emphasize
―black spot‖ in a way), where ponderomotive forces do not
that we discuss conditions of metal penetration into glass
impact on that drop and the weight of this part of the drop
capillary, in case of poor degree of moistening and adhesion
can be counterbalanced by cohesion and surface tension of
between them. Increase of casting rate of micro- and
metal m only, while during microwire casting it can be
nanowires is limited by viscosity of glass g and metal m ,
counterbalanced by surface tension of glass g, as well. A and microwire diameter itself. In case of too poor viscosity
definite impact on balance of forces influencing on metal of any of components, slippage of metal or glass layers on a
inside of the microbath is contributed by the border between them may takes place.
abovementioned pressure difference (p0 - p), if pressure Fig.1 shows dependencies of minimal diameter d=2r on
inside of an empty capillary is close to vacuum gage a number of parameters of core-formative material and rate
pressure. of capillary drawing vs. Hands-on experience shows, that
Experiments carried out during microwire casting show minimal diameters of obtained micro- and nanowires are
that in the case of metals with low capillary constant а = easily achieved in case of metals with greater adhesive to
2m  (g m) (e.g., Pb and Bi), the metal drop is likely to glass, since in that case metal penetration into a capillary is
leak out of a microbath. This takes place, e.g. during Bi- facilitated as well as its acceleration up to required speed vs,
based microwire casting at every slightest vertical oscillation which can be even greater.
or insufficient glass viscosity close to the bottom of a Thus, in order to produce cast nanowires with minimal
microbath. We suppose that it takes place when the diameter cross-section, both core and coating thickness, proper
of a primary stretching cone in the bottom part is greater selection of glass-metal couple is required, which ensure
than some critical value, which exceeds 2, i.e. dimensions minimal inter-phase tension between glass and melted metal
of a ―black spot‖ of expulsive forces of electromagnetic field in a microbath.
of inductor. Usually, it lays within the range from 0.05 up to Usually such a selection allows to achieve inter-phase
0.2 mm. tension (at temperature of casting) about 0.5…0.7 of surface
As a first approximation balance of forces at entrance to a tension m of such a melted metal in vacuum. Quantitative
stretching cone impacting on penetration of metal into a assessment of typical casting process (and microbath
capillary can be presented in the following way: dimensions) provides r about a couple of microns for many
materials at casting rate up to 5 m/sec. E.g., in case of Bi

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

estimated value of initial minimal microwire core diameter on the critical zone of inflection glass surface microbath also
di = 2r = 3.5 m. sharply decrease (fig. 3).

45 1,8
3 1,6
3 rc/R0
40
1,4
1,2
35 2

d, m
1,0
30 0,8 1
0,6
d, m

25 2 0,4
0,2
20 18 20 22 24 26 28 30

15 1
Vs, m/s 4
10 1 - kg/s
2
5 ξ/R0 = 0,005
2
2 - kg/s
5 2 6 1
3 - kg/s
2
5 10 15 20 25 30
Vs, m/s
3
Fig 1. Dependence of minimum of core diameter on stretching speed for
different surface tension values. H/R0 = 0,1

However, after the melt entered the capillary and during

the continuation of the process of nanowire drawing, the X = x/R0
condition of further joint flow of the glass capillary with the
melt inside changes, and the reduction of the thread diameter
Fig 2. Influence parameters H and  on drop shape.
becomes possible. If the melt mass in the microbath does not
exceed the critical mass, the geometric parameters of the Values of H/R0 : 1 – 0,1; 2 – 0,2; 3 – 0,03; 4 – 0,5; 5 – 1; 6 – 2.
drawn micro- and nanowires depend mainly on properties of
the glass tube (its geometry, viscosity, and surface tension)
and main parameters of the technological process (speed of
capillary drawing, strength of an electromagnetic field of the
inductor, micro-bath temperature, and speed of the tube
feeding). In that case, in accordance with formula (2),
reduction of core diameter of micro- and nanowire is
possible, e.g. at increase of speed and tempearture of
microbath. It is worth to mention that such a reduction starts
from some initial diameter of stretching cone, a core-
formative material has already penetrated in.
Fn1
Therefore, the geometry of the primary and secondary
stretching cones has priority for nanowire formation. Ft1
According to the formula (5) increasing the height of melt Fs1
Fn2
drops in microbath (usually H is comparable to the drop
diameter 2R0) capillary diameter, suitable for entry the metal
into it must also decrease. But in case if magnitude of mgH
is much less that mvs its impact is small in this process.
2
Ft2
The value of H is critical to the shape of the drop and the Fs2
diameter of the secondary stretching cone, which in turn
determine the diameter of the drawn out glass capillary and
x
the microwire thread after entering of metal in the capillary.
The calculations executed in [9] according to formula
Fig.3. Influence of a melt pressure force on the shape of a primary
(3) have been carried out at a relation of parameters, specific
stretching cone (for the small drop – on the left, for the big drop – on the
for typical casting process of a resistive microwire. For right).
example, it was assumed that the length of the primary
stretching cone L is comparable with the dimensions of Correspondingly, the normal component of this force to
metal drop (L  H). The new calculations made for the the surface of the glass envelope of the primary stretching
cone is reduced, the diameter throughout its length
conditions of small values of L< 2H, showed that in this
decreases. This provides a reduction of the inner diameter of
case the radius of the stretching cone significantly decrease
the drawn out of the capillary and the received microwire
(see fig.2) which should ensure ceteris paribus decrease in
thread.
diameter of microwire thread cast to nanometric dimensions.
The obtained conclusions were experimentally checked
To reduce the length of L, it is proposed to reduce the on the existing equipment for casting microwire with a core
height of the melt drop. In this case, the pressures of the melt from pure (the anode) copper. To do this, after the formation
of microbath, the metal drop was decreased by so-called

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 German-Moldovan Workshop on Novel Nanomaterials for Electronic, Photonic and Biomedical Applications, Chişinău, 7-8th of July, 2011

"Reset" 2/3 of its mass to achieve a more flat (i.e., flattened III. CONCLUSION
in the vertical direction) of the form microbath. The carried out analysis and preliminary experiments
Then, the capillary extraction process is continued demonstrated principal potential of production of cast
until filling it with metal. The obtained microwire had a nanowire with nano-core diameter up to 100 nanometers by
diameter of about 200 ... 300 nm (fig. 4) at the drawing means of Taylor-Ulitovsky manufacturing method.
rate 4 m/s. Improvement of the described technology in combination
with selection of compatible materials can ensure further
reduction in both core diameter and overall diameter of
nanowire.
REFERENCES
[1] Nanotechnologies market: state and prospects. Under
general edition ESNL-2008 UMNITS ―Sokolinaia
Gora‖. M.MIREA-IKAR, (2008), 100.
[2] E.Badinter, N.Berman, I.Drabenko and others. Cast
microwire and its properties, Shtiintsa, Kishinev (1973).
[3] A.Ioisher, I.Nesterovsky. Microwire and devices of
resistance, Ed. IX (1972), 25-33.
[4] N.B. Brandt, D.V. Gitsu, A.M. Ioisher, B.P.
Kotrubenko, A.A. Nikolaeva. Prib. Tekn. Exp.,3,
(1976), 2561.
[5] K..Yu. Arutunov, N.P.Danilova, A.A. Nikolaeva,
J.Appl.Phys., p.2, v.76, No 10 (1994), 7139-7141.
[6] R.Zuberek, H.Szymezak, A.Zhukov, M. Vazques and
Fig.4. Cross-section of obtained copper microwire.
others. J. Magn. Mater. (2007), Vol.316, 890-894.
For further reducing these dimensions and obtaining of [7] S.Zotov, K.Kabisov, I.Silkis. Microwire in instrument-
nanowires with diameters around 100 nm or less it is making, Ed. IX ―Cartea moldoveneasca‖, Kishinev
necessary to undertake further experiments with other high- (1974), 3-17.
frequency inductors: with the larger cone angle, larger [8] E.Badinter, T.Huber, A.Ioisher, A.Nikolaeva, I.Starush.
diameter and a smaller lower opening. Proceedings of SPIE - Volume 5401. Micro- and
This is required to form a shallow drop with a sufficiently Nanoelectronics 2003, K.Valiev, A.Orlikovsky, Editors,
large amount of metal (not less than 140 mm3). It is May 2004, 257-268.
necessary to use also glass pipes with smaller viscosity. [9] Yu.Chugaevsky. Microwire and devices of resistance, v.
III ―Cartea moldoveneasca‖, Kishinev (1965), 16-
26.

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International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Smart Self-healing Eco-friendly Nano and

Nano-composite Protective Coatings
Abdel Salam Hamdy MAKHLOUF
Center of Research Excellence in Corrosion, King Fahd University of Petroleum & Minerals
Dhahran 31261, Saudi Arabia
[email protected]

Abstract – This paper reports our achievements in designing high performance eco-friendly coatings
technologies for light-weight materials through international collaborations with USA, Italy, France,
Romania, UK and Germany
Aluminum and its alloys are used widely in aerospace, automotive and packaging applications. The demand
for weight savings for automotive and aerospace materials has focused attention on magnesium alloys.
Several automobile manufacturers (Ford, GM, Chrysler, Volkswagen, Opel, FIAT) have co-operated to
develop new magnesium alloys for manufacturing less energy-consuming and hence, less polluted
automobiles. Because of its growing use in the transportation industry, the world demand and production of
magnesium have been growing steadily. Magnesium alloys have a variety of excellent properties. However,
Mg alloys remain very susceptible to corrosion despite their superior mechanical properties.
Chromate has been reported as the most efficient widespread conversion coatings for many metallic
substrates. However, the waste containing hexavalent chromate has many limitations due to the
environmental consideration and health hazards.
The aim of this article is to deepen the current understanding of corrosion and protection of aluminum and
magnesium and their alloys and to provide a base for future research work in this field. It will also report the
recent development in designing eco-friendly conversion coatings based on cerate, stannate, zirconate,
vanadate or molybdate conversion coatings as alternatives to the process involving toxic chromate.

Index Terms – Aerospace and automotive industry, chrome-free coatings, corrosion protection, surface
treatments.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Nanowires of Silicon Carbide and 3D SiC/C

Nanocomposites With Inverse Opal Structure
G.A. EMELCHENKO, A.A. ZHOKHOV, V.M. MASALOV, E.A. KUDRENKO, A.N. TERESHENKO,
E.A. STEINMAN, I.I. KHODOS1, V.I. ZINENKO1, Yu.A. AGAFONOV1
Institute of Solid State Physics, Russian Academy of Sciences 142432 Chernogolovka, Moscow District,
Russia
1
Institut of Microelectronics Technology and High Purity Materials,Russian Academy of Science, 142432,
Chernogolovka, Moscow District, Russia
E-mail: [email protected]
Abstract – Synthesis, morphology, structural and optical characteristics of SiC NWs and SiC/C
nanocomposites with an inverse opal lattice have been investigated. The samples were prepared by
carbothermal reduction of silica (SiC NWs) and by thermo-chemical treatment of opal matrices (SiC/C) filled
with carbon compounds which was followed by silicon dioxide dissolution. It was shown that the nucleation of
SiC NWs occurs at the surface of carbon fibers felt. It was observed three preferred growth direction of the
NWs: [111], [110] and [112]. HRTEM studies revealed the mechanism of the wires growth direction change.
SiC/C- HRTEM revealed in the structure of the composites, except for silicon carbide, graphite and
amorphous carbon, spherical carbon particles containing concentric graphite shells (onion-like particles).

growth in a hexagonal-prism shape as shown in fig. 1(b).

I. INTRODUCTION
Studies on the synthesis of nanostructures with new
functional properties expand the area of their potential use (a) (b) (c)
and, therefore, highly desirable. We have studied synthesis,
morphology, structural and optical characteristics of SiC
nanowires and SiC/C nanocomposites with an inverse opal
lattice.
II. EXPERIMENTAL (d) (e) (f) (g)
Carbothermal reduction of silica is most useful method for
the synthesis of SiC NWs. In this work we used both silica
and colloidal carbon in carbothermal reduction method as a
Si and C sources, respectively.
SiC/C composites in silicon dioxide were obtained using
an opal matrix which was a three-dimensional close-packed
Fig. 1. (а)- FESEM image of the NWs general view; (b,c) – FESEM
system of monodisperse sphere-shaped (globules) silicon images of the single hexagonal prism-shaped wire and bamboo-like wire,
dioxide particles (240 - 280 nm in diameter). The samples respectively; (d-g) – TEM bright-field images of the NWs types.
were prepared by thermo-chemical treatment of opal
matrices filled with carbon compounds which was followed Electron microscopy studies have shown that ―smooth‖
by silicon dioxide dissolution [1]. The samples were studied wires could have different growth axes depending on the
by electron microscopy, x-ray diffraction, wire‘s diameter. The NWs with diameter size < 100 nm
photoluminescence, IR and Raman scattering spectroscopy. (―thin‖ wires) have high-density of SFs. The growth axis of
The samples implantation has been carried out by He + ions the wire coincide with normal to the close-packed planes and
with energy 40 keV and doses of 1013-1015 ions/cm2. so with [111] crystallographic direction of 3C – structure.
The NWs with diameter size >100 nm (―thick‖ wires) can
III. SIC NANOWIRES have either the [110] or the [112] growth axis.
Fig. 1(a) shows FESEM images of the synthesized (a) (b)
product general view on the carbonic felt surface. From the
image, the product consists of the wires with a
diameter of 20-200 nm and a length of tens to hundreds of
micrometers. Figures 1(c-g) further reveals, that the
nanowires have different types of the morphology. From the
TEM images (d-g), all the wires have a well-pronounced
striped structure, which indicates the presence of twins and Fig. 2. (a) - FESEM image of the carbon felt before synthesis; (b) –
magnified view of the carbon fiber surface.
stacking faults (SFs) in the wires. Mainly, the three types of
the wires morphologies were assigned: «smooth» (fig.1e,f), The carbon substrate consists of carbon fibers with
«bamboo-like» (fig.1d, с) and ―Y-types‖ (fig.1 g) wires. In a diameter of 5 – 8 μm (fig.2 a). Figure 2b shows a
turn, «smooth» wires have SFs, which placed either magnified FESEM image of the fiber surface before the SiC
perpendicular (fig.1e) or at an angle to the growth axis of the wires synthesis. From the image, the fiber surface is
SiC wires (fig.1f). In general case, the ―smooth‖ wires covered by a randomly distributed ball-shaped ―hillocks‖

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with a size of 20 – 50 nm (however the hillocks with a size the upper domain has the side boundary with the [112]
of 300 nm are observed at scanning of the fiber surface). The direction (white lines show the traces of the {111} planes).
EDX analysis reveals a low concentration (~0.08 atomic %) Though the average growth axis of the wire is [112], because
of Si of the initial carbon fiber. The silicon is uniformly of such type domains are predominant in the wire.
distributed over the fiber surface and Si content varies within Thus, the certain type of 3C-structure twin domains in the
the range 0.05 – 0.1 at. %. Taking ―thick smooth‖ wires generates the crystallographic
(a) (b) orientations of the SiC close-packed planes and the wire‘s
growth direction, respectively.
The SiC NWs with core (SiC) – shell (SiO2) structure
were reported in many works. The physical properties of
such wires very differ from the ―bare‖ ones. In this report,
the core-shell wires were produced via annealing of the
initial ―bare‖ SiC wires at the temperature of 850 0C for 4 h
in air.
IV. SIC/C NANOCOMPOSITES WITH INVERSE OPAL
STRUCTURE
(c) The electron microscopy data revealed a highly porous
periodic structure which was a three-dimensional replica of
the voids of the initial opal lattice (Fig. 4, 5).
High temperature treatment (1770 – 1870К) causes
sintering of the composite with 15% shrinkage calculated by
the change of the diameter of the silicon dioxide sphere.
Etching-out of silicon dioxide results in formation of highly
porous structure (figure 4), whose density is
estimated as 0.03 g/cm3 (~1.3% of graphite density). The
specific surface measured by the BET method was 275 -430
m2/g in dependence of silica globule size. All the inside cuts
demonstrate a three-dimensional replica of the voids of the
initial opal lattice (figure 4, 5). The pictures show distinct
void semispheres with oval-shaped holes pointing to the sites
of the silicon dioxide sphere contact in the initial opal
Fig.3. (a) –dark field TEM image of [110] orientation of the wire; structure. Three holes in each semisphere can be seen in
(b)-dark field TEM image of [112] orientation of the wire;
figure 4 and in figure 5 there are four holes which
corresponds to the structure of the opal (111) and (100)
(c)-HREM image of the twin part showing change the growth direction faces. Beside such windows smaller random holes (defects)
depending on the direction of the lateral boundaries of twin domains.
occur in the sphere shells (figure 2). The shell thickness
into account un-uniform distribution of the SiC crystallites estimated by SEM pictures varies from 4 nm до 10 nm.
over carbon fibers we assume that some hillocks‖ can be The hexagonal silicon carbide was found to be non-
places of silicon agglomerations and the templates for uniformly distributed throughout the volume, its greater part
further SiC NWs nucleation. located in the surface layer up to 50 micron deep.
Figure 3 (a, b) shows TEM dark-field images of the ―thick Correlation of the data of element and diffraction analysis
smooth‖ wires. From figure 3a, the boundaries of SFs yields the following data on the phase composition of the
({111} close-packed planes in cubic structures) are inclined sample after etching in HF solution: The SiC content in the
at the angle of 550 (1250) with respect to the wire growth sub-surface layer is ~55% wt., inside the sample 1% wt., the
axis and so the boundaries normal makes the angle 35 0 with carbon content on the sample surface was ~32% wt., in the
the growth axis. This angle is close to the crystallographic bulk ~90% wt. ; the silicon dioxide content on the sample
angle between the [111] and the [110] directions of a cubic surface and in the bulk varies about 10% wt. There is a
structure. Hence, the growth axis of the wire is the [110]. In natural explanation of the large amount of silicon carbide in
the case of the wire (fig. 3b), the boundaries normal of the the surface layer compared to that in the bulk. The reaction
close-packed planes is inclined at the angle 190 with respect of carbothermal reduction of SiO2 with SiC formation
to the wire growth axis, which corresponds to the angle requires removal of gaseous carbon oxide which is realized
between the [111] and the [112] directions of a cubic in subsurface layers and hindered in the sample bulk on
structure. Therefore, the wire growth axis is [112]. closure of nanopores in the course of sintering.
Figure 3c shows HRTEM image of the region of the wire As to the SiO2 phase state, it is worth mentioning the
with [112] growth direction. From image, there is defect-free absence of narrow diffraction peaks is indicative of the
section with the twin 3C-structure in the wire. The bottom amorphous state of silicon dioxide in our samples.
domain has the side boundary with the [110] direction, while

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The data of x-ray diffraction, IR and Raman scattering ORD (Fig. 6, curves 1 and 2). It should be noted that the
spectroscopy enabled us to assume that the composite had orange-red dots (ORD), were detected in only one of the 4
hexagonal diamond fragments. The assumption of the samples of the series.
presence of the diamond phase in the composite based on the Band with maximum of about 2.16 eV (574 nm) (Fig. 6,
x-ray data was confirmed by RS and IR spectroscopy. The curve 2), 0.40 eV FWHM, similar to the band, as observed
RS spectrum of the sample under study consists of two 1318 in [1]. Radiation of ORD (curve 1) represents a broader band
cm-1 (halfwidth 75 cm-1) and 1258 cm-1 (halfwidth 40 cm-1) with a maximum of about 2.12 eV (585 nm), which admits
the expansion (see inset in Fig. 6) into two bands with
maxima at about 2.17 eV (571 nm) and 2.0 eV (620 nm),
which are characteristic for two types of N - V centers in
diamond: the neutral (NV)0 center (575 nm) and negatively
charged (NV) - center (638 nm) [2,3].
Peaks shift and the large width of the lines indicate the
small size of the radiation centers, comparable with 5-nm
nanodiamonds [4]. While studies temporal instability of the
PL centers have been found. About a few months of ORD
disappeared in the samples. It should be noted that the
comparison samples used in the irradiation with helium ions,
did not show an orange-red luminescence.
In order to identify structural fragments of the diamond
samples were investigated by transmission electron
microscopy, high resolution (HRTEM). At the structure of
the composites, except for silicon carbide, graphite and
Fig. 4 (111) side cut of SiC/C inverse opal upon etching in HF amorphous carbon, spherical carbon particles containing
solution concentric graphite shells (onion-like particles) were found.
In [5] have shown that when such particles are heated to
lines. The intensity of the second line is by an order of 700°C and irradiated with electrons so their nuclei can
magnitude less than that of the first. The IR transmission transform into a diamond. The distance between carbon
spectrum of the composite shows a 2000 cm-1 band which is
planes in onions decreases as we move from the outer to
in the region of intrinsic absorption of the diamond crystal
inner shells in the range of 0.34 nm - 0.22 nm. This decrease
lattice. No such absorption line is observed in the spectra of
in the interplanar distance is the result of compression of the

Fig. 6. PL spectra of two typical orange-red dots (curves 1 and 2) and site
Fig. 5. (100) side cut of SiC/C inverse opal upon etching in HF without ORD.
solution.
irradiated particles, which leads to the formation of diamond
particles in the nucleus. In [5] the pressure inside the particle
different graphite types. The weak intensity and large
was estimated, which can exceed the equilibrium pressure of
halfwidth indicate that the phase is strongly disordered and
the transition of graphite - diamond. The formation of
the crystalline sizes do not exceed several nanometers.
diamond nuclei was observed for many onions -like
Implanted samples show weak photoluminescence in the
particles, with the number of shells of more than 15. The
blue - green region of about 3.1 - 2.5 eV (400 - 500 nm).
size of crystalline diamond in the nucleus varies from 2 nm
Annealing after implantation at temperature of 800° C in an
to 50 nm. At room temperature, however, the lattice of the
inert atmosphere leads to the emergence of local dots in the
irradiated onions -like particles broken because of the many
sample, glowing orange-red (ORD). PL spectra of two
defects such as boundaries, which reduce the stability of
typical points are given in Fig. 6 (curves 1 and 2). Curve 3
onions [5].
(Fig. 6) measured with the sample area, where there were no
Fig. 7 shows a composite image of SiC / C, containing
glowing orange-red. Its intensity in the blue spectral region
onion-like particles. Interplanar distance in the nucleus
is almost two orders of magnitude below the intensity of
corresponds to the graphite phase of carbon. On one of

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twenty different parts of the sample giant onion-like particle Such small size of particles logically explains their
with diameter of 100 nm was observed. Fig. 8 shows images temporary instability. It is possible to assume, that the kernel
of the upper half of the particle. Apparently, a giant onion- is formed in the form of a diamond phase as a result of high-
like particle formed at the site of the octahedral voids in the temperature processing a composite opal - carbon. In due
opal lattice, completely filled with carbon, since the size of course the thermodynamic instable phase of diamond is
the octahedral cavities is 0.42DSiO2, where DSiO2 is ball transformed to graphite at room temperature. Implantation of
diameter. a composite by ions of helium initiates N – V centers
We used in this study silica spheres about 260 nm in size. formation in a diamond phase that ORD luminescence
Dimensions of oktaporous in this matrix corresponds to the confirms. After transformation of diamond in graphite ОRDs
inscribed sphere of diameter about 100 nm. As seen from the also disappear.
images (Fig. 8), the continuity of the graphite layers In the investigated samples we could not to detect
disrupted in many places. There are areas of disorientation fragments of a diamond phase, including and in kernels of
onion-like-particles. It is no wonder if to consider the lowest
concentration ОRDs in samples (1 ОRD per cm2), high
localness of HRTEM method and thermodynamic instability
small (2-3 nanometers) diamond clusters.

V. CONCLUSION
The SiC NWs were synthesized via carbothermal
reduction method using both the colloidal graphite and the
colloidal SiO2 as carbon and silicon sources, respectively. It
was detected the SiC NWs of the two types: ―smooth‖ and
―bamboo-like‖ wires. The ―smooth‖ wires with the diameter
< 100 nm have the [111] growth direction, while the wire
with diameter > 100 nm can have either the [110] or the
[112] growth direction. SiC/C-HRTEM revealed in the
structure of the composites, except for silicon carbide,
graphite and amorphous carbon, spherical carbon particles
Fig. 7 Spherical carbon particles, consisting of concentric graphite containing concentric graphite shells (onion-like particles). It
shells (onion-like particles), HRTEM. was established that the onion-like particles formed during
the manufacture of SiC / C nanocomposite at high
temperature treatment. It is shown that after implantation
and disordering the graphite layers at the atomic level, which
followed by heat treatment samples exhibit of the
is consistent with observations in [5].
luminescence characteristic for the N - V centers in
Analyzing results of measurements of set of parts of a
diamond. It is suggested that the diamond crystallites formed
composite, it is possible to note, that the typical size of
in the center of the onion-like particles during high
temperature treatment of the composite.
This work was supported by RFBR grant № 10-02-00460.
REFERENCES
[1] G.A. Emelchenko, A A Zhokhov, V M Masalov et al,
SiC/C nanocomposites with inverse opal structure,
Nanotechnology 2010, 21, №47, p. 475604
[2] Davies, G. & Hamer, M. F. Optical studies of 1.945 eV
vibronic band in diamond. Proc. R. Soc. Lond. A 348,
285–298 (1976).
[3] YI-R. Chang, H.-Y. Lee, K. Chen et al., Nature
nanotechnology, 2008, v. 3, p. 284-287
[4] C. Bradac, T. Gaebel, N. Naidoo, M. J. Sellars, J.
Twamley, L. J. Brown, A. S. Barnard,T. Plakhotnik, A.
Fig. 8. SEM image of giant onion-like particle with diameter of
100 nm (upper half of the particle) V. Zvyagin and J. R. Rabeau Nature Nanotechnology v.
5 (2010) 345-349
onion-like particles makes about 10 nanometers. The kernel [5] F. Banhart and P.M. Ajayan, Nature 382 (1996) 433
in such particle has the size about 2 nanometers according to
data [5].

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ZnO Growth Technologies:Current Status and

Perspectives
Oleg LUPAN
Technical University of Moldova
[email protected]

Abstract – Development of new technologies for ZnO nanomaterials and thin films is of critical importance
for further fundamental investigations and practical applications. We discuss on the main technical control of
the synthesis of zinc oxide and its properties, which are of significance in understanding the growth
mechanism and further developing ZnO-based devices. Next, we present a brief summary of recent research
activities, current status and progress in developing improved control of technological processes for zinc
oxide as advanced material.

Index Terms – ZnO, nanostructures, thin films, synthesis.

doped ZnO due to low-doping efficiency and others.

I. INTRODUCTION
Semiconducting metal oxide functional nanomaterials are
of potentially broad fundamental and technological interests II. PROBLEMS AND SOLUTIONS
in science ranging from the quantum physics to For reliable device applications, a major problem is the
optoelectronics [1,2]. Bulk crystals are of importance for lack of reproducible and reliable n- and p-type conductivity
making substrates of high quality and for enhanced devices with shallow donor or acceptor states in ZnO, respectively. It
with extended lifetime. However, size reduction to the is expected that doping low-dimensional crystals will lead to
nanometer range causes quantization of density of states, new physics and chemistry as these complex assemblies are
which alters the intrinsic properties of crystalline materials. investigated [13]. Just like their bulk counterpart, doping of
Scientific interest for studying the behavior of low- semiconductor nanocrystals by impurity atoms permits
dimensional matter (micro-nano-scale) has accelerated the tailoring their behavior, which can enable their new
elaboration of a number of new advanced multifunctional application in nano-electronics and nano-optoelectronics
materials with well defined structures, sizes and properties. [14]. However, multiple previous reports indicated dopant
These novel electronic, magnetic or optical performances of could be difficult for nanocrystals [14]. It has to be
the materials ranging from micro to nano-scale, along with mentioned that by a simple addition of a transition metal
multifunctionality derived from small size effect, have compounds to the growth solution does not result in
contributed extensively to different fields of device incorporation of dopants. These difficulties could be due to
applications, especially for optoelectronics, medical the fact that the surface-bound dopants may have different
diagnostics, and chemical sensing. Zinc oxide is one of geometries, and exchange coupling interactions with the
technologically important materials, which presents semiconductor band electrons than substitutionally
significant practical and scientific importance for different incorporated dopants have, and the target physical properties
areas [1-4]. For example, ZnO exhibits various applications of the material may therefore be compromised. Enormous
in gas sensors, electrodes for dye-sensitized solar cells efforts have been directed to this area of research by
DSSCs, light-emitting devices, luminescent materials, and different research groups worldwide.
thin-film transistors [1-12]. To show potential utilities of Currently several dopants are considered as the most
zinc oxide material, we noted some typical applications of promising dopant for p-type ZnO, like Sb, Ag, P, Li, Cu.
ZnO low-dimensional structures in Table I (here we present Another approach is co-doping of elements, which can
our results only). enhance the solubility of the doping atoms and produce
shallower defect levels. At the same time it is still
TABLE I. OUR RECENT REPORTED APPLICATIONS ON ZNO LOW- controversial about co-doping, since it requires a complex
DIMENSIONAL STRUCTURES (OUR RESULTS ONLY). decision on multiple aspects related to the impurity impact
Authors Year Application Refs on the crystal structure or the formation of possible
Lupan et al. 2007 Single Tripod-Nanosensor [5]
Lupan et al. 2008 Nano-photodetector [6]
secondary phase in the doped region, and the uniformity in
Lupan et al. 2008 Single Nanorod-sensor [7] distribution for the dopant. Extensive research efforts have
Lupan et al. 2009 Single tetrapod - microsensor [8] been made for the design and control of ZnO crystals with
Lupan et al. 2010 Individual Nanowire-nanosensor [9] low-dimensions via innovative strategies. Zinc oxide one-
Lupan et al. 2010 Nanowire-DSSC [10] dimensional (1D) nano-structures are important due to their
Lupan et al. 2010 Nanowire-LED [11]
conduction behavior of quantum particles and large aspect
Lupan et al. 2011 Tunable-LED [12]
ratio which permits for distinct structural performance as
Thus, understanding its technological aspects is of well as greater chemical reactivity. It is reported that
importance for solving great difficulties in achieving stable different ZnO nanowires/nanorods can be synthesized easily

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by using a pattern on any kind of substrate. However, for the vapor deposition; vapor phase transport, which includes
monocrystalline-based optoelectronic device fabrications, it vapor solid (VS) and vapor liquid solid (VLS) growth; metal
is important to control the growth of ZnO single crystalline organic chemical vapor deposition (MOCVD); chemical
nanowires directly on film in order to eliminate the strain vapor deposition; thermal oxidation of pure Zn and
effect derived from lattice mismatch between mono- condensation; field assisted thermal decomposition [1]. In
crystalline substrates and ZnO single crystalline low- Appendixes A-M - some morphological and structural
dimensional structures. In this way, the film may serve as a properties of the ZnO low-dimensional structures have been
convenient pathway for the transport of electrons, phonons, shown. Detailed technological description for these low-
and photons. Another significant problem is defect chemistry dimensional structures and their characteristics has been
or possibility to control defects in ZnO material. By solving reported in our works [15-30].
it, it will be possible to tune the functional properties. The These new developments of the technological methods are
most abundant point defects in ZnO are interstitial zinc atom believed to offer new perspectives for zinc oxide crystal and
(Zni) or oxygen vacancy (VO). Therefore, it is of importance nanostructures growth by well established techniques.
to carry out more comprehensive study of the technically
control over the synthesis technique in order to allow exact
IV. CONCLUSION
control over the defects, the type conduction and the
ZnO low-dimensional structures are attractive building-
emission properties with the possibility to elaborate and
blocks for applications in a micro-nano- devices like sensors,
fabricate nano-ZnO -based electrical, magnetic and optical
photodetectors, energy generators, solar cells, light-emitting
nanodevices.
devices as well as artificial structures for tissue engineering.
III. GROWTH OF ZNO Within the next decade, zinc oxide nanostructures will move
Zinc oxide material posses several types of fastest growth into industrial applications, if its growth and performances
directions [1]. The preferred crystallization could be can be well controlled. Also, if synthesized low-dimensional
understood by considering that ZnO wurtzite crystals have structures will be integrated in devices by using different
different growth rates for different planes too: V >V > approaches, e.g. focused ion beam nanoliphography [29],
_
( 0 001) (10 1 1) self-assembly, electric-field assisted assembly, etc.
V _ 
[1,15]. Due to different growth rates, the controlled Aligning of the grown nanorods and nanowires can be
(10 1 0 ) realized using a specific template. Simplest way used to
synthesis of preferred nanoarchitecture for specific make ordered nanowire arrays during of growth is ZnO film
applications can be realized by a well control of the grown on substrate is to create on the surface equal
synthesis process [15]. The crystal synthesis on a specific conditions to form seeds and grow to form uniformly
surface in the aqueous solution is based on heterogeneous distributed nucleus and finally nanorods [15]. It is
nucleation and subsequent growth. Considering these anticipated that the ZnO branched rods will find many
directions and the polar surfaces due to atomic terminations, applications in novel nanodevices and are expected to
zinc oxide exhibits a variety of nanostructures that can be promote synthesis of nanorod p-n junctions.
synthesized by controlling the growth rates along these Future work: Our future research efforts will be directed
directions. It is well known that a crystal posses different towards synthesizing oriented one – dimensional nanorods,
kinetic parameters for different crystal planes, which are which will facilitate construction of semiconductor oxide-
emphasized under controlled growth conditions. Thus, based nanodevices with well-ordered alignment, which are
synthesis techniques and regimes are very important for extremely important for scientific, technological and
synthesis of a specific structure. industrial application. Development of single doped ZnO
The growth techniques for zinc oxide nanostructures can nanorod LED for light emission sources. Also, high
broadly be classified as: sensitivity and selective nanosensors as well.

1. solution phase synthesis and APPENDIX A

2. gas phase synthesis.

In the solution growth procedures, the synthesis of the

material is carried out in a liquid. In most of reports they are
in aqueous solutions and the process is referred to as
hydrothermal synthesis. Due to the fact that the
heterogeneous nucleation takes place at a low level of
supersaturation of the complex solution, we can grow
different ZnO nanoarchitectures by controlling the reactant
Fig. A. (a) SEM image of the single ZnO Nanorod grown by an aqueous
concentration, process temperature, and pH value [15]. This technique at 97 C from ZnSO4 and NaOH solution. Also directions are
technique can be represented by: template assisted growth; indicated on SEM image. (b) Stick-and-ball representation of zinc oxide
spray pyrolysis for growth of thin films; electrophoresis; crystal structures.
electrodeposition; sol-gel route; hydrothermal [1,15].
In the gas phase growth procedures: gas phase synthesis is
realized in the gaseous environment in a closed chamber. In
most of the reports such kind of growth is carried out at
elevated temperatures from 450 C to 1450 C. The
following gas phase methods has been reported: physical

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APPENDIX B APPENDIX E

Fig. B. SEM image of the ZnO Nanowires branched in complex structures

grown by an aqueous technique at 97 C from ZnSO4 and NaOH solution. Fig. E. SEM image of the Mn-doped ZnO nanorods synthesized in a
hydrothermal process at 97 C aqueous solutions.
APPENDIX C
APPENDIX F

Fig. F. SEM image of the Ag-doped ZnO nanorods synthesized in a

hydrothermal process at 95 C from ZnSO4, AgNO3 and NH4OH solution.
Fig. C. SEM image of the ZnO branched needles synthesized in a
hydrothermal process at 77 C from ZnSO4 and NH4OH solution. APPENDIX G
APPENDIX D

(a) (b)

F
ig. G. (a) XRD pattern of ZnO nanorod arrays as-prepared on glass
Fig. D. SEM image of the self-assembled nanorods grown by hydrothermal
synthesized by the aqueous-solution method. (b) XRD pattern of doped ZnO
technique.
nanorod arrays on glass synthesized by the aqueous-solution method
showing shift of the peaks due to lattice parameters changes.

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APPENDIX h APPENDIX J

Fig. J. X-ray diffraction -2 scan of the ZnO nanorods grown on

GaN/sapphire (0001) substrate by hydrothermal technique.

APPENDIX K

Fig. H. Deconvolution of the 300-600 cm-1 region with Raman peaks using Fig. K. Room-temperature Raman spectra of ZnO nanorods hydrothermally
Gaussian fit of Micro-Raman scattering spectra of: (a) Sb-doped ZnO grown on GaN substrate.
nanorods and (b) Ag-doped ZnO nanorods.
APPENDIX L
APPENDIX I

Fig. I. Raman shift of ZnO nanorod arrays on Si substrate synthesized by Fig. L. I-V characteristics of the ZnO nanorods/p-GaN heterojunction in the
the hydrothermal method showing the good crystalline quality of the dark measured at 300 K.
material to be used in a nano p-n junction applications.
APPENDIX M

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individual ZnO nanowire with fast response at room

temperature,‖ Sensors and Actuators B: Chemical, vol.
144(1), pp. 56-66, January 2010.
[10] O. Lupan, V.M. Guérin, I.M. Tiginyanu, V.V. Ursaki,
L. Chow, H. Heinrich, T. Pauporté, ―Well-aligned
arrays of vertically oriented ZnO nanowires
electrodeposited on ITO-coated glass and their
integration in dye sensitized solar cells‖, Journal of
Photochemistry and Photobiology A: Chemistry, vol.
211(1), pp. 65-73, March 2010.
[11] O. Lupan, Th. Pauporté, B. Viana, Low-Voltage UV-
Electroluminescence from ZnO-Nanowire Array/p-GaN
Light-Emitting Diodes, Advanced Materials, vol.
22(30), pp. 3298–3302, August 2010.
[12] O. Lupan, T. Pauporté, B. Viana, P. Aschehoug,
―Electrodeposition of Cu-doped ZnO nanowire arrays
and heterojunction formation with p-GaN for color
tunable light emitting diode applications,
Fig. M. Room-temperature Micro-Raman scattering spectrum of the zinc Electrochimica Acta, In Press,
oxide nanorods grown by hydrothermal technique on sapphire substrate
with single crystal structure.
doi:10.1016/j.electacta.2011.02.004 online Feb. 2011.
[13] A. P. Alivisatos, ―Semiconductor Clusters,
Nanocrystals, and Quantum Dots,‖ Science, vol. 16, pp.
ACKNOWLEDGMENTS 933-937, February 1996.
Dr. Lupan would like to acknowledge Professors [14] D. J. Norris, A. L. Efros, S. C. Erwin, ―Doped
I.Tighineanu, Th.Pauporté and L.Chow for their guidance of Nanocrystals,‖ Science, vol. 319(5871), pp. 1776-1779,
my post-doctorate research in their laboratories in Moldova, 28 March 2008.
France and U.S.A., respectively. Also, their enormous [15] O. Lupan, L. Chow, G. Chai, B. Roldan, A. Naitabdi, A.
support of all performed scientific research and detailed Schulte, H. Heinrich, ―Nanofabrication and
discussions of our experimental data are gratefully characterization of ZnO nanorod arrays and branched
acknowledged. microrods by aqueous solution route and rapid thermal
REFERENCES processing,‖ Materials Science and Engineering: B, vol.
[1] I. M. Tiginyanu, O. Lupan, V. V. Ursaki, L. Chow, M. 145(1-3), pp. 57-66, December 2007.
Enachi, ―Nanostructures of Metal Oxides.‖ [16] L. Chow, O. Lupan, Guangyu Chai, ―FIB fabrication of
Comprehensive Semiconductor Science & Technology, ZnO nanotetrapod and cross-sensor,‖ Physica Status
Chapter 3.11, pp. 396-479, 2011. Solidi (b), vol. 247(7), pp. 1628–1632, July 2010.
[2] C. Burda, X. Chen, R. Narayanan, M. A. El-Sayed, "The [17] O. Lupan, L. Chow, S. Shishiyanu, E. Monaico, T.
chemistry and properties of nanocrystals of different Shishiyanu, V. Şontea, B. Roldan Cuenya, A. Naitabdi,
shapes," Chem. Rev., vol. 105(4), pp. 1025-1102, 2005. S. Park, and A. Schulte, ―Nanostructured zinc oxide
[3] Z. L. Wang, ―Zinc oxide nanostructures: growth, films synthesized by successive chemical solution
properties and applications,‖ J. Phys.: Condens. Matter., deposition for gas sensor applications,‖ Materials
vol. 16, pp. R829–R858, 2004. Research Bulletin, vol. 44, pp. 63-69, 2009.
[4] U. Ozgur, D. Hofstetter, H. Morkoc, ―ZnO Devices and [18] V.V. Ursaki, O.I. Lupan, L. Chow, I.M. Tiginyanu,
Applications: A Review of Current Status and Future V.V. Zalamai, ―Rapid thermal annealing induced
Prospects,‖ Proceedings of the IEEE, vol. 98(7), pp. change of the mechanism of multiphonon resonant
1255-1268, July 2010. Raman scattering from ZnO nanorods,‖ Solid State
[5] O. Lupan, G. Chai, L. Chow, ―Fabrication of ZnO Communications, vol. 143, pp. 437-441, 2007.
nanorod-based hydrogen gas nanosensor,‖ [19] L. Chow, O. Lupan, H. Heinrich, G. Chai, ―Self-
Microelectronics Journal, vol. 38, pp. 1211-1216, assembly of densely packed and aligned bilayer ZnO
December 2007. nanorod arrays,‖ Appl. Phys. Lett. vol. 94, pp. 163105,
[6] O. Lupan, L. Chow, G. Chai, L. Chernyak, O. Lopatiuk- April 2009.
Tirpak, H. Heinrich, ―Focused-ion-beam fabrication of [20] O. Lupan, L. Chow, G. Chai, H. Heinrich, ―Fabrication
ZnO nanorod-based UV photodetector using the in-situ and characterization of Zn–ZnO core–shell
lift-out technique,‖ Physica Status Solidi (a), vol. microspheres from nanorods,‖ Chemical Physics
205(11), pp. 2673–2678, Nov. 2008. Letters, vol. 465(4-6), pp. 249-253, November 2008.
[7] O. Lupan, G. Chai, L. Chow, ―Novel hydrogen gas [21] O. Lupan, G.A. Emelchenko, V.V. Ursaki, G. Chai,
sensor based on single ZnO nanorod,‖ Microelectronics A.N. Redkin, A.N. Gruzintsev, I.M. Tiginyanu, L.
Eng., vol. 85, pp. 2220-2226, 2008. Chow, L.K. Ono, B. Roldan Cuenya, H. Heinrich, E.E.
[8] O. Lupan, L. Chow, G. Chai, ―A single ZnO tetrapod- Yakimov, ―Synthesis and characterization of ZnO
based sensor,‖ Sensors and Actuators B: Chemical, vol. nanowires for nanosensor applications,‖ Materials
141(2), pp. 511-517, September 2009. Research Bulletin, vol 45(8), pp. 1026-1032, August
[9] O. Lupan, V.V. Ursaki, G. Chai, L. Chow, G.A. 2010.
Emelchenko, I.M. Tiginyanu, A.N. Gruzintsev, A.N. [22] O. Lupan, L. Chow, G. Chai, A. Schulte, S. Park, O.
Redkin, ―Selective hydrogen gas nanosensor using Lopatiuk-Tirpak, L. Chernyak, H. Heinrich,

57
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―Biopolymer-assisted self-assembly of ZnO ZnO Nanowire Arrays on p-GaN for Efficient UV-
nanoarchitectures from nanorods,‖ Superlattices and Light-Emitting Diode Fabrication,‖ ACS Appl. Mater.
Microstructures, vol. 43(4), pp. 292-302, April 2008. Interfaces, 2010, 2 (7), pp 2083–2090, July, 2010.
[23] O. Lupan, Th. Pauporté, ―Hydrothermal treatment for [27] O. Lupan, T. Pauporté, L. Chow, B. Viana, F. Pellé,
the marked structural and optical quality improvement L.K. Ono, B. Roldan Cuenya, H. Heinrich, ―Effects of
of ZnO nanowire arrays deposited on lightweight annealing on properties of ZnO thin films prepared by
flexible substrates,‖ Journal of Crystal Growth, vol. electrochemical deposition in chloride
312(16-17), pp. 2454-2458, August 2010. medium,‖ Applied Surface Science, vol. 256(6), pp.
[24] O. Lupan, T. Pauporté, L. Chow, B. Viana, F. Pellé, 1895-1907, January 2010.
L.K. Ono, B. Roldan Cuenya, H. Heinrich, ―Effects of [28] O. Lupan, T. Pauporté and B. Viana, ―Low-Temperature
annealing on properties of ZnO thin films prepared by Growth of ZnO Nanowire Arrays on p-Silicon (111) for
electrochemical deposition in chloride Visible-Light-Emitting Diode Fabrication,‖ J. Phys.
medium,‖ Applied Surface Science, vol. 256(6), pp. Chem. C, 2010, 114 (35), pp 14781–14785, August
1895-1907, January 2010. 2010.
[25] O. Lupan, L. Chow, L. K. Ono, B. Roldan Cuenya, G. [29] G. Chai, O. Lupan, L. Chow, ―Focused ion beam
Chai, H. Khallaf, S. Park, A. Schulte, ―Synthesis and fabrication of carbon nanotube and ZnO nanodevices‖
Characterization of Ag- or Sb-Doped ZnO Nanorods by in Nanofabrication Using Focused Ion and Electron
a Facile Hydrothermal Route,‖ J. Phys. Chem. C, vol. Beams Principles and Applications, Edited by Ivo Utke,
114 (29), pp 12401–12408, July, 2010. Stanislav Moshkalev and Phillip Russell ISBN13:
[26] O. Lupan, Th. Pauporté, B. Viana, I. M. Tiginyanu, V. 9780199734214 ISBN10: 0199734216 752 pages, Nov
V. Ursaki and R. Cortés, ―Epitaxial Electrodeposition of 2011.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

High-Pressure Study of YVO4 Nanoboxes

F.J. MANJÓN1, O. GOMIS2, S. RAY1, S. F. LEÓN-LUIS3, U.R. RODRÍGUEZ-MENDOZA3, V.
LAVÍN3, A. SEGURA4, D. MARTÍNEZ-GARCÍA4, and Ch. FERRER-ROCA4
1
Instituto de Diseño para la Fabricación y Producción Automatizada, MALTA Consolider Team,
Universitat Politècnica de València, Camí de Vera s/n, 46022 València (Spain), e-mail:
[email protected]
2
Instituto 2Instituto de Centro de Tecnologías Físicas, MALTA Consolider Team, Universitat
Politècnica de València, Camí de Vera s/n, 46022 València (Spain)
3
Instituto de MALTA Consolider Team and Departamento de Física Fundamental y Experimental,
Electrónica y Sistemas, Universidad de La Laguna, E-38200 San Cristóbal de La Laguna, Santa Cruz
de Tenerife (Spain)
4
Instituto de Ciencia de Materiales de la Universidad de Valencia, MALTA Consolider Team,
Universitat de València, C/. Dr. Moliner 50, 46100 Burjassot, València (Spain)

Abstract – YVO4 nanoboxes doped with Eu ions (4 at%) have been studied by means of X-ray diffraction,
Raman and photoluminescence measurements under high pressure. Photoluminescence measurements in
nanoboxes provide evidence that Eu ions locate at different symmetry sites in the nanoenvironment than in
bulk crystal. On the other hand, Raman scattering measurements under pressure provide evidence that
YVO4 nanoboxes undergo a monoclinic distortion of the zircon structure prior to their phase transition
towards the scheelite structure at high pressure.

Index Terms – high pressure, vanadates, X-ray diffraction, Raman scattering, photoluminescence.

YVO4 is a very interesting material which finds an nanocrystals than in the bulk likely due to the occupation of
extensive use in material science and technology due to its different symmetry sites by Eu ions in nanocrystals.
outstanding optical properties. YVO4:Nd3+ is used in Additionally, a possible intermediate monoclinic phase
industrial diode pumped solid state lasers [1]. The resulting from the distortion of the zircon phase and
improvement of luminescence properties in nanosized and occurring between the zircon and scheelite phases could be
pressure-treated materials has opened an enormous working present in nanocrystals unlike in the bulk as recently
field in phosphors [2] and the study of rare-earth ions in the suggested to occur in zircon-type chromates [8].
nano-environment of ABO4 compounds is important for the
development of phosphors with enhanced luminescence
REFERENCES
efficiency by combining the promising optical properties of
[1] W. Koechner, Solid-state Laser Engineering, Springer,
rare-earth ions and nanoparticles [3,4].
New York, 2006.
Bulk YVO4 crystallizes in the zircon structure (space
[2] G. Chen, N.A. Stump, R.G. Haire, J.R. Peterson, M.M.
group S.G. #141) and it undergoes two pressure-induced
Abraham, J. Phys. Chem. Solids 53 (1992) 1253.
phase transitions: a first one towards the scheelite structure
[3] A.J. Silversmith, W. Lenth, R.M. Macfarlane, Appl.
(S.G. #81) above 7.5 GPa [5,6] and a second one towards the
Phys. Lett. 51 (1987) 1977.
fergusonite structure (S.G. #15) above 23 GPa [7]. Knowing
[4] A. Patra, C.S. Friend, R. Kapoor, P.N. Prasad, Appl.
the phase transitions in nanocrystals could give a better
Phys. Lett. 83 (2003) 284.
insight into the relation between compositional, structural
[5] A. Jayaraman, G. A. Kourouklis, G. P. Espinosa, A. S.
and optical properties in order to design better phosphors or
Cooper, and L. G. Van Uitert, J. Phys. Chem. Solids 48
even provide novel nanocrystal phases which could be
(1987) 755.
retained in metastable way, like diamond, at ambient
[6] X. Wang, I. Loa, K. Syassen, M. Hanfland, and B.
conditions with enhanced optical properties with respect to
Ferrand, Phys. Rev. B 70 (2004) 064109.
parent materials.
[7] F.J. Manjón, P. Rodríguez-Hernández, A. Muñoz, A. H.
We have synthesized Eu-doped YVO4 nanoboxes with
Romero, D. Errandonea, and K. Syassen, Phys. Rev. B
zircon structure and 25 ± 5 nm lateral size. Nanoboxes have
81 (2010) 075205.
been characterized by X-ray diffraction, Raman scattering,
[8] A.K. Mishra, N.Garg, K.K. Pandey, K.V. Shanavas,
and photoluminescence under pressure up to 18 GPa. The
A.K. Tyagi, and S.M. Sharma, Phys. Rev. B 81 (2010)
pressure behaviour of nanocrystals has been compared to
104109.
that of bulk material [2,5-7]. We have found that the zircon-
to-scheelite phase transition occurs at a much higher
pressure in nanocrystals as compared to the bulk and that Eu
ions show a different photoluminescence spectrum in

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Collective Elementary Excitations of 2D

Magnetoexcitons Taking Into Account Excited
Landau levels.
S.A.MOSKALENKO1, M.A.LIBERMAN2, E.V.DUMANOV1, S.RUSU1, F.CERBU1
1
Institute of Applied Physics of the Academy of Sciences of Moldova, Academic Str. 5,
Chisinau, MD2028, Republic of Moldova
2
Departmant of Physics, Uppsala University, Box 530, SE-751 21, Uppsala, Sweden
[email protected]

Abstract – The collective elementary excitations of the two-dimensional magnetoexcitons in a state of Bose-
Einstein condensation (BEC) with wave vector k  0 were investigated in the frame of the Bogoliubov
theory of quasiaverages. The starting Hamiltonian of the electrons and holes lying on the lowest Landau
levels (LLLs) contains the supplementary interactions due to the virtual quantum transitions of the particles
to the excited Landau levels (ELLs) and return back. As a result the interaction between the magnetoexcitons
with k  0 does not vanish and their BEC becomes stable as regards the collapse. The energy spectrum of
the collective elementary excitations consists from two exciton-type branches (energy and quasienergy
branches) each of them with energy gap and roton-type section, from the gapless optical plasmon branch and
from the acoustical plasmon branch, which reveals the absolute instability in the range of small wave vectors.

Index Terms – Bose-Einstein Condensation, elementary excitations, magnetoexciton, plasmon

there were no soft branches of neutral excitations in IQL.

I. INTRODUCTION The energy gap  for formation of a quasielectron-
Properties of atoms and excitons are dramatically quasihole pair has the scale of Coulomb energy EQ  e2 /  l ,
changed in strong magnetic fields, such that the distance where  is the dielectric constant of the background.
between Landau levels c , exceeds the corresponding However delta was found to be small  0.1EQ . The lowest
Rydberg energies R y and the magnetic length branch was called as magnetoroton [13] and can be modelled
as a quasiexciton [5]. As was mentioned in [5] the traditional
l  c / eH is small compared to their Bohr radii [1,2].
methods and concepts based either on the neglecting of the
Even more interesting phenomena are exhibited in the case electron-electron interaction or on self-consistent
of two-dimensional (2D) electron systems due to the approximation are inapplicable to IQL. In a strong magnetic
quenching of the kinetic energy at high magnetic fields, with
field the binding energy of an exciton increases from R y to
the representative example being integer and fractional
Quantum Hall effects [3-5]. The discovery of the FQHE [6- Il .
8] changed fundamentally the established concepts about There are two small parameters of the theory. One of them
charged elementary excitations in solids [5]. The notion of determines how strong the magnetic field strength H is, and
the incompressible quantum liquid (IQL) was introduced in it verifies whether the starting supposition of a strong
Ref.[7] as a homogeneous phase with the quantized densities magnetic field is fulfilled. This parameter is expressed by the
v  p / q , where pis an integer and q  1 is odd having ratio Il / c  1 . Here I l is the magnetoexciton ionization
charged elementary excitations with a fractional charge potential, c is the cyclotron frequency eH /  c calculated
e*  e / q . These quasiparticles were named as anyons. A
with the reduced mass  and the magnetic length l .
classification for free anyons and their hierarchy were
Another small parameter has a completely different origin
studied in [9,10]. An alternative concept to hierarchical
and is related with the concentration of the electron-holes(e-
scheme was proposed in [11], where the notion of composite
h) pairs. In our case it can be expressed as a product of the
fermions (CF) was introduced. The CF consists from the
electron bound to an even number of flux quanta. In the filling factor v  v2 and of another factor (1  v2 ) which
frame of this concept the FQHE of electrons can be reflects the Pauli exclusion principle and the phase-space
physically understood as a manifestation of the IQHE of CFs filing(PSF) effect. This compound parameter v2 (1  v2 ) in
[11]. The statistics of anyons was determined in [10,12]. It the case of Bose-Einstein condensed excitons can take the
was established that the wave function of the system changes form u 2 v2 , where u, v are Bogoliubov transformation
by a complex phase factor exp[i ] , when the
coefficients and u 2  (1  v2 ) . The both small parameters
quasiparticles are interchanged. For bosons   0 , for
will be used below. But in the case of FQHE the filling
fermions   1 and for anyons with e*  e / 3 their
factor v  v2 basically determines the underlying physics
statistical charge is   1/ 3 . As was shown in Ref.[13], and it can not be changed arbitrarily. Instead of the

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

perturbation theory on the filling factor v the exact II. HAMILTONIAN OF THE SUPPLEMENTARY
numerical diagonalization for a few number of particles INTERACTION
N  10 proved to be the most powerful tool in studies of The Hamiltonian of the Coulomb interaction of the electrons
such systems [5]. The spherical geometry for these and holes in the frame of lowest Landau levels(LLLs) has
calculations was proposed [10, 14], considering a few the form:
number of particles on the surface of a sphere with the radius 1
Hˆ   WQ  ˆ (Q) ˆ (Q)  Nˆ e  Nˆ h 
R  Sl , so as the density of the particles on the sphere to 2 Q (1)
be equal with the filling factor of 2DEG. The magnetic
 e Nˆ e  h Nˆ h  Hˆ suppl
monopole in the center of the sphere creates a magnetic flux
through the sphere 2S0 , which is multiple to the flux where WQ is the Fourier transform of the Coulomb
quantum 0  2 c / e . The angular momentum L of a interaction in the frame of LLLs, Nˆ e and Nˆ h are the
quantum state on the sphere and the quasimomentum k of operators of the numbers of electrons and holes on the LLLs.
the FQHE state on the plane obey the relation L  Rk . They are determined below. Ĥ suppl is the supplementary
Spherical model is characterized by continuous rotational
indirect attractive interaction between the particle lying on
group, which is analogous with the continuous translational
the lowest Landau levels(LLLs) in view of their virtual
symmetry in the plane.
transitions on the excited Landau levels(ELLs) and their
Properties of the symmetric 2D electron-hole (e-h) system
return back [22]:
(i.e. h  0 ), with equal concentrations for both 1
components, with coincident matrix elements of Coulomb H suppl    e  e ( p, q; s )a †p aq† aq  s a p  s 
2 p,q,s
electron-electron, hole-hole and electron-hole interactions in
1
 h  h ( p, q; s)b†pbq†bq  s bp  s
a strong perpendicular magnetic field also attracted a great
 (2)
attention during last two decades [15-22]. A hidden 2 p,q,s
symmetry and the multiplicative states were discussed in
many papers [19, 23, 24]. The collective states such as the   e  h ( p, q; s )a †p bq†bq  s a p  s
p,q,s
Bose-Einstein condensation (BEC) of two-dimensional
magnetoexcitons and the formation of metallic-type Here the creation and annihilation operators a†p , a p for
electron-hole liquid (EHL) were investigated in [15-22]. The electrons and bq† , bq for holes were introduced. The matrix
search for Bose-Einstein condensates has became a elements of indirect interaction i  j ( p, q, z ) are described by
milestone in the condensed matter physics [25]. The
remarkable properties of super fluids and superconductors the common expressions [22]
 ( p, q, z; n, m)
are intimately related to the existence of a bosonic i  j ( p, q, s)   i  j (3)
condensate of composite particles consisting of an even n , m n ci  m cj
number of fermions. In highly excited semiconductors the In the case of electron-electron and hole-hole interaction the
role of such composite bosons is taken on by excitons, which expression (3) has the form[22]:
i i ( p, q, z; n, m)   Wt , kWz t , exp  i ( p  q  t )l 2  
are bound states of electrons and holes. Furthermore, the
excitonic system has been viewed as a keystone system for t , , (4)
exploration of the BEC phenomena, since it allows to control
particle densities and interactions in situ. Promising  exp  i ( p  q  t  z )l  (t  i ) (t  z  i )
2 nm nm

candidates for experimental realization of such system are but in the case of electron-hole interaction is:
semiconductor quantum wells (QWs) [26], which have a e  h ( p, q, z; n, m)   Wt , kWz t , exp  i (   )( p  q)l 2  
number of advantages compared to the bulk systems. The t , , (5)
coherent pairing of electrons and holes occupying only the (t  i ) n (t  i ) m (t  z  i ) n (t  z  i ) m ,
lowest Landau levels (LLLs) was studied using the Keldysh- where
Kozlov-Kopaev method and the generalized random-phase s 2
k2 l2
2 e2 
approximation [20, 27]. The importance of the excited Ws ,  e 2
,
Landau levels (ELLs) and their influence on the ground  0 S s2  k 2 (6)
states of the systems was first noticed by the authors of the Ws , k  W s ,  k  W s , k  Ws ,  k
papers [16-19]. The influence of the excited Landau levels
(ELLs) of electrons and holes was discussed in details in The Hamiltonian of supplementary indirect attractive
paper [21, 22]. The indirect attraction between electrons (e- interaction (2) has the form:
1 1
e), between holes (h-h) and between electrons and holes (e-
h) due to the virtual simultaneous quantum transitions of the
H suppl 
2
Bi i N 
2N
 s,
i i ( s,  ) 

interacting charges from LLLs to the ELLs is a result of their    e ( s,  )  e ( s,  )   h ( s,  )  h ( s,  )   (7)

Coulomb scattering. The first step of the scattering and the  
1
   e  h ( s,  )  e ( s,  )  h ( s,  )
return back to the initial states were described in the second
order of the perturbation theory. N s ,
Instead of density operators for electrons and holes we can
introduce their in-phase and in opposite-phase linear
combinations

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

ˆ (Q)  ˆ e (Q)  ˆ h ( Q); initial Hamiltonian was broken by the help of the unitary
transformation Dˆ ( Nex ) following the Keldysh-Kozlov-
Dˆ (Q)  ˆ e (Q)  ˆ h ( Q);
Kopaev method [27]. We can shortly remember the main
1 (8)
ˆ e (Q)   ˆ (Q)  Dˆ (Q)  ; outlines of the Keldysh-Kozlov-Kopaev method [27], [33] as
2 
it was realized in the papers [20, 21]. The unitary
1
ˆ h (Q)   Dˆ (Q)  ˆ ( Q)  transformation Dˆ ( Nex ) was determined by the formula (8)
2
They lead to the following relations [20]. Here N ex is the number of condensed excitons. It
ˆ e (Q) ˆ e (Q)  ˆ h (Q) ˆ h (Q)  transforms the operators a p , bp to another ones  p ,  p , as is

1 shown in the formulas (13), (14) [20], and gives rise to the
  ˆ (Q) ˆ (Q)  Dˆ (Q) Dˆ (Q)  ; BCS-type wave function  g (k ) of the new coherent
2 


Q
 e  h (Q)  ˆ (Q) Dˆ (Q)  Dˆ (Q) ˆ (Q)   macroscopic state represented by the expression (10) [20].
These results are summarized below
   e  h (Q)  ˆ (Q) Dˆ (Q)  Dˆ (Q) ˆ (Q)   0; Dˆ ( N )  exp[ N (d † (k )  d (k ))]
ex ex
Q
 g (k )  Dˆ ( N ex ) 0
and to the final expression
ˆ Dˆ †  ua  v( p  kx †
1 1  p  Da
H suppl  Bi i N 
2
 V (Q) ˆ (Q) ˆ (Q)
4N Q
p p )bk  p
2 x
ˆ Dˆ †  ub +v( kx (14)
1  p  Db  p )ak†x  p

4N
Q
U (Q) Dˆ (Q) Dˆ (Q) p p
2
kx †
(9) a p  u p  v( p  )  kx  p
where 2
U (Q)   i i (Q)   e  h (Q); bp  u  p  v(
kx
 p ) k†x  p
V (Q)   i i (Q)  e  h (Q); (10) 2
 i  j ( s,  )    i  j ( s,  ) exp(i l 2 )

a p 0  bp 0  0;
The estimations show that  p  g (k )   p  g (k )  0
U (0)  2 Ai i ; V (0)  0;
 ik y tl 2
1 u  cos g; v  sin g; v(t )  ve (15)
N Q
 U (Q)  Bi i  (0) N ex v 2
g  2 l 2 nex ; nex   g  v; v=Sinv;
It means that one can suppose the dependences S 2 l 2

Q2 l 2 The developed theory [20, 21] is true in the limit
U (Q)  U (0)e 2
; V (Q)  V (0)  0 (11) v2  Sin2 v , what means the restriction v2  1 . In the frame
III. BOSE-EINSTEIN CONDENSATION OF of this approach the collective elementary excitations can be
MAGNETOEXCITONS IN TWO ALTERNATIVE studied constructing the Green‘s functions on the base of
DESCRIPTIONS operators  p ,  p and having deal with the transformed
Bose-Einstein condensation(BEC) of 2D magnetoexcitons ˆ ˆ †( N ) .
cumbersome Hamiltonian H  D( Nex ) HD ex
was considered in Ref.[20, 21] in the frame of Keldysh-
Kozlov-Kopaev method [27], when the influence of the IV. EQUATIONS OF MOTION FOR THE TWO-
ELLs was neglected. The main results of this description PARTICLE OPERATORS AND FOR THE
will be remembered below. CORRESPONDING GREEN‘S FUCTIONS
The creation d † ( P) and annihilation d ( P) operators of The starting Hamiltonian in the quasiaverages theory
the 2D magnetoexciton have the form: approximation has the form
1
Hˆ   WQ   (Q)  (Q)  Nˆ e  Nˆ h   e Nˆ e  h Nˆ h 
1

 iP tl 2
d † ( P)  e y a † Px b† Px ;
N t t t  2 Q
2 2
(12)
 N  ei d † (k )  e  i d (k )   Bi i N 
1 1
 (16)
iPy tl 2
d ( P)  e b P a P ; 2
N t t  x t  x
2 2
1 1
The energy of the two-dimensional magnetoexciton  
4N Q
V (Q) ˆ (Q) ˆ (Q)   U (Q) Dˆ (Q) Dˆ (Q)
4N Q
Eex ( P) depends on the two-dimensional wave vector P and
The density fluctuation operators (24) with different wave
forms a band with the dependence vectors P and Q do not commute, which is related with the
Eex ( P)   I ex ( P)   I l  E ( P);
e2  helicity or spirality accompanying the presence of the strong

P2l 2
 P 2l 2  Il 
 0l 2
; W Q
 I l (13) magnetic field [18]. They are expressed by the phase factors
I ex ( P)  I l e 4
I0  ; Q
in the structure of operators (6) and by the vector-product of
 4 
two 2D wave vectors P and Q and its projection on the
To introduce the phenomenon of Bose-Einstein
direction of the magnetic field. These properties
condensation (BEC) of excitons the gauge symmetry of the

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

considerably influence structure of the equations of motion d ( P) , d † ( P) , ˆ ( P) and Dˆ ( P) . At the same time these
for the operators and determine new aspects of the 2D
Green‘s functions are two-particle Green‘s functions,
electron-hole (e-h) physics.
because the summary operators are expressed through the
The equation of motion for the creation and annihilation
products of two Fermi operators. In this sense the Green‘s
operators d  ( P), d ( P) (12) and for the density fluctuation functions (18) are equivalent with the two-particle Green‘s
operators (8) will be deduced, when the BEC takes place on functions introduced by Keldysh and Kozlov in their
the state k  0 . They are: fundamental paper [27], forming the base of the theory of
d high density excitons in the electron-hole description. But in
i d ( P )  [d ( P ), Hˆ ]  (   E ( P )  ( P))d ( P)  difference on [27] we are using the summary operators,
dt
 [ P  Q ]z l 2 
which represent integrals on the wave vectors of relative
2i  W (Q) Sin   ˆ (Q )d ( P  Q)  motions.
Q  2  The equations of motion for the Green‘s functions in a
1  [ P  Q ]z l 2  special case, when the BEC of magnetoexcitons takes place
  U (Q)Cos   D(Q)d ( P  Q)
N Q  2  on the state with k  0 , are:
(   i    E ( P)  ( P))G1 ( P,  )  C
D( P)
 N ei  kr ( P, 0)   ei ; (17)  [ P  Q ]z l 2 
N 2i  W (Q ) Sin    (Q )d ( P  Q ) X  
d †
Q  2 
i d ( P )  [d † ( P ), Hˆ ]  (   E ( P )   ( P))d † ( P)  1  [ P  Q ]z l 2 
dt   U (Q)Cos   D(Q)d ( P  Q) X    G4 ( P,  )e ;
i

 [ P  Q ]z l 2  †
N Q  2 
2i  W (Q) Sin   d ( P  Q ) ˆ (Q )  (   i    E ( P)  ( P))G2 ( P,  )  C
Q  2   [ P  Q ]z l 2 
 [ P  Q ]z l  †
2 2i  W (Q ) Sin   d ( P  Q )  (Q ) X
†

1
  U (Q)Cos 

 d ( P  Q ) D (Q ) Q  2 
N Q  2  
1
d † ( P  Q) D(Q) X   G4 ( P,  )e  i ;
N 
 i  i D ( P )
 N e  kr ( P, 0)   e ;  [ P  Q ]z l 2 
N (   i )G3 ( P,  )  C  i  W (Q ) Sin  
d
Q  2 
i ˆ ( P)  [ ˆ ( P ), Hˆ ]   ( P  Q )  (Q)  (Q)  ( P  Q)
dt   X 
 [ P  Q ]z l 2  N N 
 i  W (Q) Sin   [ ˆ ( P  Q ) ˆ (Q )  ˆ (Q ) ˆ ( P  Q )]  i  [ P  Q ]z l 2  D ( P  Q ) D (Q ) D (Q ) D ( P  Q )
Q  2    U (Q)Sin    X ;
 [ P  Q ]z l 2 
2N Q  2  N N 
i
  U (Q)Sin  2   D( P  Q) D(Q)  D(Q) D( P  Q)  ;  [ P  Q ]z l 2 
2N Q   (   i )G4 ( P,  )  C  i  W (Q) Sin  
d ˆ
Q  2 
i ˆ
D( P )  [ Dˆ ( P ), H ]  D(Q)  ( P  Q) D( P  Q)  (Q)
dt   X 
 [ P  Q ]z l 2  N N 
i  W (Q ) Sin   [ ˆ (Q) Dˆ ( P  Q)  Dˆ ( P  Q) ˆ (Q)]  i  [ P  Q ]z l 2  D (Q )  ( P  Q )  ( P  Q) D(Q)
Q  2    U (Q)Sin    X
i  [ P  Q ]z l 2  ˆ
2N Q  2  N N 
  U (Q) Sin   [ D (Q ) ˆ ( P  Q )  ˆ ( P  Q ) Dˆ (Q )] 2 e  i G1 ( P,  )  ei G2 ( P,  )  ;
2N Q  2 
  i i †
2 N e d ( P)  e d ( P )  ;  V. DYSON EQUATION AND SELF-ENERGY PARTS
Following the equations of motion (49) we will introduce Using Zubarev‘s procedure [29] for the Green‘s function
four interconnected retarded Green‘s functions at T  0 [28, we obtain a closed system of Dyson equation for the Green‘s
29] functions in the forms:
4
G ( P, t )  d ( P, t ); Xˆ † ( P, 0) ;
11 j 1
G1 j ( P,  ) jk ( P,  )  C1k ; k  1, 2,3, 4 (20)

G12 ( P, t )  d † ( P, t ); Xˆ † ( P, 0) ; The self-energy parts  jk ( P,  ) contain the different

ˆ ( P, t ) ˆ † average values of the two-operator products. They were
G13 ( P, t )  (18)
; X ( P, 0) ; calculated using the ground state wave function  g (0)
N
taken with k  0 and have the expressions:
Dˆ ( P, t ) ˆ †
G14 ( P, t )  ; X ( P, 0) ; D(Q) D(Q)  4u 2 v 2 N ;
N
  (0)  2v 2 ( Bi i  2 Ai i  (0));
The average will be calculated at T  0 in HFB (21)
D(Q)d (Q) N  d † (Q) D(Q) N  2uv 3 N ;
approximation using the ground state wave function  g (k )
(14). d (0)  d † (0)  uv N ;   ((0)   )v
The Green‘s functions (18) will be named as one-operator
Green‘s functions because they contain in the left hand side
of the vertical line only one summary operator of the types

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

All these averages are extensive values proportional to N or acoustical plasmon branch. It reveals the absolute instability
of the spectrum in the range of small and intermediary
N , they essentially depend on the small parameters of the
values of the wave vector k and has a very small real values
types u 2 v2 or uv3 , or uv . tending to zero in the limiting case k→∞. The optical
The cumbersome dispersion equation is expressed in general plasmon dispersion law is gapless with quadratic
form by the determinant equation: dependence in the range of small wave vectors and with
det ij ( P,  )  0; (22) saturation-type dependence in the remaining part of the
spectrum.
We introduced some simple approximations which allow
calculating our complicate equation (22). They are
P2 l 2 0.15

( P)  (0); U ( P)  U (0)e 2 , U (0)  2 Ai i . Following
these transformations we obtained results that are shown in
the Figures 1, 2, 3. It is spectrum of collective elementary 0.10

Il
excitations. Three of them are energy branches, whereas
another three are quasienergy branches representing the
mirror reflection of the energy branches. Between three 0.05

energy branches two of them are excitonic branches and one

of them is the acoustic plasmon branch. One-exciton energy
branch has an energy gap due to the attractive Hartree-type 0.00
interaction terms, which it is needed to be got over during 0.0 0.5 1.0 1.5 2.0 2.5 3.0

the excitation as well as a roton-type section in the range of pl

the intermediary values of the wave vectors. At higher Fig. 3. The dispersion law of optical plasmon branch in the presence of the
values of the wave vector its dispersion law tends to BEC of magnetoexcitons on the wave vector k  0 , calculated in HFBA,
saturation. Another two-exciton energy branch is interpreted
the filling factor v  0,1 .
2

by us as being the previous one-exciton energy branch

accompanied by the excitation of an condensate exciton with
wave vector k=0, the extraction of which from the Hartree- VI. CONCLUSION
type attractive environment needs also energy. The energy spectrum of the collective elementary
excitations of a 2D electrom-hole (e-h) system situated in a
0.6
strong perpendicular magnetic field in a state of Bose-
0.4
Einstein condensation (BEC) with wave vector k  0 was
0.2 investigated in the frame of Bogoliubov theory of
quasiaveraes. The starting Hamiltonian describing the e-h
Il

0.0
system contains not only the Coulomb interaction between
0.2
the particles lying on the lowest Landau levels, but also the
0.4 supplementary interaction due to their virtual quantum
0.6
transitions from the LLLs to the excited Landau levels and
return back. This supplementary interaction generates after
0.0 0.5 1.0 1.5 2.0 2.5 the averaging on the ground state BCS-type wave function
p the direct Hartree-type terms with attractive character, the
Fig. 1 The exciton branches of the energy spectrum of collective elementary exchange Fock-type terms giving rise to repulsion as well as
excitations of the Bose-Einstein condensed magnetoexcitons on the wave
the similar terms arising after the Bogoliubov u  v
k  0 , calculated in HFBA, the filling factor v  0,1 .
2
vector transformation. The interplay of these three parameters gives
rise to the resulting different from zero interaction between
0.15 the magnetoexcitons with wave vector k  0 and to stability
of their BEC as regards the collapse. It influences also on the
0.10
energy spectrum as well as on the collective elementary
0.05 excitations. It consists from four branches. Two of them are
excitonic-type branches, one of them being the usual energy
Il

0.00
branch whereas the second one is the quasienergy branch
0.05
representing the mirror reflection of the energy branch,
which will be described below. Another two branches are the
0.10 optical and acoustical plasmon branches. The exciton energy
branch has an energy gap due to the attractive interaction
0.15
0 1 2 3 4 5 6
terms, which is needed to be got over during the excitation
pl
as well as a roton-type section in the range of intermediary
Fig. 2. The dispersion law of acoustical plasmon branch in the presence of values of the wave vectors. At higher values of wave vector
the BEC of magnetoexcitons on the wave vector k  0 , calculated in its dispersion law tends to saturation. The optical plasmon
dispersion law is gapless with quadratic dependence in the
HFBA, filling factor v  0,1 .
2
range of small wave vectors and with saturation-type
The third energy branch taking part in this set is the dependence in the remaining part of the spectrum. The

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

acoustical plasmon branch reveals the absolute instability of [18] A.B.Dzyubenko and Yn.E.Lozovik, Fiz. Tverd. Tela
the spectrum in the range of small and intermediary values (Leningrad) 25, 1519, (1983); 26, 1540, (1984) [Sov.
of the wave vectors. In the remaining range of the wave Phys. Solid State 25, 874, (1983); 26, 938, (1984)];
vectors the acoustical plasmon branch has a very small real J.Phys. A, 24, 415, (1991).
value of the energy spectrum tending to zero in the limiting [19] D.Paquet, T.M.Rice, and K.Ueda, Phys. Rev. B 32,
case of great wave vectors. 5208, (1985); T.M.Rice, D.Paquet and K.Ueda, Helv.
Phys. Acta 58, 410, (1985).
REFERENCES
[20] S.A.Moskalenko, M.A.Liberman, D.W.Snoke, and
[1] M.A.Liberman and B.Johanson, Uspekhi Fiz. Nauk 165,
V.Botan, Phys. Rev. B, 66, 245316, (2002);
121 (1995).
[21] S.A.Moskalenko, M.A.Liberman, D.W.Snoke, V.Botan
[2] Dong Lai, Rev. Mod. Phys. 73, 629 (2001).
and B. Johansson, Physica E 19, 278, (2003); V.Botan,
[3] H.L.Stormer, Rev. Mod. Phys. 71, 875-889 (1999).
M.A.Liberman, S.A.Moskalenko, D.W.Snoke and
[4] Perspectives in Quantum Hall Effects, edited by S. Das
B.Johansson, Physica B 346-347 C, 460, (2004).
Sarma, and A. Pinczuk (John Wiley & Sons, Inc., New
[22] S.A.Moskalenko, M.A.Liberman, P.I.Khadzhi,
York, 1997).
E.V.Dumanov, Ig.V.Podlesny and V.Botan, Sol. State
[5] E.I.Rashba, Pure and Applied Chem. 67, 409, (1995).
Comm. 140/5, 236, (2006); S.A.Moskalenko,
[6] D.C.Tsui, H.L.Stormer, and A.C.Gossard, Phys. Rev.
M.A.Liberman, P.I.Khadzhi, E.V.Dumanov,
Lett. 48, 1559, (1982).
Ig.V.Podlesny and V.Botan, Physica E, 39/1, 137-149,
[7] R.B.Laughlin, Phys. Rev. Lett. 50, 13, (1983).
(2007)
[8] A.H.MacDonald, E.H.Rezayi, and D.Keller, Phys. Rev.
[23] V.M.Apalkov and E.I.Rashba, Phys. Rev. B 46, 1628,
Lett. 68, 1939, (1992).
(1992); ibid. 48, 18312, (1993); idem., Pisma Zh. Eksp.
[9] F.D.M.Haldane, Phys. Rev. Lett. 51, 605, (1983).
Teor. Fiz. 54, 160, (1991); ibid. 55, 38, (1992).
[10] B.I. Halperin, Phys. Rev Lett 52, 1583, (1984).
[24] X.M.Chen and J.J.Quinn, Phys. Rev. Lett. 70, 2130,
[11] J.K.Jain, Phys. Rev. Lett. 63, 199, (1989).
(1993).
[12] D.Arovas, J.R.Schriffer, and F.Wilczek, Phys. Rev.
[25] Bose-Einstein Condensation, edited by A.Griffin,
Lett. 53, 722, (1984).
D.W.Snoke, and S.Stringari (Cambridge University
[13] S.M.Girvin, A.H.MacDonald and P.M.Platzman, Phys.
Press, Cambridge, 1995).
Rev. B 33, 2481, (1986).
[26] L.V.Butov, A.L.Ivanov, A.Imamoglu, P.B.Littlewood,
[14] F.G.H.Haldane and E.H.Rezayi, Phys. Rev. Lett. 54,
A.A.Shashkin, V.T.Dolgopolov, K.L.Campman, and
359, (1985).
A.C.Gossard, Phys. Rev. Lett. 86, 5608, (2001).
[15] I.V.Lerner and Yu.E.Lozovik, Zh. Eksp. Teor. Fiz. 78,
[27] L.V.Keldysh, and A.N.Kozlov, Zh. Eksp. Teor. Fiz. 54,
1167, (1980).
978, (1968) [Sov.Phys.- JETP 27, 52, (1968)].
[16] I.V.Lerner and Yn.E.Lozovik, J. Low Temper. Phys. 38,
[28] A.A.Abrikosov, L.P.Gor`kov and I.E. Dzyaloshinskii
333, (1980).
Methods of quantum field theory in statistical physics
[17] I.V.Lerner and Yn.E.Lozovik, Zh. Eksp. Teor. Fiz. 80,
(Dover, New York, 1975).
1488, (1981) [Sov.Phys.-JETP 53, 763, (1981)].
[29] D.N.Zubarev Sov.Phys.Uspekhi Fiz.Nauk 71, 71(1960)

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Influence of Adsorption of Organic Molecules

on the PL Spectra of Porous Nanostructure and
Carbon Nanotubes, Covering the Surface of
Silicon.
V.G. LITOVCHENKO, T.I. GORBANYUK

V. Lashkaryov Institute of Semiconductor Physics of NAS Ukraine

Prospect Nauki, 41, 03028 Kiev, Ukraine; e-mail: [email protected]

Surface layers can be very sensitive to adsorption of of non-polar amino acids with hydrophobic radical. Glycine
organic molecules, introduced from liquid solution. So, it is a class of polar amino acids with hydrophilic radical. As a
will be play the role of the detector for different, sometime result of our experimental studies it was showed that the
ecological dangerous, molecules included organic. photoluminescense intensity decreases during methionine
Our research has been focused on the preparation and adsorption on Sipor/Me(MeOx) composite, while the adsorbed
characterization of layered semiconductor structures based molecules of glycine leads to an increase in intensity
on porous silicon (Sipor) with embedded nanoclusters of photoluminescense, i.e. the signal is changing in two
catalytic (Pd, W, Ni), noncatalytic (Cu) and metal-oxide opposite directions.
(CuOx, NiO, WOx) by means of I(V) characteristics and PL It was aslo found that the sensor structures with porous
spectra undo organic molecule adsorption and H2S gas silicon filled by palladium, is more sensitive to glycine,
adsorption. The distribution of catalytically active metal on while the filling of the pores by copper leads to increased
the thickness of porous silicon studied by secondary ion sensitivity to methionine. The structures with W and WO3
mass spectroscopy (SIMS). The thin metal films were clusters in Sipor are more sensitive to adsorption of hydrogen
deposited by dc magnetron sputtering from Pd, W, Ni, Cu sulfide. Selectivity fo these structures in relation to different
target in Ar on unheated Sipor/cSi substrate. The morphology types of adsorption of organic compounds makes them
of catalytic active composite has been characterized by AFM promising for producing multi sensor.
and SEM. A possible mechanism of adsorption sensitivity and
The adsorption of the donor (glycine, H2S) and acceptor selectivity of layered semiconductor structures based on
(methionine) types of molecules was investigated in porous silicon filled by different metal clusters to adsorbed
concentration range of 6,7– 67 mol/l and 1-100 ppm for . amino acids and H2S gas was proposed.
H2S. Methionine is essential amino acids, belongs to a class

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Photoelectric Converters: Current State Analysis

and Prospects of Evolution
Y.I. YAKIMENKO1, G.M. MLADENOV2, V.M. SPIVAK1, A.V. BOGDAN1, V.M.KOVAL1
1
National Technical University of Ukraine “Kiev Polytechnic Institute”, Kiev, Ukraine
2
Institute of Electronics, Bulgarian Academy of Sciences, Sofia, Bulgaria
[email protected]

Abstract – This review provides the analysis of current state and prospects of evolution of photoelectric
converters (PEC). There are shown the directions, ways and means of PEC research and development. It is
discussed the state of research in Ukraine and industrialized countries, given the forecast of changes in the
efficiency of converting solar energy into electricity as well as the cost of industrial production of solar cells.
It is shown the comparative characteristic properties of amorphous and nanocrystalline silicon solar cells.
The recommendations about promising areas of research and development to improve the efficiency of solar
cells are included.

Index Terms – nanocrystalline silicon, nanomaterials, photoelectric converters, photovoltaics, solar power.

mechanisms to stimulate development of solar

I. INTRODUCTION energy;
In recent years, the subjects of nanotechnology and  the existence of a scientific and technical human
nanomaterials are the scientific priorities of industrialized resources, which can ensure development and
countries. The development of nanotechnology and establish mass production of highly competitive
nanomaterials is considered as a new industrial revolution. In solar energy equipment, as well as construction
the coming decades, the efficiency of nanotechnology will and operation of solar power plants.
determine the status of every developed nation in the world. Photoelectric converter production grows 25-30% per
Ukrainian government does not stand apart from these year. It is forecasted that their production reaches a value
trends. In a joint order of Ministry of Education and Science 16 GW in 2012.
of Ukraine and National Academy of Sciences of the The forecast of photovoltaics development is shown in
November 26, 2009 №1066/609 ―The approval of the main Fig.I.
research directions and the most important issues of
1200
Electric power (GW)

fundamental research in 2009-2013 in Ukraine‖ the sections

grow s
1.4.5. ―Nanophysics and nanotechnology‖, and 1.6.5. 1000
rate 25%
―Nanostructured (nanodisperse, nanocrystalline) materials‖ 800
are specially underlined. 600
The silicon photoelectric converters (PEC) efficiency at grow s
400
level 25-28% and a unit cost 2,0-2,5$/W of generated electric rate 15%
power, impacted on the development of photovoltaic systems. 200
The main directions in this area include photoelectric 0
converters based on monocrystalline, multicrystalline, 2000 2020 2040 2060
amorphous silicon, triple-A3B5 semiconductor compounds,
Year
systems Cu-In-Se [1-5].
Fig I. The prospect of photovoltaic systems
II. THE ANALYSIS OF PROBLEMS AND THE
FORECAST OF PHOTOVOLTAICS DEVELOPMENT IN Table I shows the forecasted volumes and the dynamics
UKRAINE. of photovoltaics development in Ukraine for the period up
The overcoming of major obstacles to the development of to 2030.
solar energy - the high cost of electricity and thermal energy, Taking into account the current level of technology of
which is generated by solar plants, will be implemented due to converting solar energy into electricity and heating as well
a gradual increase in the cost of fossil fuels and the as the possible progress in this area over the period up to
introduction of the environmental component in rates for 2030, we can conclude that a significant contribution to the
electricity and heating. overall energy balance of the country can be made at the
The key factors that have influenced on promoting of the expense of large-scale introduction of two key
use of solar energy in the world till year 2030: technologies:
 the compliance with the Kyoto protocol on  first phase 2011-2015 – solar photoelectric power
greenhouse gas emissions; plants electricity production distant from the
 Government support of scientific and technical power network. The second phase 2015-2030 –
organizations specializing in the development of operation in the united energy system of Ukraine.
highly efficient solar-energy equipment. Creating the  the production of low-grade energy by solar
necessary legal and economic conditions and installations for partial or full supply of hot water

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in the warm season (April-October) for industrial and Leading Japan companies (Sharp, Kyocera, Mitsubishi)
agricultural enterprises, households, fitness and spa produce photoelectric modules on the basis of
facilities, schools, etc. multicrystalline, monocrystalline, amorphous silicon, and
 cover 45% of world production of photoelectric systems
TABLE I. KEY PARAMETERS OF PHOTOVOLTAICS IN UKRAINE (Fig.III) [6].
FOR THE PERIOD UP TO 2030
Year Capacity Electricity production
(MW) thousand kWh India
China
2010 60 102000 8,30% 1,50%
USA Japan
2015 120 8,50% 45,30%
204000
2020 200 340000
2025 300 510000 Europe
2030 400 680000 28,30% else Asia
Middle 5,70%
East Australia
Moreover, we assume the use of solar energy in industrial 0,40% 1,90%
processes: for the production of fresh water, in water-pumps,
in high-temperature metallurgy, in solar refrigeration and
domestic refrigeration, in solar dryers and in air-conditioning. Fig. III. The distribution of world production of photoelectric systems
Nevertheless, for the period until 2012 the use of solar energy based on multicrystlline, monocrystalline silicon. [6]
in these technologies will not make a significant contribution
to the overall energy balance of the country. According to the USA program SAI (―Solar America
It should be noticed that the development strategy of Initiative‖) [7], it is provided a strong support for U.S.
photovoltaics in the world's leading countries (USA, Japan, companies and universities (more than 10 billion $),
Germany, Australia, India, China, etc.) has a goal to cover engaged in the development and large-scale production of
consumption up to 30%. The concept of global energetic photoelectric modules and systems
(Fig.II) clearly shows the future grows of solar energy.

1600
1400 geothermal
solar
1200
Energy (exaJ)

biochemical
1000
800 w ind

600 hydro
nuclear
400 gas
oil
200
coal
0
1980 2000 2020 2040 2060 2080
Year

Fig II. The concept of global energetic evolution

TABLE II. FORECAST OF CHANGES IN CONVERSION EFFICIENCY AND THE COST OF PEC.
PEC type Modern level Efficiency, % Efficiency, % Efficiency, %
2010. 2020. 2030.
PEC based on monocrystalline silicon 13-16 (19) 16 (20) 19 (25) 22 (25)
Thin-film silicon solar cells 10 (14,7) 12 (15) 14 (18) 18 (20)
CIS (Cu-In-Se) – PEC 10–12 (18,9) 13 (19) 18 (25) 22 (25)
PEC based on A3B5 compounds 38,9 (40,2) 28 (40) 35 (45) 40 (50)
Electrochemical PEC (10,5) 6 (10) 10 (15) 15 (18)

. In the scientific aspect it is defined the development of: thermphotoelectric converters; new types of concentrating
new low-cost materials with high efficient capacity, chemical systems, etc.
stability, efficiency of industrial processes; thin films of To ensure the competitiveness of photoelectric systems
semiconductor and organic semiconductors; silicon wafers (PES) with other sources of energy (fossil fuels, nuclear
thinner than 100 mcm; silicon solar cells with conversion power, other renewable energy) it is necessary to reduce the
efficiency 25%; nanostructured materials; multitransition PES; cost of a watt peak power of at least 2 times (less than

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2,8$/W) and increased to year 2030 the production volume in the use of energy-intensive processes, such as thermal
1000 times [8-9]. Also, it must be taken into consideration the diffusion processes, screen printing, in which the operating
prevalence of the basic material in the nature, environmental temperatures reach 1070-1300K. There is a need of creating
cleanliness, not only finished PES, but their production new heterostructure converters using cheap materials, low-
processes, energy costs of production and a payback period. labor and low-energy processes.
Nowadays, more than 90% of the total production of the The decision of increasing the conversion efficiency of
PES is flat-panel modules made of crystalline and PEC for well-known technologies is usually associated with
multicrystalline silicon. At this stage of development of an increasing of the complexity of production, costs of
photovoltaics in the light of the above, silicon has a leading energy and materials, which leads to an inevitable increase
position. In this direction, it is planned to increase the in price. It is usually used the silicon with a high carrier
conversion efficiency from 12-16% to 20-22% due to lifetime, which is typical for higher quality, and hence,
improved design and technological parameters and to reduce more expensive silicon. In this aspect it is necessary to
the consumption of silicon by more than 2 times, since 50% of develop low-cost technological process that would ensure
the module is the initial price of silicon wafers. It should be the improvement of this parameter.
noted that, the use of concentrator and bilateral PEC can be an The conversion efficiency of today's photoelectric
effective way to reduce the cost [10]. Table II shows the converters on silicon is relatively low, because of
forecast of increasing the conversion efficiency of the basic conversion losses of short and infrared solar radiation,
types of PEC [11]. losses as a result of surface and bulk recombination, as well
According to expert estimates in the coming decades it is as optical reflectivity. It highlights the need for new
expected a real "boom" in the industry. It should be noted that methods of converting short-wave radiation, technological
the main objectives of this production – improving conversion methods of passivation, gettering and nanostructuring of
efficiency and reducing the cost of generated electricity – are surfaces.
impossible without providing cheap raw materials in sufficient The solution of these problems will give the opportunity
quantity and of reducing energy consumption in the to organize highly profitable production of photoelectric
manufacture process. Highly efficient photoelectric converters converters and modules; stand-alone energy sources for
based on gallium arsenide and related materials because of the different purposes; combined photothermogenetarors, that
high cost should be used to power spacecrafts. produce both electricity and heating; irrigation systems;
The main raw materials for photovoltaic production are drinking water production; photoelectric electrolyzers,
polycrystalline, multicrystalline and monocrystalline silicon, portable photoelectric devices for disinfection, etc.
which cost has increased recently. Also there are problems One of the way to reduce the cost of photoelectric
with the shortage of raw materials. The cost of the silicon in modules is to create on their basis the architectural blocks.
the price of photoelectric converters (PEC) is at least 50%. It Energy architectural glass blocks are manufactured for
is necessary to develop new technological approaches for different purposes (for example, ASI Glass, Austria):
reducing the amount of materials used in production combined  shading to reflect light;
with flexible adjustment of production to manufacture ultra-  lighting, light transmission;
thin wafers of ―solar‖ and nanocrystalline silicon. In this case,  heat;
the risk of production of basic products is dramatically  solar panels to produce electricity.
decreasing.
Modern production of photoelectric converters is based on

TABLE III. PARAMETERS OF THIN-FILM SILICON PEC.

Parameters Crystalline Si (thin Amorphous Nanocrystalline Organic
films) silicon silicon Semiconductors
Unit cost, $/W 2,4-2,7 2,0-2,4 1,7-1,8 1,5

The prospects of reducing 1,75 1,25 0,9-1 0,5

the costs, $/W

Conversion efficiency, % 15-20 10–13,6 14-16 5-7

All this can be accomplished with the use of optical

coatings and thin-film solar cells. For example, by changing III. THE USE OF NANOSTRUCTURED CRYSTALLINE
the conditions of film deposition ITO (transparent conductive SILICON TO CREATE THIN-FILM PEC
coatings based on oxides of indium and tin), we can control The construction in which a film battery is placed
the opacity of different regions of the spectrum [12]. ITO film between the glasses remains, but solar battery runs on
can serve as an excellent reflector of infrared (heat) radiation, nanocrystalline silicon with improved technical
ie, implement cooling. By changing the conditions of its performance. Foe example, the U.S. company UNI-Solar
deposition, we can ensure the transmission of infrared manufactures thin-film modules on the basis of amorphous
radiation, ie provide heating. The closest prototype unit to silicon (the nearest prototype of the proposed production).
produce electrical energy is a solar cell based on amorphous In 2006 their solar battery‘s capacity was 25 MW. In 2010 -
silicon – ASI Thin Film Solar Cells. the planned production capacity was 300 MW, ie increased
by 12 times.

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Table III shows the comparative characteristics of the  improving the manufacturing technology of PEC
parameters of thin-film silicon PEC.In nanocrystalline films in order to reduce material and energy costs of its
by changing the size of the nanocrystallites and the band gap production;
can be optimized the layer structure of the PEC for the  the appliance of new materials in PEC technology.
conversion of various ranges of the spectrum, and thus, From the authors point o view, the following ways to
theoretically increase the conversion efficiency of 50-60%. improve the efficiency of PEC are possible:
These achievements become possible when the technology of 1. Development of technological methods of
thin-film solar cells based on nanocrystalline semiconductors, producing photoelectric structures that preserve
in particular, nanocrystalline silicon is developed. the quality of the original semiconductor. The
Table IV shows the comparative analysis of properties of solution of this problem gives a rise of carrier
nanocrystalline silicon and amorphous silicon (on the basis of lifetime, which accordingly increases the rate of
which, a large-scale production lines are opened in Japan and collection of photogenerated charge carriers.
USA). 2. Creating a specially located doped regions in the
Thin-film photovoltaic modules can significantly improve semiconductor material that create the so-called
the specific energy characteristics: the conversion efficiency at pulling electric field in three-dimensional space,
8% - 600W/kg, 9% - 1250 W/kg, 10% - 2000 W/kg. That is which increases the mobility of charge carriers in
why they are seen as a close future of photovoltaic systems, the direction of current collectors.
including space purposes. 3. The extension of the PEC absorption spectrum in
the direction of the ultraviolet and infrared spectral
IV. CONCLUSIONS AND CHALLENGING AREAS OF regions.
RESEARCH AND DEVELOPMENT 4. Decrease the series resistance of the contact
The results of our studies led to creating the photoelectric transition zones and contacts.
converters with an efficiency of more than 21% 5. The use of new, more efficient optical and
(monocrystalline silicon wafers with size of 100x100 mm). protective coatings.
The main directions of improving the parameters of 6. Creation of new types of heterojunctions using
photoelectric converters are: alloys of amorphous and nanocrystalline silicon.
 optimization of the parameters of existing converters;
TABLE IV. COMPARATIVE CHARACTERISTICS OF THE PROPERTIES OF AMORPHOUS AND NANOCRYSTALLINE SILICON [12-16]
Parameters Amorphous Nanocrystalline Nanocrystalline silicon
silicon silicon (Section III of this paper)
1. Band gap, eV 1,75 1,96–2,2 1,85–2,25 (depending on the
size of crystallites and the
properties of the interface)
2. Electron mobility, сm2/V·s 0,1 40 42-45
3. Hole mobility, сm2/V·s 0,001 0,2 0,22-0,25
4. Photosensitivity (the ratio of 7· 103 5· 105 (5,6–6,4)· 105
photoconductivity to dark
conductivity)
5. Photosensitivity heterostructures 12 45 79-135
in the visible range, mA/lm
6. Photosensitivity of the 0,3-0,35 0,4-1,1 6,95
heterostructures at a wavelength of
350 nm, А/W
7. Degradation level, % 30-35 10-15 8-10
8. Manifestation of the degradation yes no no
effect Staebler–Wronski
9. Toxicity of the process yes yes no

наук Украины Ю.И. Якименко. – Киев-София:

REFERENCES Аверс, 2011. – 394 с
[1] Наноэлектроника: монография в двух книгах. Кн. [3] Green M.A. Third generation photovoltaic –
1. Введение в наноэлектронные технологии / Г. theoretical and experimental progress // Proc. of
М. Младенов, В. М. Спивак, Е. Г. Колева, А. В. the 19 th European Photovoltaic Solar Energy
Богдан.– Киев-София: Аверс, 2010. – 334 с. Conf. and Exhibition. – 2004. - Paris (France). - P.
[2] Наноэлектроника: монография в 2 кн. Кн. 2. 12 - 19.
Наноструктурированные материалы и [4] Roca F., Carabe J. Silicon heterojunction cells //
функциональные устройства /Ю.И. Якименко, А. Proc. of the 19 th European Photovoltaic Solar
Н. Шмырева, Г. М. Младенов, В. М. Спивак, Е. Г. Energy Conf. and Exhibition. - Paris (France). -
Колева, А. В. Богдан; под общей редакцией 2004. - P. 1321 - 1328.
действительного члена Национальной академии [5] Longo C., De Paoli M. Dye – Sensitized Solar
Cells: A Successful Combination of Materials // J.

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International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Braz. Chem. Soc. - 2003. - Vol. 14, № 6. - P. 889 – [10] Gasman L. Thin film and organic PV: New
901. Applications for solar energy // Nanomarkets. -
[6] Aratani F., Goto S. The Present status and future 2006. - P. 1- 61.
direction of technology development for photovoltaic [11] Arya R.R. Technology and market challenges to
power generation in Japan // Proc. of the 20 th mainstream thin – film photovoltaic modules and
European Photovoltaic Solar Energy Conf. - applications // Proc. of the 19 th European
Barcelona (Spain). - 2005. - P. 2846 - 2849. Photovoltaic Solar Energy Conf. - Paris (France). -
[7] Barnett A., Honsberg C., Kirkpatrick D. New US 2004. - P. 2024 – 2029.
Ultra High Efficiency R&D Programme // Proc. of [12] Repmann T., Appenzeller W. Advanced PECVD
the 21 th European Photovoltaic Solar Energy Conf. - processes for thin film silicon solar cells on glass
Dresden (Germany). - 2006. - P. 124 - 128. // Proc. of the 19 th European Photovoltaic Solar
[8] Swanson R.M. A Vision for crystalline silicon solar Energy Conf. - Paris (France). - 2004. - P. 1334 -
cells // Proc. 19 th European Photovoltaic Solar 1339.
Energy Conf. - Paris (France). - 2004. - P. 968 - 974. [13] Jun K.N., Stiebig H. Аmorphous silicon multilayer
[9] Унтила Г.Г., Кост Т.Н., Чеботарева А.Б., Закс solar cell deposited by PECVD method // Proc. of
М.Б., Ситников А.М., Солодуха О.И. Новый тип the 14 th European Photovoltaic Solar Energy
высокоэффективных двусторонних кремниевых Conf. - Paris (France). - 2004. - P. 1387 - 1390.
солнечных элементов с внешними шинами и [14] Hofmann M., Glunz S., Preu R., Willeke G. 21% -
проволочной контатной сеткой // Физика и efficient silicon solar cells using amorphous
техника полупроводников. - 2005. - Т.39, Вып.11. silicon rear side passivation // Proc. of the 21 th
- С. 1393 - 1398. European Photovoltaic Solar Energy Conf. -
Dresden (Germany). - 2006. - P. 124 - 128.

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Synthesis and Characterization of Colloidal PbS

Quantum Dots in Gelatin
Anatolie MITIOGLU, Cornel GHERMAN, Renata LASCOVA,
Anatolii CUHARUC, Anatolie GAVRILUŢA, Leonid CULIUC
Institute of Applied Physics of the Academy of Sciences of Moldova
[email protected]
Abstract – Colloidal solutions of lead sulphide (PbS) quantum dots (QDs) stabilized in gelatine were
obtained using a novel simple method. Nanoparticle sizes were tuned during the synthesis by means of
reaction temperature. In addition, the effect of acidity of solution, of reagents concentrations and of S to Pb
molar ratio was investigated. Transmission electron microscopy (TEM) and energy-dispersive X-ray
spectroscopy (EDX) was used to characterize the size and composition of PbS nanoparticles. Also, the
peculiarities of photoluminescence (PL) spectra of PbS QDs in gelatine were studied. It was observed that PL
spectrum consists of a relatively narrow excitonic band with the maximum located at 0.95– 1.3 eV depending
on the QDs size.
Index Terms – colloidal solution, gelatin, lead sulfide (PbS), photoluminescence, quantum dots.

range of 800-1500 nm.

I. INTRODUCTION II. MATERIALS AND METHODS
Specific properties of nano-sized materials and the Materials. The materials used in this work such as
progress of the last two decades in nanotechnology sodium sulfide Na2S∙9H2O (ACS reagent), gelatin powdered
necessitates to face the task of finding methods of (Ph. Eur.) and lead (II) nitrate (ACS reagent) were purchased
commercial production of different nanomaterials with from Aldrich and used without further purification.
controllable properties for various applications, including Synthesis of colloidal solution of PbS QDs.
those based on nanocrystals. In a typical experiment, preparation of colloidal solutions
Among important group IV–VI semiconductors, PbS QDs of PbS QDs stabilized with gelatin consists of three steps:
have attracted considerable attention owing to their I) producing an aqueous solution of gelatin (0.1-20 % by
especially small direct band gap (0.41eV) and larger mass) and lead (II) nitrate (10-4-0.1 M): 1 gr of gelatin was
excitation Bohr radius (18 nm) [1] and have been widely dissolved in 10 mL of 0.1 M Pb(NO3)2 upon slight heating in
used in many applications such as photography, Pb2+ ion- a conical flask;
selective sensors, IR detectors and solar absorbers [2–4]. II) heating the solution up to the required temperature (in
Recently, these nanomaterials have received great the range 20 ’ 90 °C) while stirring;
attention for their promising use in medicine. A key issue in III) adding to the solution obtained 1 mL of the aqueous
evaluating the utility of these materials is assessing their solution of 10-3-1 M Na2S dropwise, keeping stirring at the
potential toxicity - due to their inherent chemical temperature indicated. This step lasts about 5 min.
composition [1]. In addition, PbS QDs are an example of Optical characterization.
nanomaterials that have been shown to be useful as an The photoluminescence (PL) emission spectra were
alternative to luminescent dyes for biological imaging, due investigated using a grating monochromator and a
to their bright luminescence, narrow emission, broad UV photodetectors (IR photomultiplier ФЭУ-62, for
excitation and high photostability. wavelengths λ<1.1µm and/or InGaAs photodiode – 1µm <λ
So far various methods for the preparation of < 1.6µm).
semiconductor QDs in liquid media have been proposed [3, Taking into account the fact that the emission spectrum of
5, 6]. Most of them use different surfactants as stabilizers for PbS QDs is located in the near IR region [7], He-Ne laser
QDs, thus determining their chemical and physical (L1 = 633nm) and the second harmonic of YAG:Nd laser
properties, such as solubility, aggregative and kinetic (L2 = 532 nm) were used as excitation sources.
stability, as well as stability against photocorrosion; they can The absorption spectra in the same region were recorded
change the position of the optical absorption edge or by means of Shimadzu UV-3600 spectrophotometer. In
activate/suppress luminescence. order to ensure that the PL emission corresponds to the
In this work, we propose a novel easy method of the radiative recombination of excitons, the comparison between
synthesis of PbS QDs in aqueous solutions of a natural the emission and absorption spectra was carried out [8].
polymer, gelatin, and present the results of our investigation
III. RESULTS AND DISCUSSION
of their optical properties affected by synthesis conditions
Photoluminescence properties of gelatin stabilized PbS
such as concentration of reagents, germination and growth
nanoparticles.
temperature, molar ratio S/Pb and pH of the solution.
The PL properties of gelatin stabilized PbS nanoparticles
The modification of the reaction of formation PbS QDs
in different applications are investigated and described in
offers a possibility to obtain the QDs sized in the range of 2-
several papers and books [9-11].
20 nm; the size can be estimated from the excitonic bands in
In this work the PL spectra of the colloids prepared have
photoluminescence/optical absorption spectra within the
been recorded and the QDs sizes correlated to the position of

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the spectral maxima.

The solutions of PbS nanoparticles exhibit clear exciton
peaks and bright band-edge exitonic luminescence at room
temperature located in the near-IR spectral range (Fig. 1).
The PL broad bands are mostly attributed to the
recombination of the carriers trapped in surface states of
bare PbS QDs. These surface defects are associated with
Pb2+ and S2- vacancies (such as nonstoichiometric defects
and dangling bonds), that can induce nonradiative transitions
or radiative emission [12], resulting in the degrading of
luminescence properties.
h, eV
1.5 1.4 1.3 1.2 1.1 1 0.9
1.0

0.8
IPL, un. arb

0.6
Fig. 2. TEM micrographs of PbS nanoparticles in gelatin.
0.4

0.2

0.0
800 900 1000 1100 1200 1300 1400 1500
, nm
Fig. 1. Photoluminescence of PbS QDs synthesized in gelatin.

Generally, the PL of these QDs is intricate because it is

sensitive to the synthesis conditions, crystalline sizes and
shapes. Fig. 3. EDX spectrum of the PbS nanoparticles in gelatin.
TEM analysis.
The particles sizes of the synthesized colloids were 1135
determined by TEM. The typical micrograph in Fig. 2 shows
PbS QDs of about 4 nm in diameter coated with gelatin 1130
chains. This suggests that the core-shell products exhibit
1125
PL peak, nm

uniform sphere-shaped particles.

Fig. 3 shows the EDX spectrum of the synthesized PbS 1120
QDs in gelatin. The strong peaks for Pb and S in the
spectrum confirmed the main components of the PbS QDs. 1115
EDX analysis also indicated the presence of copper (Cu) on
1110
the surface of PbS QDs, which was due to the copper
substrate used. 1105
Desirable changes in size of QDs in a broad range (2-20 0 3 6 9 12 15 18 21
nm) can be achieved by modifying the acidity of the gelatin
solution, reagents concentrations, S to Pb molar ratio or the Fig. 4. PL emission peak dependence on gelatin concentration.
synthesis temperature. The changes in particle sizes were
When the gelatin concentration was set in the range 0.5
proved by the shift of the position of the maxima of
- 12%, the maximum of the excitonic PL remained
excitonic luminescence spectra in the range 800-2000 nm.
practically unchanged, which means that the final diameter
Influence of gelatin concentration on PL properties.
of the particles was unaffected.
The concentration of gelatin was varied in order to study
The results obtained might be interpreted by the increased
its effect on the PbS QDs formed and on their optical
efficiency of the passivation of surface states of the
properties.
nanoparticles: greater concentrations of gelatine result in a
In Fig. 4 the PL peak dependence on gelatin
larger number of chemical bonds between gelatine
concentrations for the samples at ambient temperature are
molecules and the surface atoms having dangling bonds.
presented. The PL emission peaks are seen to shift to shorter
Besides, according to [13], gelatine immobilizes QDs,
wavelengths.
increasing their dipole interactions because of lower
In our experiments, when the gelatin concentration was
mobility.
raised up to 12 – 20% a slight displacement of the maximum
Influence of the synthesis temperature on PL
position of the band of excitonic PL towards the shorter
properties.
wavelength was noticed, signifying a decrease of the average
As can be seen in Fig. 5, with the raise of the synthesis
diameter of QDs.

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temperature from 20 to 90 °C, the maximum of the

photoluminescence spectrum was found to become 1300
monotonously displaced from the lowest wavelength value
of 900 nm to the highest of 1300 nm, by means of increasing
the crystals diameter. 1200

PL peak, nm
1240
1100

1200
PL peak, nm

1000
1160

2 4 6 8 10 12
1120
pH
1080 Fig. 7. PL emission peak dependence on solution pH.

IV. CONCLUSIONS
1040 A novel easy method for the synthesis of colloidal lead
10 20 30 40 50 60 70 80 90
oC
sulphide nanocrystals in gelatin is presented. TEM studies
Temperature, showed that the sizes of QDs obtained were within 2 – 20
F
ig. 5. PL emission peak dependence on reaction temperature. nm and EDX spectroscopy confirmed the elemental
Influence of S to Pb molar ratio on PL properties. composition of nanoparticles. The sizes were tuned during
The growth of the ratio of S:Pb from 1:4 up to 4:1 leads, the synthesis by modifying the acidity of the solution,
reagents concentrations, S to Pb molar ratio and the
first, to the increase of the luminescence wavelength (crystal
synthesis temperature.
diameter), reaching the max. at the ratio 2:1, after which it
starts to decrease (Fig. 6). V. ACKNOWLEDGMENTS
It is worthwhile mentioning that ―better‖ synthesis This research was supported by SCSTD within the frame
conditions, in terms of narrower QDs‘ size distribution due of the state program ―Nanotechnologies and nanomaterials‖.
to the improved separation of nucleation and growth stages,
were found to lie in the region of smaller S:Pb ratios [14]. REFERENCES
[1] A.M. Derfus, W.C.W. Chan, S.N. Bhatia, Nano Lett. 4,
1300 11 (2004).
[2] Wang A., Pan A., Yin H., He Y., Xu Z., Zou B., Mater.
Lett. 60, 1242 (2006).
1200
[3] Patel A.A., Wu F., Zhang J.Z., Torres-Martines C.L.,
PL peak, nm

Mehra R.K., Yang Yi, Risbud S.H., J. Phys. Chem. B

104, 11598 (2000).
[4] Ji Y., Ma X., Zhang H., Xu J., Yang D., J. Phys.:
1100
Condens. Matter 15, 7611 (2003).
[5] Bakueva L.; Gorelikov I.; Musikhin S.; Zhao X.;
Sargent E. H.; Kumacheva E., Adv. Mater 16, 926
1000 (2004).
0 1 2 3 4 [6] X. Zhao, I. Gorelikov, S. Musikhin, S. Cauchi, V.
Ratio S2-/Pb2+ Sukhovatkin, E. H. Sargent, and E. Kumacheva,
Langmuir 21, 1086 (2005).
Fig. 6. PL emission peak dependence on S:Pb ratio.
[7] Zhang, S.; Cyr, P. W.; McDonald, S. A.; Konstantatos,
Influence of pH solution on PL properties. G.; Sargent, E. H., Applied Physics Letters 2005, 87.
The experimental data presented in Fig. 7 show that the [8] Gaponenko S. V., Optical properties of semiconductor
decrease of the solution pH from 13 to 4 did not result in a nanocrystals – Cambridge University Press, 1998.
significant change in the dimensions of the produced QDs. [9] Gau H., Herminghaus S., Lenz P., Lipowski R., Science
However, an increase of the crystals dimensions was 283, 46, 1999.
observed at lower pH. [10] Zhao M.Q., Sun L., Crooks R.M., J. Am. Chem. Soc.
The method presented here has some advantages over 120, 4877, 1998.
other known synthetic procedures, namely: [11] Beecroft L. L., Ober C.K., Chem. Mater. 9, 1302, 1997.
[12] Chestnoy N., Harris T.D., Hull R., Brus L.E., J.
- it is simple and fast;
Phys.Chem. 90, 3393, 1986.
- the final size of the QDs can be easily controlled;
[13] Wang Y., Chen H., Ye C., Hu Y., Mater. Lett. 62, 3382
- there is no need in complex and expensive equipment;
(2008).
- it uses non-toxic and non expensive reagents; [14] Abel K.A., Shan J., Boyer J-C, Harris F., Veggel F.
- no harmful residues are formed and, last, but not least, Chem. Matter 20, 3794-3796 (2008).
- the obtained nanocrystals are soluble in polar
environments, such as water.

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Synthesis of AAO Nanotemplate and Its

Properties
Natalia TSYNTARU*, Berkay KAVAS**, Jean-Pierre CELIS*
*
Katholieke Universiteit Leuven, Leuven, Belgium
**Istanbul Technical University, Istanbul, Turkey
[email protected]

Abstract – The objective of this study is to synthesize and to characterize anodized aluminium oxide (AAO)
nano-templates suited for large area device applications. The wear performance and the mechanical
properties of well-ordered nanoporous AAO obtained after a two step anodizing process in sulphuric acid
were investigated. Pores with different aspect ratios were obtained at cell voltages of 15 V and 21V. Ppore
diameters of ~16 nm and ~ 27 nm were noticed. The mechanical behaviour of such anodized aluminium
oxides (AAO) was determined by nanoindentation at 2 -200mN normal loads. The tribological behaviour of
these nano-templates was studied under reciprocating (ball on flat) sliding against alumina counter-balls. The
dependence of the properties of AAO-templates on the small pore diameter is discussed

Index Terms – anodized aluminium oxide; friction and wear; hardness; pore diameter.

constant current density of 500 mA.cm-1 for 1 min in an

I. INTRODUCTION
electrolyte consisting of perchloric acid (60 wt %) and
Due to the rapid development in nanotechnologies, a lot of
ethanol (abs.) in a volumetric ratio of 1:4. Temperature was
attention is given to the preparation and characterization of
kept at ~10 oC [7, 8]. [9]. Perchloric acid was used to
anodic aluminium oxide (AAO) membranes. AAO is a
achieve the proper low pH and to ensure that Al ionizes into
nanostructured material which can be of interest in many
Al3+ and does not form oxides [10]. It must be noted that the
fields like catalysis, chemical sensors, biosensors, filters,
edges of the sample were electrically isolated.
templates for self-assembly, and humidity sensors [1, 2]. The
2.2. Anodizing
AAO film can also be used as a support for measuring
Two step anodizing was performed in a 20 wt % sulphuric
mechanical properties of nanocarbon tube ropes [3]. AAO
acid electrolyte using a two electrode electrochemical cell
films are potentially advantageous for tribological
set up with a magnetic stirrer rotating at 500 rpm. The
applications since the nanoporous structure can be used as a
temperature was kept at ~ 1 oC during anodizing.
reservoir or a template for solid lubricants and nano-tubes or
Electropolished samples were cleaned in de-ionized water
nano-fibers to form self lubricating structures [4]. AAO
and anodised at a potential of either 15 or 21V for 10 min.
microstructures can be classified into two types: a relatively
After a first anodizing step, samples were rinsed with de-
pure alumina type (inner layer) consisting entirely of Al 2O3,
ionized water and immersed in a solution of chromic acid
and an acid anion-contaminated type (outer layer) resulting
(1.8 wt%) and phosphoric acid (6 wt %) for 10 and 15 min
from the incorporation of anions into the alumina structure
respectively, at ~60 °C to achieve a removal of the oxide
during anodizing [5]. These phases present in the AAO
layer. In this way, we achieved a prepatterning of the
structures are important when using AAO membranes in
aluminium surface for pores to grow inwards during the
applications requiring a high mechanical strength. Friction
second anodizing step at a constant potential of either 15 or
and wear performance of filled-in AAO films were
21 V for 97 and 20 min respectively at ~ 1 °C. The AAO
previously studied [6].
thickness was ~17 µm (Fig.1.). Pore sizes 16 and 27 nm.
However, a better understanding of wear and friction
properties of AAO and how the behaviour of AAO changes
with further processing, are still needed. In this
investigation, AAO films have been synthesized with narrow
pores, and tribological and mechanical studies of these AAO
films supported by an aluminium substrate have been
performed. 17 µm

II. EXPERIMENTAL
2.1 Sample preparation
Prior to anodizing, commercial pure Al sheet (% 99.99,
Alfa Aesar Johnson Matthey GmbH) was cut into round
pieces with a diameter of 9 mm that perfectly match in a
sample holder. Samples were ultrasonically degreased in
acetone and ethanol followed by a rinsing with deionised Fig.1. Cross section on AAO with a thickness of 17 µm (light grey area:
water. Anodizing was done on a surface with low roughness. AAO, dark grey area Al).
Hereto aluminium samples were electropolished at a
2.3. Tribological and mechanical characterisation

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

For the investigation of tribological properties at meso- and 3.2. Tribological performance of as-received AAO films
macro-loads, we used Falex Modular Universal Surface In order to determine the tribological behaviour of
Tester (MUST) and a KUL-MTM fretting mode I apparatus amorphous [5] as-produced AAO films supported on
[11]. The counterbody was a 5 mm corundum ball aluminium substrate, fretting test were carried out. The
reciprocating on AAO samples at a frequency of 1 Hz. The evolution of the coefficient of friction with fretting cycles is
stroke length was 100 µm. Tests were repeated at least three given in Fig. 3. It shows the dependence of the coefficient
times at normal loads between 40 mN and 1,000 mN to of friction on the pore diameter and normal load applied.
reveal the tribological behaviour at low and rather high The coefficient of friction increases steeply at the beginning
loads. Test temperature was kept constant at 23 oC. Humidity of the sliding tests. After around 80-100 cycles at meso-
was 50% RH. Samples were cleaned before fretting tests for loads, a steady state is reached during which the coefficient
degreasing them, and after fretting tests ultrasonically in
of friction is approximately the same for both pore sizes. The
ethanol for 7-10 min to remove the debris. Samples were
coefficient of friction for AAOs with the same pore
examined using scanning electron microscopy (SEM, Philips
diameter, remained practically the same independently the
XL-30), Field Ion Beam SEM (FIB-SEM) and white light
interferometer (VeeCo) before and after wear tests. load applied. At high loads of 1,000 mN, the coefficient of
Chemical composition was identified by energy-dispersive friction is higher probably due to of debris formed during the
spectroscopy (EDS). fretting tests. At a smaller AAO pore diameter namely 16
Nanoindentation was performed at six different loads as 2, 5, nm, this effect is more obvious (Fig. 3a). Since we used a
20, 50, 100 and 200 mN using Berkovich nanoindenters counterbody also made of alumina, the coefficient of friction
(CSM Instruments). Loading and unloading rates were as can reach high values, but it also assures that no chemical
twice as the maximum load applied. Indentation marks were reaction will occur in the sliding contact. However, after
examined by optical microscopy and SEM. reaching a peak value, the coefficient of friction decreases
slightly especially at a normal load of 1,000 mN (Fig. 3).
III. RESULTS AND DISCUSSION
3.1. Influence of sample preparation procedure
The anodizing of aluminium was done on samples with a 1.4
low surface roughness. Indeed, anodising reactions take
1.2 Pore diameter: 16 nm
place at the surface of the anode, and a low surface
roughness is a must to get a uniform anodizing rate at each 1.0
Coefficient of friction

spot. SEM and white light interferometer investigation

performed before and after electropolishing, revealed how 0.8
this pre-treatment influences the surface roughness.
Roughness values, Ra and Rz were ~740 nm and ~7 µm 0.6

prior to electropolishing. After electropolishing Ra and Rz 40 mN

0.4 80 mN
were ~140 nm and ~1.5 µm respectively. SEM images of the 1000 mN
two types of surfaces are given in Fig.2. 0.2

0.0
0 150 300 450
Number of cycles

Fig. 3. Evolution of AAO coefficient of friction at meso- and macroscale

loads.

To reveal the wear mechanism during the running-in

period, short sliding tests of 50 cycles were done. Wear
tracks observed using SEM (Fig.4) revealed that the pores
were filled up with very fine debris formed in the sliding
contact. Some pores could still partially be seen underneath a
b very thin debris layer covering the surface. It can be noticed
that the pores were obtained without any serious damage to
the tubes.
To study the propagation of wear, wear tracks after 500
fretting cycles (steady state part) were analyzed (Fig 5).
These experiments show that a tribolayer is formed by a
progressive degradation of the AAO top layer and by filling
up the pores with nanosized debris. This tribolayer consists
of a compacted bed of wear particles and has a partially
Fig. 2. SEM images of the aluminium surface before (a) and after layered structure which we observed after 500 fretting
electropolishing (b). cycles. That tribolayer is not equally spread over the whole
wear track area (Figures 4 and 5).

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

40 mN

80 mN
Fig. 4. SEM images of AAO (pore diameter 27 nm) after 50 fretting cycles.

a b c

d e f
Fig. 5. SEM images of wear tracks on AAO membrane (pore diameter 27nm) after 500 sliding cycles at normal loads of 40, 80 and 1000 mN at low
magnification (a, b and c) and high magnification (d, e and f) respectively

Ultrasonic cleaning of the tested samples in ethanol after coefficient of friction at the start of the sliding tests can be
the wear tests, did not allow to remove the bed of debris linked to the formation of this tribolayer. On further sliding,
from the surface. This reveals that the debris iss sticky, compacted small worn debris may cause abrasion wear and a
adhering locally on some parts of the wear track and on the high coefficient of friction.
counterbody (not shown here), resulting in a complex wear
mechanism being a combination of abrasive and adhesive 3.2. Nanoindentation
wear, and in a high coefficient of friction. The increasing Nanoindentation tests were performed over a wide range

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of normal loads (2-200 mN) to study the mechanical hardness at low loads are smaller which can be linked to the
behaviour of anodized aluminium oxides. The investigation ‗hole effect‘ described in [14]. This research shows that the
of nanoindentation imprints and surrounding areas was done elastic modulus and hardness vary when the normal load is
by using SEM. The study did not reveal major cracks inside increased. The difference is thought to be due to the
and outside the indentation imprints (Fig. 6). Considering anisotropy which is not accounted for in the indentation
that alumina is a ceramic material, the actual mechanism of method and also due to the influence of the aluminium
deformation within the material during indentation comes substrate underneath the AAO film.
into question. A high magnification SEM image of an 12000
indentation in an AAO film is shown in Fig. 6, in which a
pore crushing is evident as the mechanism caused permanent
deformation in the material. The corner of the imprint seen 10000 a
in Fig. 6, is surrounded by a regular pore structure, while the

Hit (O&P), MPa

pores appear to be deformed within the imprint due to an 8000
overall collapse of the porous structure. Rather than through 27 nm
pure material plasticity, the overall structure of the AAO 16 nm
membranes is progressively deformed on indenter loading. 6000

a
4000

2000
0 500 1000 1500 2000 2500
Maximum penetration depth

100
b
27 nm
Eit (O&P), MPa

80 16 nm
b
60

40

20
0 500 1000 1500 2000 2500
Maximum penetration depth
Fig. 6. Nanoindentation imprints at 2, 20 mN (a and b) respectively and
surrounding area on AAO templates at pore diameter 27 nm. Fig. 7. Hardness (a) and elastic modulus (b) as a function of indentation
depth recorded on 17 µm thick AAO membrane produced at 15 and 21 V.

Data on hardness and elastic modulus are plotted in Fig.8 IV. CONCLUSION
versus indentation depth. At low indentation depth, a large Well-ordered nanoporous AAO film was obtained with
scatter in hardness (e.g. 9.5±0.8 GPa and 5.4±0.5 GPa for relative small pore diameters of 16 and 27 nm. It was been
2mN, Fig.7 a) and elastic modulus (97±5 GPa for 2mN Fig.7 shown that AAO films subjected to meso- and macro-load
fretting tests form very fine debris on their surface. Debris
b) are observed. It is noticed that at on AAO with a 16 nm
produced during sliding on the surface fill up the pores in a
pore diameter, the scatter is large. This scatter may be due to
the high surface roughness and the presence of different first stage, followed by the formation of a tribolayer.
structures (such as remains of electrolytes) inside the pores. Major cracks were not observed inside or along the edges
At large indentation depth, hardness and elastic modulus of the wear tracks. Cracks which formed during fretting at
exhibit a lower scatter. The hardness varies between 3 and 6 1000 mN don't propagate and are only located at the edges
of the wear track. This effect can be linked to the aluminium
GPa and the elastic modulus between 30 and 65 GPa. The
hardness and Youngs‘ modulus of AAO nanotemplate are in supporting the AAO template and which is a softer material
good agreement with values reported by other researchers than the AAO film. The variation in the coefficient of
[12]. However, the values are significantly lower than the friction with pore size and normal load was not considerably
values found in literature for pure, well crystalline corundum high. The wear mechanism did not change with increasing
or sapphire, which are usually in the range between 20 and applied loads due to a similarity in the tribofilm formed
under meso- and macro-load sliding testing.
25 GPa [13]. This difference is mainly attributed to the
porous structure, which is responsible for the unique Hardness and Young‘s modulus of highly ordered
mechanical response of the membranes. alumina were measured by nanoindentation. The hardness
It is noticed that with increasing pore diameter, the and elastic modulus values depend on the load applied.
Hardness can reach up to 10 GPa at 2 mN on AAO films

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with a 16 nm pore diameter. At increasing loads the [5] M. Kylan McQuaig Jr., Alejandro Toro, William Van
nanopores collapse in ‗shear bands‘, rather than being Geertruyden, Wojciech Z. MisiolekJ, Mater Sci 46,
cracked as observed around the indent, suggesting that the 243–253, 2011
pores in the alumina lead to a higher toughness in the [6] J.P. Tua, C.X. Jiang, S.Y. Guoc, X.B. Zhaoa, M.F. Fu,
transverse direction. Wear 259, 759–764, 2005
[7] G.D. Sulka, S. Stroobants, V. Moschalkov, G. Borghs,
ACKNOWLEDGMENTS and J.-P. Celis, J. Electrochem. Soc., 149 (7), D97-
This research was funded by a FP7 grants: D103, 2002
―NANOALLOY‖ (Marie Curie IIF contract n° 252407), [8] G.D. Sulka, K. G. Parkola, Thin Solid films, 515, 338–
―NANOCOAT‖ (FP7-SME-2010 contract n°262078), and 345, 2006
―TEMADEP‖ (IRSES contract n° 05-104-7540). [9] H. Adelkhani, S. Nasoodi, A.H. Jafari, Int. J.
REFERENCES Electrochem. Sci., 4, 238 – 246, 2009
[1] M. Almasi Kashi, A. Ramazani, M. Raoufi, A. [10] Di Ma, Shuying Li, Chenghao Liang, Corrosion
Karimzadeh, Thin Solid Films 518, 6767-6772, 2010 Science 51, 713-718, 2009
[2] Te-Hua Fang, Tong Hong Wang, Chien-Hung Liu, [11] H. Mohrbacher, J.-P. Celis and J.R. Roos, Tribo. Int., 28
Liang-Wen Ji, Shao-Hui Kang, Nanoscale Res Lett 2, (5), 296-278, 1995
410-415, 2007 [12] Z. Xia, L. Riester, B. W. Sheldon, W. A. Curtin, J.
[3] J.-P. Salvetat, G. Andrew, D. Briggs, J.-M. Bonard, Liang, A. Yin and J. M. Xu, Rev.Adv.Mater.Sci., 6,
R.R. Bacsa, A.J. Kulik, T. Stöckli, N.A. Burnham and 131-139, 2044
L. Forró, Phys. Rev. Lett. 82, 944. 1999 [13] AB Sinani, NK Dynkin, LA Lytvinov, PV Konevsky,
[4] H. Kim, D. Kim, W. Lee, S. Jai Cho, J.-H. Hahn, and EP Andreev, Bull Russ Acad Sci Phys, 73, 1380, 2009
H.-S. Ahn, Surf. Coatings Techn., doi:10.1016/j. [14] S. Ko et al., Thin Solid Films 515, 1932–1937, 2006
surfcoat.2010.07.056, in Press.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Analysis of the Behavior of PVDF Layers

Deposited under Various Conditions
Victor COJOCARU1, Alexei KATASHEV2, Horia-Nicolai TEODORESCU 1, 3
1
‗Gheorghe Asachi‘ Technical University of Iasi, Faculty of Electronics, Communications and I.T., Romania
2
Riga Technical University, Biomedical Engineering and Nanotechnologies Institute, Riga, Latvia
3
Institute of Computer Science of the Romanian Academy, Iasi, Romania
[email protected], [email protected], [email protected]

Abstract–We analyze the surface and piezoelectric properties of PVDF films deposited on the surface of Si
wafer by solution casting under various conditions of temperature and electric field.
Index Terms – PVDF, Kelvin Probe, AFM

B)Probe microscopy
I. INTRODUCTION
In scanning probe microscopy, the surface micro-relief and
In this paper we present a preliminary study of the
its local properties are explored by scanning with a needle-
piezoelectric properties of polyvinylidene fluoride (PVDF)
shaped probe. The tip of the probe has tens nanometers in
film materials grown on Si substrate under various
diameter. The distance between the tip and the scanned area
conditions. Our targets for this research are to test the
is 0.1-10 nm.
possibility to elaborate new ultrasound and piezoelectric
To verify the piezoelectric properties of PVDF material we
sensors, based on PVDF materials.
used a scanning probe microscope Solver P47H-PRO that
In 1969, Kawai, [1] have discovered that, applying a strong
provides spatial resolution of 0.1nm (as evaluated by minimal
electrical field on PVDF, the piezoelectric effect can be
scanning step). In comparison with scanning electron
observed. This was an important step for the development of
microscopy (SEM), atomic force microscope has several
electro-active polymer sensors. PVDF is a ferroelectric
advantages. The electronic microscope (SEM) gives a pseudo
polymer; its dipoles can be „aligned‖ by an external electrical
three-dimensional image for the test area, while AFM give a
field, thus polarization is being kept [2].
really three-dimensional topography.
Such films are intended to be used as pyroelectric and
Furthermore, the non-conducting areas viewed by AFM
electro-acoustic transducers. Piezoelectric films of this
don‘t need to have a conductive metal layer, which often lead
polymer are flexible and have high mechanical strength.
to deformation of the surface. For normal operation in SEM,
Moreover, they have low acoustic impedance that is
it is necessary that the sample is placed in a vacuum, while
comparable with one of the biological tissues, a low acoustic
most microscope AFM modes can be implemented in air or
resistance and a high elastic constant. Besides, sensors made
even in the liquid. One of the drawbacks is that AFM can
of PVDF are good for wet environment [3].
scan a small area of the sample [5].
This research is relevant to the need for new ultrasonic and
pyroelectric sensors for bioengineering applications and other
C)Kelvin probe method (MKS)
domains where small dimensions sensors are need.
The Kelvin probe method is used to visualize distribution
II. METHOD of the electric potential over the surface of specimen. The
A)PVDF film Kelvin probe method works in two steps. In the first step the
PVDF is a polymer with the degree of crystallization being topography is determined. For the second pass, the probe is
around 50%. As other poly-crystals, PVDF polymer is a moved over the sample at certain distance from its surface to
structure with amorphous areas. Addition of copolymer, such determine the surface electrical potential (x) . For this, the
as TrFE, highly increases the degree of crystallinity [7]. console is put into vibrations by applying to the probe a
PVDF film strongly absorbs infrared radiation in the range of voltage V that contains static and dynamic components.
7 - 0.20 microns, corresponding to the wavelength spectrum
Vvar f  Vdc  Vac sin(wt ) (1)
emitted by the human body. PVDF is mechanically strong
and flexible material with a density of approximately 1780
Z Z
kg/m3.
To increase piezoelectric response, PVDF film is stretched ω Vac
in one or both directions, so its size increases several times. ΔZ
Elastic coefficients (such as Young's modulus) are
Vdc
determined by the strain. For example, if the film was
stretched at 140° C to a 4:1 ratio, Young's modulus is 2.1 Z Ф
GPa, and if the ratio is 6.8:1, the modulus is 4.1 GPa [4].
Another way to achieve high polarization is poling in a strong
electric field (over 300 kV/cm), thick films have to be heated Fig.1.Kelvin probe method (MKS)
in this process up to 100oC.
The capacitive force, that forces console to vibrate, is
given [6] by:

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Fcap  (1 / 2) * (Vtip  (x)) 2 * (dC / dz) , (2)

where Cz is the capacitance between the sample and console.
The force

Fcapw  (dC / dz * (Vdc  (x) * Vac ) sin(wt) (3)

which comprises the first harmonic, leads to console
oscillations with the same frequency w [5].
For every surface point, the feedback system change DC
component of the probe voltage (Vdc) until the w component
of console oscillation (and w force component) disappears
and Vdc(x) becomes equal with F(x). Thus the Vdc(x) Fig.4. Surface of the sample, crystallised at the temperature 20 0 C, without
electric field. Scan size 30x30 m, surface topography (left) range 0150
distribution will reflect the surface potential distribution over
nm, surface potential (right) range –50  +180 mV
the sample area.
III. EXPERIMENTS
For our experiments, aimed to obtain cheap and easy-
manufactured ultrasonic sensors, the PVDF – TrFE
copolymer films (molar ratio 70:30) were deposited on the
surface of commercial Si wafer by solution casting. The 1 l
drop of PVDF-TrFE solution in dimethylformamide was
placed over the SI substrate and dried in air either at room
temperature or at 135oC. Some samples were dried in a weak
electric field (600 V/cm).

Fig. 5. Surface of the sample, crystallised in electric field (E = 600 V/cm) at

a temperature of 1350 C. Scan size 30x30 m, surface topography (left)
range 0300 nm, surface potential (right) range –700  - 300 mV

Thus the tip will move with the frequency, equal to one of
the alternating voltage, while the amplitude of movement
PVDF depends on the magnitude of electric field, piezoelectric
sample properties of the material and mutual orientation of the
electric field and polarization vector of the measured object
Fig.2. PVDF sample.
[6]. The images of piezoelectric response (figs. 6, 7) are
obtained by depicting the amplitude of the tip oscillations in
arbitrary units.

Fig.3. Surface of the sample, crystallised in electric field (E = 600 V/cm,) at

the temperature 200 C, Scan size 30x30 m, surface topography (left) range
0250nm, surface potential (right) range –60  +90 mV

The topography of the obtained films as well as

distribution of the surface potential can be seen at Fig. 3-5.
We used the method of piezoelectric response force
microscopy to evaluate piezoelectric response of the film. It
is widely applied to study ferroelectric materials and allows
exploration of its domain structure. The method is based on
Fig.6. Piezoelectric response (relative units) of the sample, crystallised in
the evaluation of the impact of the local electric field under electric field (E = 600 V/cm) at a temperature of 135 0 C (left), profile of the
the tip. sample (right).
The tip is brought in contact with the specimen surface
and alternating voltage is applied to the tip. The voltage Fig. 6 demonstrates piezoelectric response of the obtained
produces local electric field under the tip, which in turn PVDF film. Non-uniformity of image implies different
cause piezoelectric specimen to shrink and expand piezoelectric properties of small (0.1-0.5 m) film areas that,
periodically hereby moving the tip itself. probably, may be interpreted as PVDF domains. The
different response over the film may be explained by
different orientation of the domains. To validate this

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supposition, additional DC electric potential was applied AUTHORS‘ CONTRIBUTIONS

between the tip and sample. Figure 7 demonstrates The first author (VC) conducted experiments, collected the
increment in magnitude of piezoelectric response due to data under the supervision of the second author and wrote a
introduction of both negative and positive voltage. From major part of the paper. The second author (AK) conducted
this, one may suggest, for instance, that PVDF domains are some AFM experiments, provided the whole guidance and
initially poorly oriented. Application of electric field causes planning for the experiments, interpreted results and
them to become more aligned more, thus the specimen under contributed writing the paper. The third author originated the
the tip becomes more polarized and its piezo-response idea of the study, helped interpreting some of the results and
increases. contributed to writing the paper.

REFERENCES
[1] J. Tribol, Effects of Applied Potential on Friction of a
Piezoelectric Material, Oct. 2007, Vol. 129, Issue 4, 836
Ubias = - 9V (5 pages)
[2] Ye.Bormashenko, R. Pogreb, O. Stanevsky, and Ed.
Bormashenko, Vibrational spectrum of PVDF and its
interpretation, Polymer Testing, Vol. 23, Issue 7,
October 2004, pp. 791-796
Ubias = + 9V [3] A. Batagiannis, M. Wübbenhorst, J. Hulliger, ―Piezo-
and pyroelectric microscopy‖, Current Opinion in Solid
State and Materials Science, Vol. 14, Issue 5, October
2010, pp 107-115
[4] D. Saikia, and A. Kumar, ―Ionic conduction in P(VDF-
HFP) / PVDF–(PC+DEC)–LiClO4 polymer gel
Fig.7. Change of the piezoelectric response of PVDF film (relative units)
electrolytes‖, Electrochimica Acta, Vol. 49, Issue 16, 15
due to bias voltage applied to the probe (areas indicated with arrows) July 2004, pp. 2581-2589
[5] A.V. Shirinov, and W.K. Schomburg, ―Pressure sensor
IV. CONCLUSIONS from a PVDF film‖, Sensors and Actuators A: Physical,
The experimental analysis demonstrated that the Vol. 142, Issue 1, 10 March 2008, pp. 48-55
piezoelectric properties of PVDF films, grown on Si substrate [6] http://www.ntmdt.ru/spm-principles/view/kelvin-probe-
by solution casting depend strongly on the film growth microscopy, accessed 02.2011
conditions. Under proper growth conditions, the ferroelectric [7] Q. M. Zhang, V. Bharti, G. Kavarnos, M. Schwartz.
properties may be suitable for the use in micro-sensors. (Ed.), "Poly (Vinylidene Fluoride) (PVDF) and its
V. ACKNOWLEDGMENT Copolymers", Encyclopedia of Smart Materials,
The first author thanks for being granted with a BRAIN Volumes 1-2, John Wiley & Sons, 2002. 807-825.
scholarship that contributed to financing some of these
studies and to Riga Technical University, Biomedical
Engineering and Nanotechnologies Institute, for allowing him
to follow a doctoral study stage at this university.

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Exciton Luminescence in In0.3Ga0.7As/GaAs

Quantum Well Heterostructures
Eli KAPON1, Alexandru MEREUŢA1, Andrei DOROGAN2, Nicolae DRAGUTAN2,Tatiana VIERU2,
Nicolae SYRBU2
1
Swiss Federal Institute of Technology in Lausanne, Lausanne, Switzerland
2
Technical University of Moldova, Kishinev, Moldova
[email protected]

Abstract – Radiation maxima were observed in photoluminescence spectra of GaAs/ In 0.3 Ga0.7As/ GaAs in
case of 632.8nm and 532nm He-Ne laser excitation conditioned by the recombination from ground (e1-hh1,
e1-lh1) and excited (e2-hh2, e2-lh2) states of polarionic excitons in quantum wells. The doublet character of
e1-hh1, e1-lh1 transitions can be explained by the interaction of excitons in quantum wells. Radiation maxima
are revealed in the region of 1.5eV energy conditioned by recombination transitions E b-hh1, Eb-lh1of the
GaAs buffer layer.
Index Terms – quantum wells, heterostructure, exciton, luminescence.

I. INTRODUCTION
In quantum wells intersubband and intrasubband optical
transitions are possible, as well as processes of quantum
wells "photoionization", accompanied by a transition from
size-quantized discrete states in overbarrier states of the
continuous spectrum.
II. EXPERIMENTAL METHOD
The luminescence spectra were measured at 10 and 300K
temperature with excitation lines of 632.8nm He-Ne and
532nm laser at high-aperture (1:2) МДР-2 and double
diffraction spectrometer СДЛ-1.
III. EXPERIMENTAL DATA AND DISCUSSIONS
The transitions between different subbands of size
quantization of the V-zone into C-zone, caused by light with
ёω>Eg, can generate a whole family of electronic transitions a)
and hence the bands of interband absorption and
luminescence [1 – 3]. Figure 1 shows the luminescence
spectra of In0,3Ga0,7As/GaAs structure excited with a He-Ne
laser line 632.8nm. At room temperature and low level of
excitation the luminescence is practically absent. The
luminescence is detected at 200K temperature and with
further temperature decreasing the luminescence intensity
increases. The emission maximum 1.163eV (200K) while
the temperature is shifted to the energy of 1.2032eV (30K),
has a FWHM equal to 10meV and is conditioned by the
transitions e1-hh1 (e1-lh1) from the quantum well layers A
and B of In0.3Ga0.7As/GaAs structure. In the high-energy
region of In0.3Ga0.7As/GaAs structures with quantum wells it
is observed an emission band at 1.342eV (300K), which is
shifted to higher energies with temperature decreasing (fig.
2). At 30K temperature it was revealed a narrow peak at
1.4131eV due to radiative recombination of electrons with
heavy holes Eb-hh1 and the maximum Ех1 at 1.5433 eV, b)
which, we believe, is due to radiative recombination from a Fig.1 a) - The luminescence spectra of In0.3Ga0.7As/GaAs structure with
discrete level of Ex1 excitons located in the continuum region quantum wells at different temperatures (30-200K) and 632.8 nm He-Ne
laser excitation line; b) - Temperature dependence of the energy maxima of
at the level of heavy and light holes.In order to increase the radiation for In0.3Ga0.7As/GaAs structure with quantum wells excited with
intensity the light was focused on the surface area. Radiation 632.8nm He-Ne laser line.
maxima at 1.2071 eV and 1.2201 eV, which are due to
exciton recombination in quantum wells from the e1-hh1 and e1-lh1 states are detected at high
intensities and 10K temperature in the long wave region. In
this case, the splitting of the heavy (hh1) and light (lh1)

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holes in the quantum well is equal to 13.0 meV and the value EP and ES polarization there are detected, as low-energy
of FWHM is 5 meV. (1.2003eV) as high-energy (1.2138eV) peaks.

Fig.2 The luminescence spectra of In0.3Ga0.7As/GaAs structure with

quantum wells at 10K excited with a 632.8 nm He-Ne laser line (curve b is
shown not to scale).

Radiation maxima at the energies 1.2750, 1.3336 and Fig.3 Temperature dependence of the levels of exciton polaritons in a
1.3798 eV, which are due to transitions e1-hh1, e2-hh2 and quantum well
e3-lh2, respectively, are also found at 10K temperature.
Intense emission lines at 1.5030eV energies and a weak
shoulder at 1.4899eV energy and an intense maximum at
1.5433eV are found at these temperatures in a higher-energy
region. The first two peaks are conditioned by bulk excitons
in GaAs buffer layer, i.e. Eb-hh1 and Eb-lh1 transitions. In
the related articles [1-3] the luminescence energy of the
exciton transitions from the GaAs buffer layer at 8K
temperature is detected at the energy 1.500-1.505 eV, which
agrees with our determined value of 1.5030eV. The zones‘
splitting value of the heavy and light holes defined by the
location of high-energy transitions is 13.1eV, which,
practically, agrees with the splitting value (13.0 meV)
determined from the maxima conditioned by the e1-hh1 and
e1-lh1 transitions. The most short-wave radiation maximum
at 1.5433eV we believe is due to recombination transitions
from discrete energy states of the quantum well located in
the Ek1 continuum to the heavy holes zone hh1.
Fig.4 Luminescence spectra of In0.3Ga0.7As/GaAs structure with quantum
Temperature dependences of the detected transitions e1- wells at 10K and excitation with 532 nm laser line, Un-Ep curve corresponds
hh1 (e1-lh1) and Ek1-hh1, Ek1-lh1 are presented in figure 3. to the excitation of unpolarized light and radiation in the P-polarization;
Transition energies are shifted to higher energy almost curve Un-ES is unpolarized radiation excitation in the S-polarization; Ep-ES
corresponds to the excitation of P-polarized radiation in the S-polarization; f
linearly with temperature decreasing in the range 100-200K. - the curve measured in unpolarized light and with the intensity increased up
The transitions energy e1-hh1 (e1-lh1) and Eb1-hh1 (lh1) to 10 times.
vary linearly in the temperature range 100-10K, and the
transitions energy Ex1-hh1 (lh1) remains linear. The different When excited with EP polarized light and a recorded
temperature coefficient of the transitions‘ shift is linked with luminescence at ES and EP there can be found also high-
the difference of the coefficients of linear displacement of energy radiation maximum, but the emission intensity
the heavy and light hole‘s zones, effective mass of heavy decreases because of reducing the intensity of the exciting
and light hole levels and exciton polariton levels in quantum light. In the study of photoluminescence spectra of localized
wells [1 - 3]. excitons in GaAs/AlGaAs (001) quantum wells in the optical
near-field regime it was observed the exchange splitting of
Peaks at 1.2003 and 1.2138 eV are detected in the
the doublet el-hh1 (Is) into two components polarized along
luminescence spectra at 10K and 532nm laser line excitation
the [100] and [110], i.e. the phase of these waves varies by ±
in unpolarized light, which are due to the transitions e1-hh1
90 °. The emission maxima e1-hh1 and e1-lh1 (fig. 4) have a
and e1-lh1 (fig. 4). It is evident that the luminescence
doublet character in the luminescence spectra considered by
maxima at 1.2003 and 1.2138 eV have the doublet character
us at 10K temperature. The luminescence maximum (1.2133
with a splitting of a several meV order In the luminescence
eV) is observed at lower energies in the ES polarization than
spectra excited by unpolarized light and recorded in case of
in the EP polarization (1,2166 eV).

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IV. CONCLUSIONS REFERENCES

Photoluminescence spectra of GaAs/In0.3Ga0.7As/GaAs [1] N. N. Ledentsov, M. Grundmann, N. Kirstaedter, O.
nanostructures are formed by the recombination of exciton Schmidt, R. Heitz, J. Bohrer, D. Bimberg, V. M.
polaritons in quantum wells from the main (e1-hh1, e1-lh1) Ustinov, V. A. Shchukin, P. S. Kopiev, Zh. I. Alferov,
and excited (e2-hh2, e2-lh2) states. S. S. Ruvimov, A. O. Kosogov, P. Werner, U. Richter,
Recombination transitions Eb-hh1, Eb-lh1 of the GaAs U. Gosele, J. Heydenreich. Sol. St. Electron., 40, 785
buffer layer and the transitions from the quantum level (1996).
located in the continuum of barrier layer E k1-hh1 contribute [2] E. L. Ivchenko. Optical spectroscopy of semiconductor
to the luminescence from the short-wave part of the nanostructures (Alpha Science International, Harrow,
spectrum. The doublet nature of the transitions e1-hh1, e1- UK, 2005).
lh1 is explained by the exchange interaction of excitons in [3] Mark Fox, Optical Properties of Solids, Oxford
quantum wells. University Press, 2001.

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Effect of Harmful Gases on the A.C.

Conductivity of Tellurium Thin Films
D.TSIULYANU, O.MOCREAC

Technical University, Department of Physics

[email protected], [email protected]
Abstract – Impedance spectra of tellurium films with interdigital platinum electrodes have been investigated
in NO2 and H2S gaseous media at room temperature. Analyses of Nyquist complex diagrams allowed
evaluating the characteristic frequency, time constant, resistance and capacity of the film in different target
gases. It is shown that the spectra of both real and imaginary parts of impedance are strongly influenced by
gaseous environment. The
gas sensitivity for impedance or its imaginary part depends on frequency, being ~50 % / ppm for nitrogen
dioxide and ~ 8 % / ppm for hydrogen sulfide respectively.
It is suggested that effect of NO2 and H 2 S results respectively from "strong" and "weak" chemisorptions
of these molecules on the surface and intra grain regions.

Keywords–- Impedance, A.C.; Tellurium, NO2 , H 2 S

I. INTRODUCTION tantalum boat onto ceramic substrates with a priory

Tellurium evaporated thin films show p- type deposited platinum interdigital electrodes (Fig. 1a). The
conductivity, which depends [1-3] on thickness, rate of electrode structure was structured at SIEMENS AG with
deposition and annealing process. Interesting electrode width of 15m and interelectrode distances of
semiconducting properties of Te films have stimulated their 45m . The evaporation of tellurium was performed at the
wide investigation and propositions for applications as thin
working pressure of 10 4 Pa . The growing velocity of the
films infrared detectors [4], strain - sensitive [5] and writing
memory [6] devices. film was in the order of 10 nm / s and the area of deposition
2
Recently, tellurium thin films have been found to be around 10 mm .
sensitive to toxic and harmful gases [7-9], which allowed The surface morphology of the films was controlled with
proposing them for the development of gas sensors [10]. a SEM TELSA BS 340 and was pointed out to be the same
Different gases may be easily detected at room temperature as in previous paper [3]. The film was encapsulated in a
using these films. Although the cross sensitivity to standard TO – 8 sockets and then the contacts were
mentioned gases is essential different, the distinguishing thermally bounded to socket pins, using the copper wires.
between them becomes important. The sockets with thin film sensing devices were put into
One of possibilities to obtain a selective detection of gases a test cell (of 10ml volume) in which the gases were injected
has been mentioned by Sbeveglieri [11] and consists in a fast
with a flow rate of 100ml / min , parallel to the film surface.
sweeping of sensitivity of a single sensor at different
Different gaseous media were obtained by using the
frequencies. The sensitivity of sensor to different gases at
different frequencies can be rather different. That is, by experimental set up described in [14]. NO2 and
monitoring a.c. conductance at specific frequencies, the H 2 S vapors with concentrations of 15 ppm and 50 ppm
sensitivity to different gas components can be enhanced
respectively were obtained by using calibrated permeation
[12]. Moreover, a.c. measurements allow obtaining
tubes (Vici Metronics, USA), which were incorporated
impedance or admittance spectra of a sensor, to calculate
subsequent into the experimental set – up. Dry synthetic air
equivalent circuit and to distinguish between contributions
was used as the carrier and reference gas.
from the surface, bulk or contacts to film conductivity [13].
A.c. measurements were carried out in frequency range of
In the present paper the a.c. conductivity of
5Hz to 13MHz using a HP4192A impedance analyzer.
microcrystalline tellurium thin films with platinum
interdigital electrodes have been investigated in dry
synthetic air, nitrogen dioxide and hydrogen sulfide gaseous III. RESULTS AND DISCUSSION
media at room temperature. An analysis of impedance
spectra in a complex interpretation has allowed to represent 3.1 Impedance behavior under dry air
the equivalent circuit, as well as to point out the effect of Before checking the effect of different harmful gases on
harmful gases on frequency dependences of real and a.c. conductivity the tellurium films were aged by 12 months
imaginary parts of impedance of the films. in normal conditions and the measurements have been
II. EXPERIMENTAL performed under synthetic dry air. Figure 1b shows the
Tellurium thin films of  100nm thickness, were prepared typical complex impedance diagram in Nyquist plot obtained
in pure synthetic dry air from a thin film device at room
by thermal vacuum evaporation of pure tellurium from
( 22  C ) temperature.

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R
Re( Z )  (2)
1   2 R2 C2
and
  C R
Im(Z )  (3)
1   2 R2 C2
From these system of equations the values of R and
C of the film can be evaluated as:
Im 2 ( Z )  Re 2 ( Z )
R  (4)
Re( Z )
and
Im(Z )
C 

 Im ( Z )  Re 2 ( Z )
2
 (5)

From equations (4) and (5) the resistance Rm , capacitance

Fig.1. a) Interdigital electrode structure used to measure the a.c.
conductivity; C m and time constant  m  (2f m ) 1 of the film can be

b) Nyquist diagram of an aged at 22 C tellurium thin film in pure estimated at characteristic frequency f m ,wich is the
synthetic dry air;
c) Suggested equivalent circuit. frequency at which the imaginary part - I m (Z ) reaches its
maximum value:
The diagram shows a slightly depressed semi – circular 1
arc with a center displaced below the real axis, owing to  m   m1   Rm C m (6)
presence of distributed elements in tellurium-based device 2f m
[13]. These elements can be related to grain boundary Because of heterogeneity of the material-electrode system
heterogeneity of polycrystalline material [15], more exactly the relaxation time (time constant)  m , estimated from the
to grain boundary and intra – grained regions [3, 9]. A
complex impedance represents a mean value for the
simplified equivalent circuit inserted in Fig. 1 (c) can complete thin film device.
interpret the Nyquist plot. The frequency independent serial
The characteristic frequency ( f m ), impedance ( Z ) and
resistance R0 is assigned to a sum of Ohmic resistance due
to electric connection, but resistance R and capacity C estimated from equation (6) the time constant (  m ) of the
are distributed to others contributors, the grain boundary sample in dry synthetic air, are listed in table 1.
resistance and capacity being the main.
3.2 Impedance behavior in gaseous media of NO2 and H 2 S .
The circle of Nyquist – diagram shown in fig. 1b is
depressed owing to the dependence of both C and R on Fig. 2 reports the spectra of the real part of impedance of
tellurium films upon exposure to different test gases.
frequency. From the left and right intercepts of semi – circle
with the Re(Z ) axis the values of R0 and Rr  R  R0 can TABLE1. CHARACTERISTIC FREQUENCY, IMPEDANCE AND R-C
VALUES AT DIFFERENT ENVIRONMENTS
be estimated. Thus, R0 was found to be very small, only
Envir fm Z m Rm Cm
about 5 Ohm. That is the arc practically passes through the onme
kHz kOhm 10 7 s kOhm pF
origin and the right intercept gives the value of nt
Rr  20kOhm .
Dry 900 13,3 1,8 19,2 9,6
For a parallel R C circuit the impedance is given air
as: 1,5 1500 7,5 1,1 11,8 9,3
1 1 R ppm
Z ( )     NO2
Y ( ) 1 1  i    C  R
 i    C 50pp 400 29 4 44,5 9
R (1)
m
R (1  i    C  R )
 H 2S
1  (  C  R ) 2
It is seen that addition of 1,5 ppm of NO2 to dry
synthetic air diminishes the real part of impedance by ~ 10
where Y ( ) is the admittance, i   1 is the
kOhm in the frequency range 1,0 - 103 kHz. On the contrary,
imaginary number ,   2f , f -the frequency.
the addition of 50 ppm of H 2 S to dry synthetic air
enhances the real part of impedance by ~30 kOhm in the
Thus, the real and imaginary parts of the impedance are:
much shorter frequency range: 1,0 – 100 kHz. This behavior
is compatible with spectra of imaginary part of impedance
(Fig. 3). They exhibit the maximums strongly influenced by

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harmful gases species. The NO2 vapors diminish the peak 3.2.1 Nitrogen dioxide
D. c. resistance of tellurium films is known to decrease
of imaginary part of impedance shifting it to higher
reversibly in presence of NO2 due to interaction of adsorbed
frequencies but the addition of H 2 S vapors results in a
species with lone – pair electrons, which from the upper part
vice-versa behavior. Analysis of these spectra allowed
of the valence band [14]. Apparently by changing from d.c.
determining the influence of tested harmful gases on all
to a.c. technique the mechanism of interaction can not be
elements of the equivalent circuit of the sample.
modified but the sensitivity (or selectivity) can be increased.
Fig. 4 shows the sensor sensitivity as a function of the
50
measurement frequency during the exposure to 1,5 ppm
40 NO2 . The sensitivity (here and further) is defined as
dry air absolute variation of measured value (impedance or
Re (Z), kOhm

30 1,5 ppm NO2

imaginary part of impedance) for a selected frequency in
50 ppm H2S

20
mixture of carrier gas with NO2 divided by the measured
value in the carrier gas at the same frequency, in percents per
10 ppm.
The response curves for either impedance or imaginary
0 part are nearly independent on frequency until
approximately 300 kHz, then go down, but sensitivity to
0 1 2 3 4
NO2 is maintained until 10 MHz.
lg f,( kHz )

Fig. 2. Effect of target gas on the real part of impedance. 60

Sensitivity , [ % / ppm ]
The values of characteristic frequency, impedance 50

and time constant  m of the film at this frequency, by 40 NO2

indicated concentrations of NO2 and H 2 S at room 30
temperature, are summarized in table 1.
20
Im (Z)
IZI
10
20
dry air 0
16 1,5 ppm NO2
- Im (Z), kOhm

50 ppm H2S 0 1 2 3 4
12 lg f, ( kHz )
8
Fig.4. Sensitivity to NO2 for impedance and its imaginary part as a
4
function of frequency.
0 The sensitivity in d.c. and impedance measurements
amounts to approximately 30 % /ppm, but evaluating the
0 1 2 3 4
imaginary part as the sensor response results in an increasing
lg f, ( kHz )
of sensitivity until ~50 % /ppm. The high sensitivity, as well
Fig. 3. Spectra of imaginary part of impedance upon exposure to
as the large frequency range of response to NO2 supports the
different test gases. early-proposed mechanism of nitrogen dioxide interaction
with chalcogenides [14], which involves strong
Listed in this table values of Rm and C m (thé résistance
chemisorption due to interaction between odd electrons of
and capacitance at characteristic frequency) have been
NO2 molecules and lone – pair electrons of tellurium based
obtained from Eq. (4) and (5) applied to the data of Fig.2 and
Fig.3. chalcogenides.
From this table, it is seen that as the environment is 3.2.2. Hydrogen sulfide
changed from dry air to its mixture with gases in question, As sensing of hydrogen sulfide by tellurium films has
the resistance Rm is mainly influenced and capacitance C m been investigated early [9], here we show only some
does not very essentially. And what is more, the addition of peculiarities related to sensitivity of such films to H 2 S at
a.c. measurements, as well as make some comments related
NO2 decreases both impedance and Rm (at characteristic
to mechanism of interaction between this gas and
frequency, which also is gas influenced) but addition of chalcogenide tellurium thin film.
H 2 S increases these parameters. In this context it becomes As have been pointed out (Fig. 2 and 3) hydrogen sulfide
interesting to analyze the frequency dependences of leads to increasing of both real and imaginary parts of
sensitivity to different target gases. impedance of the film. Fig. 5 shows the results from a.c.
impedance measurements, in which the sensor sensitivity for

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impedance and its imaginary part are, plotted as a function

of the measured frequency during exposure to 50 ppm which involves strong or "weak" forms of chemisorbtion
H 2 S . First it is observed that sensitivity of tellurium films respectively.

to H 2 S is by ten times smaller then sensitivity to NO2 . ACKNOWLEDGEMENT

Authors express their gratitude to colleagues from
Further, the sensor sensitivity evaluated from imaginary part
Institute of Physics, Munich University of Armed Forces
exhibits a maximum at frequency of around 100 kHz.
for interests and help in carrying out this work.
Evaluation of sensor response by this maximum results in an
evident increase of sensitivity. Being of about 8 % / ppm it is
REFERENCES
four times higher than the sensitivity evaluated either from
impedance or d.c. measurements.
[1] M. A. Dinno , M. Schwartz, Structural dependence of
Taking into consideration that the electron configurations
electrical conductivity of thin tellurium films, J. Appl.
of water and hydrogen sulfide are similar the interaction of
Phys, 45, 1974, pp. 3328 – 3331.
tellurium film with H 2 S is likely, to take place similar as [2] B. Chakrabarti, A.K.Pal, Electrical and
proposed early [14] mechanism of interaction of water vapor Galvanomagnetic properties of Te films, Jap. J. Appl.
with these films. Phys, vol. 19, no. 4, 1980, pp. 591 – 596.
[3] D. Tsiulyanu, S. Marian, H - D. Liess, I. Eisele,Effect of
annealing and temperature on the NO2 sensing
8 properties of tellurium based films, Sens. Actuators B
100, 2004, pp. 380-386.
Snsitivity ,[ % / ppm ]

6 [4] N.G. Shyampasad, C.H. Champness, I. Shih, Thickness

Im (Z)
dependence of photoconductivity in tellurium, Infrared
H2S IZI Phys. vol. 21, 1981, pp.45 -52 .
4
[5] M. Granveaud, Y. Petroff, On the electroresistаnce
effect in evaporated tellurium films, Phys. Stat.
2 Sol. (a), vol. 3, 1970, pp. 629 – 638.
[6] A. Milch, P. Tasaico, The stability of tellurium films
0 in moist air, Journ. Electrochemical Soc., vol.127,
no. 4,1980,pp. 884 – 891.
0 1 2 3 4 ―Electrochemical Soc‖, 127 pp. 884, 1980
lg f, ( kHz ) [7] D. Tsiulyanu, S. Marian, V. Miron, H - D. Liess, High
sensitive tellurium based NO2 gas sensor ,Sens.
Fig.5. Sensitivity to H 2 S for impedance and its imaginary part versus Actuators B 73, 2001 pp.35 - 39.
frequency. [8] D. Tsiulyanu, S. Marian, H - D. Liess, Sensing
properties of tellurium based thin films to propylamine
That is, as the molecule of H 2 S approaches the surface of and carbon oxide, Sens. Actuators, B 85, 2002,pp.232-
positive charged tellurium film, it rotates and orientates its 238.
dipole moment perpendicular to this surface with negative [9] S. Sen, V. Bhandarkar, K.P. Muthe, J. M. Roy, S.K.
pole inward. Simultaneously the free hole becomes more and Deshpande, R.C. Aiyer, S.K.Gupta, J. V. Yakmi, V. C.
Sahni, Highly sensitive hydrogen sulphide sensors
more localized at the point of the surface that H 2 S operable at room temperature, Sens. Actuators B 115
molecule approaches and a very week bond due to forces of ,2006, pp 270-275.
electrostatic polarization is formed. And what is more, the [10] D. Tsiulyanu, Chalcogenide Semiconductor Based Gas
orientation polarization of same H 2 S molecules on the Sensors, in Encyclopedia of Sensors edited by C.
surface is accompanied by their stretching along the dipole, Grimes, E.C. Dickey and M. Pishko, American
which can result in a "weak" form of chemisorbtion. Scientific Publishers, vol. 2, 2006, pp.113 -123.
[11] G. Sberveglieri, Recent developments in
IV. CONCLUSIONS semiconducting thin films gas sensors, Sens. Actuators,
A.c. conductivity of tellurium thin films is strongly B 23, 1995, pp. 103 -109.
influenced by composition of gaseous environment. The [12] U. Weimar, W. Gopel, AC measurements of thin oxide
effect of harmful gases is mainly due to variation of both sensors to improve selectivities and sensitivities‖, Sens.
real and imaginary parts of film‘s impedance. Addition of Actuators, B 26 / 27, 1995, pp.13-18.
NO2 decreases, whereas addition of H 2 S increases them [13] J.R. Macdonald, Impedance spectroscopy, Wiley, New
York, 1987.
in a large range of frequencies.
The sensitivity for either impedance or its imaginary part [14] D.Tsiulyanu, I.Stratan, A. Tsiulyanu, H.-D. Liess , I.
Eisele, Investigation of the oxygen, nitrogen and water
strongly depend on harmful gas species ( NO2 or H 2 S ) vapour cross - sensitivity to NO2 of tellurium based thin
and applied frequency, because of different mechanisms of films, Sens. Actuators B 121, 2007 pp. 406 –413.
interaction between these gases with tellurium based films, [15] C.J.F. Bottcher, S. Havrilak, S.Negami, Theory of
electronic Polarization, Elsevier, Amsterdam, 1982.

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Optical Properties of Phase Change Memory

Ge1Sb2Te4 Glasses
M.S.IOVU, E.P.COLOMEICO, V.G.BENEA, A.M.ANDRIESH
Institute of Applied Physics, ASM, Str. Academiei 5, MD-2028 Chisinau, R. Moldova
[email protected]

Abstract – Phase change memory materials are promising for the next-generation of non-volatile
flash memory that will serve in new mobile computing, entertainment and other handheld
electronics. Among them are chalcogenide glasses Ge-Sb-Te (GST) which can exist in two separates
structural states – amorphous and cristalline. Switching of the material from one to another state
can be done by heating applying an electrical pulse or by exposure to intense laser beam. We report
the changes of optical parameters of amorphous Ge1Sb2Te4 films under heat treatment and light
exposure.

Index Terms – Phase change memory materials, optical properties, refractive index

powered. Examples of non-volatile memory include

I. INTRODUCTION
read-only memory (ROM), flash memory, most types of
The discovery of chalcogenide glasses in 1955 year as
magnetic computer storage devices (e.g. hard disks,
non-crystalline semiconductors and the first systematical
floppy disks), and optical disks. ROM is memory that
investigation of this class of materials belong to Prof.
users cannot write to – traditionally it has been used to
N.A.Goriunova and B.T.Kololmiets [1,2]. The new class of
store BIOS code in computers.
non-crystalline semiconductors is the chalcogenide glasses
III. Phase Change Random Access Memory (PRAM) is
containing elements of the VI group such as S, Se, Te. The
also a type of non-volatile computer memory which
typical representatives of chalcogenide glasses are the
uses the unique behavior of chalcogenide glass - the
arsenic sulfide (As2S3) and arsenic selenide (As2Se3). The
"switching" between two states, crystalline and
chalcogenide glasses exhibit excellent electrical properties
amorphous with the application of heat. PRAM is one of
and are suitable optical materials for IR region [3]. In 1968
a number of new memory technologies that are
S.R.Ovshinsky discovered the electrical switching and
attempting to compete in the non-volatile role with the
memory (OVONIC) effects in amorphous semiconductors
almost universal Flash memory. PRAM is viewed as a
[4]. These effects stays on the bases to use the amorphous
next-generation version of non-volatile flash memory
materials as new phase change materials for optical storage
that will serve in new mobile computing, entertainment
media such as CD and DVD recordable and rewritable discs.
and other handheld electronics.
The concept of phase change memories consists in the use of
such semiconductor materials which can exist in two
Some historical aspects of development of Phase Change
separate structural stable states (for example, amorphous and
Memory Technology: [7]
crystalline). Switching of the material from one to another
state can be done by applying an electrical pulse or by
exposure to intense laser beam. Using of semiconductor  September 1966: Stanford Ovshinsky files first
materials with the same composition in amorphous and patent on phase change technology;
crystalline phases provides long life, and as such materials  January 1969: Charles H. Sie published a
were chosen the ternary alloys of the Ge-Sb-Te (GST with dissertation at Iowa State University on
the ratio 2:2:5) system and other more complicated chalcogenide phase change memory device;
chalcogenide glass [5]. Now we briefly will listed the two  June 1969: US Patent 3,448,302 licensed to
modern electronic devices: random access memory (RAM) Ovshinsky claims first reliable operation of phase
and read only memory (ROM), because they provide high- change memory;
speed storage [6].  September 1970: Gordon Moore publishes
I. Random Access Memory (RAM). RAM is used in the research in Electronics Magazine;
computer systems for main memory or primary storage.  June 1999: Ovonyx joint venture is formed to
RAM can be divided in volatile and non-volatile type of commercialize PRAM technology;
memories. Volatile memory (temporary memory), also  November 1999: Lockheed Martin works with
known as volatile storage, is computer memory that Ovonyx on PRAM for space applications;
requires power to maintain the stored information. Most  February 2000: Intel invests in Ovonyx, licenses
forms of modern RAM are volatile storage, including technology;
dynamic random access memory (DRAM) and static  December 2000: ST Microelectronics licenses
random access memory (SRAM). PRAM technology from Ovonyx;
II. Non-volatile memory (NVM) is computer memory that  March 2002: Macronix files a patent application
can retain the stored information even when not for transistor-less PRAM;

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

 July 2003: Samsung begins work on PRAM change properties are studied faceted. Special interests
technology; represent the phase change chalcogenides from the cut-of
 2003 through 2005: PRAM-related patent Sb2Te3-GeTe (Fig.1a [8]). The investigated glass
applications filed by Toshiba, Hitachi, Macronix, composition in the present work Ge 1Sb2Te4 is one of the
Renesas, Elpida, Sony, Matsushita, Mitsubishi, most stable materials for switching and memory
Infineon and more; applications.
 August 2004: Nanochip licenses PRAM II. EXPERIMENTAL RESULTS AND DISCUSSION
technology from Ovonyx for use in MEMS probe The chalcogenide Ge1Sb2Te4 phase change material was
storage; synthesized from high purity initial components Ge, Sb, Te
 August 2004: Samsung announces successful 64 (99.999 %) by conventional melt quenching method. The
Mbit PRAM array; mixture of high-purity precursors was melted in sealed
 February 2005: Elpida licenses PRAM technology evacuated quartz ampoules (p=510-6 Torr) placed in a
from Ovonyx; rocking furnace. The total weight of the synthesized sample
 September 2005: Samsung announces successful was 10 grams. The temperature of the quartz ampoule was
256 Mbit PRAM array, touts 400 µA programming slowly increased to 550 oC at the rate of 50 oC/hour and kept
current; at this temperature during 24 hours for homogenization.
 October 2005: Intel increases investment in Than the temperature was increased up to 980 oC at the rate
Ovonyx; 50 oC/hour and homogenized at this temperature during 72
 December 2005; Hitachi and Renesas announce 1.5 hours, and then quenched in the regime of the disconnected
V PRAM with 100 µA programming current; furnace. Fig.2 shows the fragment of the crystal structure of
 December 2005: Samsung licenses PRAM the Ge1Sb2Te4 [9]. Thin film samples of thickness d~12 μm
technology from Ovonyx; were prepared by flash thermal evaporation in vacuum of the
 July 2006: BAE Systems begins selling the first synthesized initial glasses onto glass substrates.
commercial PRAM, a Radiation Hardened C-RAM
512Kx8 chip;
 September 2006: Samsung announces 512 Mbit
PRAM device;
 October 2006: Intel and STMicroelectronics show
a 128 Mbit PRAM chip;
 December 2006: IBM Research Labs demonstrate
a prototype 3 by 20 nanometers;
 January 2007: Qimonda licenses PRAM
technology from Ovonyx;
 April 2007: Intel's chief technology officer Justin
Rattner is set to give the first public demonstration
of the company's PRAM (phase-change RAM)
technology;
 October 2007: Hynix begins pursuing PRAM by Fig.1. Ternary diagram of the Ge-Sb-Te with phase change materials [8].
licensing Ovonyx technology;
 February 2008: Intel and STMicroelectronics For optical transmission spectra measurements a UV/VIS
announce four-state MLC PRAM and begin (=300’800 nm) and 61 NIR (=800’3500 nm) Specord‘s
shipping samples to customers; CARLZEISS Jena production were used. For calculation of
 December 2008: Numonyx announces mass the optical constants from the transmission spectra, the
production 128 Mbit PCM device to selected computer program PARAV-V1.0 (www.chalcogenide.eu.org)
customer; was used [10].
 June 2009: Samsung's phase change RAM will go
into mass production starting in June;
 September 2009: Samsung announces mass
production start of 512 Mbit PRAM device;
 October 2009: Intel and Numonyx announce they
have found a way to stack phase change memory
arrays on one die;
 December 2009: Numonyx announces 1 Gb 45 nm
product;
 April 2010: Numonyx releases Omneo PCM Series
(P8P and P5Q), both in 90 nm;
Fig.2. Crystal structure of metastable Ge1Sb2Te4 [9].
 April 2010: Samsung releases 512 Mbit PCM with
65 nm process, in Multi-Chip-Package. Fig.3 shows the transmission spectra of as-deposited
amorphous Ge1Sb2Te4 thin films (1) and annealed at T=150
o
During this period and at the present in many research C during 2 minutes. After annealing at high temperature
centers in the world, the chalcogenide glasses with phase T=150 oC, due to the crystallization process of the

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

amorphous film the transmission decrease, and the Urbach

Absorption coefficient (x10 cm )

tail is shifted in the long wave region of spectrum. The

-1
illumination with white during 1 hour does not change the 35

3
transmission spectra of the as-deposited amorphous film. 200
30
The spot of phase change transformation of the amorphous

(h  cm-1/2 eV1/2)

25 150
material was observed when the film was illuminated with
UV laser pulses. According to [9], the samples Ge1Sb2Te4 20
100
with small addition of oxygen the crystallization phase 15 2
appear in the temperature range T=130-145 oC, and at higher 50
10
temperature (around T=275 oC) this phase is transformed 1
into the Ge1Sb2Te4 hexagonal phase. 5
Eg=1.08 eV 0
0
0.90 0.95 1.00 1.05 1.10
80 Energy (eV)
Ge1Sb2Te4

Fig.4. The dependences of the absorption coefficient  versus photon

60
energy h (=f(h) (1) and (h)1/2=f(h) (2) for as-deposited
Transmittance (%)

1
amorphous Ge1Sb2Te4 thin films (d=1.57 m).
40
Fig.5 represents the dispersion curve of the refractive index
20 n=f() for as-deposited amorphous Ge1Sb2Te4 thin films.
The points are the experimental data, and the continuum line
2 is the computer fitting curve. The plot (n2-1)-1 vs. (h)2
0 (Fig.6) allow to determine the oscillator parameters by
1000 1500 2000 2500 3000 3500
Wavelength (nm) fitting a straight line to the experimental points. By
extrapolating the fitting line towards h=0, one can obtain
Fig.3. The transmission spectra of as-deposited amorphous Ge1Sb2Te4 the static refractive index n0=3.0 and the static dielectric
thin films (1) and annealed at T=150 oC during 2 minutes (2). d=1.57 constant s = n2(0) = 9.0.
m.

Fig.4 shows the dependences of the absorption coefficient  6.5

versus photon energy h (=f(h) (curve 1) and
6.0
(h)1/2=f(h) (curve 2) for as-deposited amorphous
Refractive index

Ge1Sb2Te4 thin films derivates from the transmission spectra 5.5

using the computer program PARAV-V1.0 [8]. The optical
transmission T() for thin semiconductor films is determined 5.0
by the expression: 4.5
(1  R) 2 exp( d )
T , (1) 4.0
1  R 2 exp( 2d )
where R - is the optical reflection,  - the absorption 3.5
1500 2000 2500 3000
coefficient, and d - the thickness of the amorphous film. In Wavelength (nm)
2d
1 from the
2
the consideration that the member R e
Fig.3a. The dispersion curve of the refractive index n=f() for as-
equation (1) we can obtain the expression for calculation of deposited amorphous Ge1Sb2Te4 thin films (d=1.57 m).
the absorption coefficient
The dispersion of the refractive index is related to the
1 (1  R) 2
  ln (2)
electronic absorption spectrum through the Wemple equation
d T based on the single electronic oscillator model [13]
The optical band gap Eg for as-deposited amorphous films Ed E0
was calculated from the relation: (n 2  1)   (h ) 2 (4)
E0
( h)1/2 = A(h - Eg), (3)
where E0 is the average electronic energy gap, and Ed is the
where A – is a constant. A plot (  h )1/ 2 ~ h (Tauc plot) dielectric oscillator strength.
yields a straight line and the extrapolation of the photon Large values of the refractive index n are obtained for
energy axis (  h )1/ 2  0 give the values of the optical smaller E0 and for large Ed and leads to a large dispersion
band gap Eg. The estimated value of the optical band gap of throughout the chalcogenide glass material. From equation
the as-deposited amorphous Ge1Sb2Te4 film is Eg=1.08 eV. (4) we obtain
E0 1
For Ge1Sb2Te4 it was demonstrated that the measured
(n 2  1) 1  ( )(h ) 2 (5)
indirect band gap energies are compared to those of the Ed E0 Ed
electronic band-structure calculations [12].
Using the plot from Fig.3b, the E0 and Ed were calculated
with the values E0=0.931 eV and Ed=7.448 eV, respectively.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

The value of E0 is smaller than optical band gap Eg=1.08 eV REFERENCES

obtained from the Tauc plot (Fig.4). [1] N.A.Goriunova, B.T.Kolomiets, Structure and
properties of ternary semiconducting systems, Journal
of Technical Physics 25, 984-994 (1955) (in Russian).
0.08 [2] N.A.Goriunova, B.T.Kolomiets, New vitreous
semiconductors, USSR Academy of Sciences Letters,
0.07 Physical Series 20, 1496-1500 (1956) (in Russian).
0.06 [3] N.F.Mott, E.A.Davis, Electron processes in non-
-1

crystalline materials, Clarendon Press, Oxford (1979).

(n -1)

0.05
[4] S.R.Ovshinsky, Reversible electrical switching
2

0.04 phenomena in disordered structures, Physical Review

0.03 Letters 21, 1450-1453 (1968).
[5] Mihai A.Popescu, Ovonic materials, J. of Ovonic
0.02 Research 1, 69-76 (2005).
0.2 0.3 0.4 0.5 0.6 0.7 0.8
2 2
(h) (eV ) [6] http://www.giac.org/resources/whitepaper/architecture/1
02.php
Fig.6. The dependence (n2-1)-1 =f(h)2 for as-deposited amorphous [7] http://en.wikipedia.org/wiki/Phase-change_memory
Ge1Sb2Te4 thin films (d=1.57 m). [8] A.Velea. Tellurium based phase change materials.
Journal of Optoelectronics and Advanced Materials
11(12), 1983-1987 (2009).
III. CONCLUSIONS [9] Mihai Popescu. Structural modeling of ovonic materials.
J. of Ovonic Research 2(4), 45-52 (2006).
The X-ray diffraction patterns and optical properties of [10] Ganjoo A., Golovchak R. Journal of Optoelectronics
phase change materials Ge1Sb2Te4 were studied. It was and Advanced Materials, 10(6), 1328 (2008).
established that after annealing of the amorphous films a [11] M.Frumar, T.Kohoutek, J.Prikryl, J.Orava, T.Wagner.
high temperature (T=150 oC) take place the crystallization On the atomic structure of thin amorphous Ge-Sb-Te
and the Urbach tail is affected. Grom the transmission films. Physica Status Solidi (b) 246(8), 1871-1874
spectra the optical constants absorption coefficient α, optical (2009).
band gap Eg, and the refractive index n) of the amorphous [12] Jun-Woo Park, S.E.Eom, H.Lee et al. Optical properties
Ge1Sb2Te4 were determined. of pseudobinary GeTe, Ge2Sb2Te5, GeSb2Te4,
The static refractive index n0=3.0, static dielectric constant s GeSb4Te7, and Sb2Te3 from ellipsometry and density
= n2(0) = 9.0, average electronic energy gap E0=0.931 eV, functional theory. Phys. Rev. B 80, 115209 (2009) [14
and the dielectric oscillator strength Ed=7.448 eV were pages].
estimated from the optical measurements. [13] Y.Ruan, R.A.Jarvis, A.V.Rode et al. Wavelength
dispersion of Verdet constants in chalcogenide glasses
for magneto-optical waveguide devices. Optics
Communications 252, 39-45 (2005).

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Exchange Electron-Hole Interaction of Two-

Dimensional Magnetoexcitons under the
Influence of the Rashba Spin-Orbit Coupling
S.A. MOSKALENKO1,*, I.V. PODLESNY1, B.V. NOVIKOV2, E.S. KISELYOVA3,
I.A. LELYAKOV1, and L. GHERCIU1,3
1
Institute of Applied Physics, Academy of Sciences of Moldova, 5, Academiei str., MD-2028, Chisinau,
Republic of Moldova
2
Department of Solid State Physics, Institute of Physics, St.Petersburg State University, 1,
Ulyanovskaya str., Petrodvorets, 198504, St.Petersburg, Russia
3
Moldova State University, 60, A. Mateevici str., MD-2009, Chisinau, Republic of Moldova
*
[email protected]
Abstract – The Rashba spin-orbit coupling (RSOC) in the case of two-dimensional (2D) electrons and holes
in a strong perpendicular magnetic field was studied. The spinor-type wave functions are characterized by
different numbers of Landau levels in different spin projections. For electrons they differ by 1 as was
established earlier by Rashba [1], whereas for holes they differ by 3. Two lowest electron states and four
lowest hole states of Landau quantization give rise to eight 2D magnetoexciton states. The exchange electron-
hole interaction in the frame of these states is investigated.
Index Terms – quantum transitions, Rashba spin-orbit coupling, Landau quantization, magnetoexcitons.

eipx a0c , 0 ( y, p )
I. INTRODUCTION**  c ( R1 , p; x, y )  U c , s , p (r ) ;
Lx b1c ,1 ( y, p )
Since the mid 1980s, there has been an extensive interest
in the effects of an applied electric field normal to the layers eipx 0
 c ( R2 , p; x, y )  U c , s , p (r ) ;
on the optical properties of semiconductor quantum wells Lx c , 0 ( y, p )
(QWs) and superlattices (SLs) [2]. The electric field strength c3v , 3 ( y, q ) (1
eiqx 1
perpendicular to the layer surface gives rise to Rashba spin-  v ( R1 , q; x, y )  (U v , P , X , q ( r )  iU v , P , Y , q ( r )) ;
Lx 2 d 0v , 0 ( y, q )
orbit coupling (RSOC). The spin-orbit effects are discussed
in a special monograph [3] and papers [2, 4-9]. In the Ref. eiqx 1 v , 0 ( y, q )
 v ( R2 , q; x, y )  (U v , P , X , q ( r )  iU v , P , Y , q (r )) ;
[10-12] the energy spectrum of 2D magnetoexcitons were Lx 2 0
studied supposing that the spin polarizations of electrons and eiqx 1 c4v , 4 ( y, q )
holes take place and the spin-orbit coupling was neglected.  v ( R3 , q; x, y )  (U v , P , X , q ( r )  iU v , P , Y , q ( r )) ;
Lx 2 d1v ,1 ( y, q )
In reality, as was shown in Ref. [13], the RSOC leads to
eiqx 1 v ,1 ( y, q)
breaking of the pure spin polarizations and the new spinor-  v ( R4 , q; x, y )  (U v , P , X , q ( r )  iU v , P , Y , q ( r )) .
type states are characterized by different numbers of Landau Lx 2 0
levels for different spin projections. These numbers for )
electrons differ by 1, whereas for holes differ by 3. Spin The orthogonality each other of the conduction and
polarized states under the influence of the RSOC are valence electron Bloch wave functions is attained due to
transformed into mixed spinor components. The two lowest their orthogonal periodic parts, whereas the orthogonality of
electron states and four lowest hole states were used to the wave functions belonging to the same bands and having
construct eight lowest 2D magnetoexciton states [13]. The the same periodic parts is reached due to different numbers
direct Coulomb electron-hole interaction gives rise to the of the Landau quantization wave functions c , n ( y, p) and
binding energies and ionization potentials of the v , m ( y, p) . The conduction and valence electrons have the
magnetoexciton states. They were calculated in Ref. [10-12].
Below we will use these results to determine the exchange same electric charge — | e | and their dimensionless
electron-hole interaction. variables have the same structure
y
l
 pl and y
l
 ql . The
II. EXCHANGE ELECTRON-HOLE INTERACTION last variable looks as
y
 ql in the case of the hole wave
l
The electron-hole Coulomb interaction is calculated below
taking into account the influence of the RSOC in the frame function h, n ( y, q) due to the positive value of the hole
of conduction and valence bands. The corresponding Bloch charge | e | .
wave functions including their periodic parts are We will consider eight combinations of the electron-hole
pairs taking into account two spin-splitted electron Landau
levels e, R1 and e, R2 and four spin-splitted hole Landau
levels h, R j with j  1, 2,3, 4 . These combinations will be
**
I.V.P. thanks the Foundation for young scientists of the Academy of denoted by
Sciences of Moldova for financial support (11.819.05.13F).

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

f s  (e, Ri ; h, R j ); s  1, ,8; i  1, 2; j  1, 2,3, 4. (2) R2  R1  R enumerating the lattice nodes. Four integrations
The wave functions of eight magnetoexciton states with are effectuated separately, two on the volume v0 of the
electron states R1 and R2 and with four hole states R1 , R2 ,
lattice cell and two integrations on R1 and R on the surface
R3 and R4 can be expressed through the corresponding
of the 2D layer. In difference on the case of the direct
creation and annihilation operators. For example, in the Coulomb interaction, the integration on the lattice cell
compositions f s represented by the formulas (2), we have volume v0 of the exchange charge densities without
1

 ik tl 2
 ex (k , f s )  e y aR† , kx  t bR† , kx t ; participation of the functions describing the Coulomb
N t i 2 j 2 (3) interaction vanish due to the orthogonality of the periodic
s  1, 2, ,8; i  1, 2; j  1, 2,3, 4. parts of the Bloch functions belonging to different bands
1 1
v0 v0 v0 v0
Side by side with the direct Coulomb interaction it is d 1W ( 1 ; c, p; v, p  s)  0; d 2W * ( 2 ; c, q  s; v, q)  0.
necessary to study the exchange Coulomb e-h interaction. In
the case of Wannier-Mott excitons in the absence of external (8)
magnetic field and RSOC it gives rise to the singlet-triplet It means that in the frame of the exchange Coulomb
splitting of the exciton levels. It is due to the contact or interaction two electrons do not behave as a point charges,
short-range part of the exchange e-h interaction and is but rather as two inter-band dipoles situated on different
revealed very well experimentally in the case of ortho- and nodes ( R  0) of the lattice. To demonstrate this picture the
para-excitons in Cu2O crystal. The long-range part of this Coulomb interaction potential will be represented in the
interaction determines the longitudinal-transverse splitting of form
the three-fold degenerated dipole-active exciton levels in  1
cubic crystals as well as the polariton gap [14]. These    , R0
1 1  2
 
1
questions were not studied at all in the case of 2D
r2  r1 R   2  1  1 ( 1   2 ) 3( 1  R)(  2  R)
magnetoexcitons and more so in the presence of the RSOC.    , R  0.
They will be discussed below. The exchange e-h interaction R R3 R5
has its origin in the exchange Coulomb interaction between (9)
the conduction electron and valence electron. At first we will This representation permits to separate the contact or
consider the conduction electron in the state R1 and the short-range interaction, when both electrons are in the same
valence electron in the state R1 in the frame of Landau unit lattice cell ( R  0) , and the long-range part, where R
quantization and RSOC. differs from zero ( R  0) .
The corresponding Hamiltonian is The inter-band dipole moments appear as follows
c v
H exch   Fc  v (c, R1 , p; v, R1 , q; v, R1 , p  s; c, R1 , q  s) e
p, q, s d cv ( p, p  s)   d 1W ( 1 ; c, p; v, p  s) 1e is 1 x ,
v0 v0
a † †
a a a
c , R1 , p v , R1 , q c , R1 , q  s v , R1 , p  s , (10)
e
 d 2W ( 2 ; c, q  s; v, q) 2e 2 x .
 is 
(4) d cv* (q  s, q)  *

where v0 v0
Fc  v (c, R1 , p; v, R1 , q; v, R1 , p  s; c, R1 , q  s)
The integrations on the large-scale variable R1 involve
  d 1  d 2 c, R1 , p, (1) v, R1 , q, (2) V (1  2) v, R1 , p  s, (1) c, R1 , q  s, (2) (5)
different combinations of the Landau quantization functions
eis ( x2  x1 )
  d 1 d 2
L2x
W (1; c, p; v, p  s) n ( R1 y , p) and n ( R1 y  Ry , p) in the following
  a0*c3c*,0 ( y1 , p )v ,3 ( y1 , p  s )  b1* d 0c*,1 ( y1 , p )v ,0 ( y1 , p  s )  V (1  2) combinations
W * ( 2; c, q  s; v, q) c3* a0v*,3 ( y2 , q)c ,0 ( y2 , q  s)  d 0*b1v*,0 ( y2 , q)c ,1 ( y2 , q  s) 
G0,0;3,3 ( Ry )  G (0, p;0, q  s;3, p  s;3, q | R y )
  dR1 y ( R1 y , p )c ,0 ( R1 y  Ry , q  s )v ,3 ( R1 y , p  s )v*,3 ( R1 y  Ry , q );
*

i 2a0 c ,0

b1  ; | a0 |  | b1 |  1;
2 2
G1,1;0,0 ( Ry )  G (1, p;1, q  s;0, p  s;0, q | Ry )
1
 1
 2 2 (11)
and (6)   dR1 y ( R1 y , p )c ,1 ( R1 y  Ry , q  s )v ,0 ( R1 y , p  s )v*,0 ( R1 y  Ry , q);
2 4 *
c ,1
i  4 3d 0
c3  ; | d 0 |2  | c3 |2  1. G0,1;3,0 ( Ry )  G (0, p;1, q  s;3, p  s;0, q | R y )
3
2  9
4  48 2   dR1 yc*,0 ( R1 y , p )c ,1 ( R1 y  Ry , q  s )v ,3 ( R1 y , p  s )v*,0 ( R1 y  Ry , q );
with electron and hole SOC parameters   e Ez l ce , G1,0;0,3 ( Ry )  G (1, p;0, q  s;0, p  s;3, q | Ry )
  h Ez l 3 ch correspondingly.   dR1 y ( R1 y , p )c ,0 ( R1 y  Ry , q  s )v ,0 ( R1 y , p  s )v*,3 ( R1 y  Ry , q ).
*
c ,1

Here the exchange charge density of electron was The exchange e-h interaction is represented below as a
introduced sum of contact and long-range parts
W (r ; c, p; v, p  s)  U c, S , p (r )
1
U v, P, X , p s (r )  iU v, P,Y , p s (r ) . (7)
2
Fc  v (c, R1 , p; v, R1 , q; v, R1 , p  s; c, R1 , q  s )
(12)
 Acont ( R1 , R1 ; p, q, s)  Vl  r ( R1 , R1 ; p, q, s).
It depends on the product of two periodic parts of the
The contact part equals to
Bloch functions of electron in conduction and valence bands. Acont ( R1 , R1 ; p, q, s) (13)
We have introduced the variables 1 and  2 , changing al2 1 1 e2
Lx v0 v0
 d 1  d 1W ( 1 ; c, p; v, p  s )W * (  2 ; c, q  s; v, q) e  s ( 2 x  1 x )
 0  2  1
inside the lattice cell with the volume v0  al3 , where al is v0 v0

  a0 c3 G0,0;3,3 (0)  d 0 b1 G1,1;0,0 (0)  a0* d 0*c3b1G0,1;3,0 (0)  b1*c3*d 0 a0 G1,0;0,3 (0)  ,
2 2 2 2
 
the lattice period, as well as two continuous variables R1 and
whereas the long-range part contains a supplementary

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

1
summation on the large scale variable R  Fc v (c, Ri , p; v, R j , q; v, R j , p  k x ; c, Ri , q  k x )e y x , (20)
ik ( p  q  k ) l 2

a2 N p,q
Vl  r ( R1 , R1 ; p, q, s)  l eisRx i  1, 2; j  1, 2,3, 4.
Lx R  0
  
 dcv ( p, p  s)  dcv (q  s, q) 3 d cv ( p, p  s)  R d cv (q  s, q)  R
 
   (14) III. CONCLUSION
 R3 R5  The spinor-type wave functions of the 2D electrons and
  holes in the presence of the RSOC were used to calculate the
 | a0 |2 | c3 |2 G0, 0;3, 3 ( Ry ) | d0 |2 | b1 |2 G1,1;0, 0 ( Ry ) exchange electron-hole interaction in the frame of 2D
 a0 d 0c3b1G0,1;3, 0 ( Ry )  b1c3 d 0 a0G1, 0;0,3 ( Ry )  .
magnetoexcitons. Two lowest Landau levels for electrons
e, R1 , e, R2 and four lowest Landau levels for holes
Here the summation on the variable R can be substituted
by integration as follows al2   dRx dRy . h, R1 , h, R2 , h, R3 , and h, R4 were combined in such
R0 a way so as to form eight electron-hole states corresponding
The Hamiltonian (4) with the operators to the combinations: f1  (e, R1 ; h, R1 ); f 2  (e, R1 ; h, R2 );
bR† j , q  av , R j ,  q ; bR j , q  av†, R j ,  q ; ac , Ri , p  aRi , p ; f3  (e, R2 ; h, R1 ); f 4  (e, R2 ; h, R2 ); f5  (e, R1 ; h, R3 );
(15)
av†, R j , q av , R j , q  s  bR j ,  q bR† j ,  q  s  bR† j ,  q  s bR j ,  q   kr (s, 0). f6  (e, R1 ; h, R4 ); f7  (e, R2 ; h, R3 ); f8  (e, R2 ; h, R4 ). The
after the normal ordering of the hole operators will give rise exchange e-h interaction consists from the contact and long-
to the Hamiltonian of the exchange e-h interaction range terms. The contact interaction depends only on the
concerning the states c, R1 and v, R1 . It is integration on the elementary lattice cell, whereas the long-
range part contains a supplementary summation on the large
eh
H exch   A
p, q, s
cont ( R1 , R1 ; p, q, s)  Vl  r ( R1 , R1 ; p, q, s) 
(16) scale variable representing the distance between two lattice
nodes in the neighborhood of which the electron and hole are
 aR†1 , p bR†1 ,  p  s bR1 ,  q aR1 , q  s .
localized. In the frame of exchange Coulomb interaction
On the ways from the initial expression (4) to the final form conduction electron and valence electron do not behave as a
(16) correspondingly we have separated the quadratic free point charges, but rather as two inter-band dipoles situated
electron Hamiltonian on different nodes of the lattice.
 Fc v (c, R1 , p; v, R1 , q; c, R1 , p  s; v, R1 , q  s)
p REFERENCES
 Fc v (c, R1 , p; v, R1 , q; v, R1 , p  s; c, R1 , q  s)  a † [1] E.I. Rashba, Sov. Phys. Fiz. Tverd. Tela (Leningrad),
R1 , p aR1 , p . (17)
vol. 2, p. 1224, 1960.
It describes the influence on the conduction electron of the [2] Bang-fen Zhu and Yia-Chung Chang, Phys. Rev. B, vol.
valence electrons, which together with the electrons of the 50, p. 11932, 1994.
inner atomic shells create the effective periodic potential of [3] Roland Winkler, Spin-Orbit Coupling Effects in Two-
the lattice. The terms (17) compensate the difference Dimensional Electron and Hole Systems, Springer Tracts
between the periodic potential created by the inner atomic in Modern Physiscs: Springer, Berlin, Heidelberg, vol.
shells and the real effective periodic potential created by all 191, 228 pages, 2003.
electrons including the valence electrons [14]. The effective [4] Ralph van Gelderen and C. Morais Smith, Phys. Rev. B,
periodic potential determines the electron wave functions (1) vol. 81, p. 125435, 1994.
used in our calculations and at the same time depends in a [5] S.A. Brazovskii, Zh. Eksp. Teor. Fiz., vol. 68, p. 175,
self-conjugated way on their forms, it means on the presence 1975; Sov. Phys. JETP, vol. 41, p. 85, 1975.
of a strong perpendicular magnetic field as well as on the [6] R. Winkler, M. Merkler, T. Darnhofer, and U. Rossler,
RSOC. Above we have calculated the exchange interaction Phys. Rev. B, vol. 53, p. 10858, 1996.
matrix element for the first combination f1 of the electron [7] U. Ekenberg and M. Altarelli, Phys. Rev. B, vol. 32,
wave functions c, Ri , p and v, R j , q with i  1, 2 and p. 3712, 1985.
[8] R. Winkler, Phys. Rev. B, vol. 62, p. 4245, 2000.
j  1, 2 . For another three combinations we have obtained [9] R. Winkler, H. Noh, E. Tutuc, and M. Shayegan, Phys.
the formulas similar to the expressions (13) and (14). The Rev. B, vol. 65, p. 155303, 2002.
only differences concern the square brackets, where must be [10] S.A. Moskalenko, M.A. Liberman, P.I. Khadzhi, E.V.
written correspondingly Dumanov, Ig.V. Podlesny, and V.V. Botan, Solid State
| a0 |2 G0, 0; 0, 0 ( Ry ) for f 2  (c, R1 ; v, R2 ), Commun., vol. 140, p. 236, 2006.
[11] S.A. Moskalenko, M.A. Liberman, P.I. Khadzhi, E.V.
| d 0 |2 G1,1; 0, 0 ( Ry ) for f3  (c, R2 ; v, R1 ), (18) Dumanov, Ig.V. Podlesny, and V.V. Boţan, Physica E,
0 for f 4  (c, R2 ; v, R2 ). vol. 39, p. 137, 2007.
[12] S.A. Moskalenko, M.A. Liberman, and I.V. Podlesny,
The Hamiltonian describing the exchange electron-hole
Phys. Rev. B, vol. 79, p. 125425, 2009.
interaction has the form
[13] T. Hakioglu, M.A. Liberman, S.A. Moskalenko, and
eh
H exch   
p , q , s i 1,2 j 1,2,3,4
Fc  v (c, Ri , p; v, R j , q; v, R j , p  s; c, Ri , q  s)
(19) I.V. Podlesny, Phys. Rev. B, (submitted).
 aR†i , p bR† j ,  p  s bR j ,  q aRi , q  s . [14] S.A. Moskalenko, Introduction in the theory of high
density excitons, Chisinau, Shtiintsa, 304 pages, 1983.
The average values of this Hamiltonian were calculated
with the exciton wave functions (3). They determine the
shifts of the magnetoexciton energy levels due to the
exchange e-h interactions. They are equal to

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Magnetotransport Properties of Ultrathin

LaMnO3 Layers
Oleg SHAPOVAL, Alexander BELENCHUK, Efim ZASAVITSKY, Valeriu KANTSER,
IIEN, AS RM, str. Academiei 3/3, MD 2028, Chisinau, Republica Moldova
[email protected]
Vasily MOSHNYAGA
Erstes Physikalisches Institut, Universität Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen,
Germany

Abstract – We report the transport and magnetic properties of La-deficient ultrathin films of La1-MnO3 (LMO)
grown on SrTiO3 (STO) and engineered by using different interfacial layers. LMO layer and adjusting interface
oxide (LaO-STO and SMO) layers were grown by a metalorganic aerosol deposition technique with monolayer
accuracy. The role of LaO-TiO2 interface in the formation of ferromagnetic metallic state in very thin LMO films
was demonstrated. Ferromagnetic metallic ground state in LMO films with the thickness down to 6 monolayers is
stabilized by a combination of a La-deficiency and the interface-induced doping.

Index Terms – magnetotransport, metal-insulator transition, metalorganic aerosol deposition, oxide interfaces, thin
film.

for the A1B1O3-A2B2O3 stacked perovskites was

demonstrated for the well-known LaAlO3/SrTiO3 system
I. INTRODUCTION
[11], where AlO2-LaO-TiO2 stacked planes are electronically
To enhance the functionality of all-oxide based devices
reconstructed and show a metallic behavior, whereas the
the idea of the interface engineering of multilayered oxide
AlO2-SrO-TiO2 interface is insulating due to atomic
heterostructures was put forward in the last few years.
reconstruction.
LaMnO3 (LMO) is one of the promising materials used for
the interfacial design of different multilayer systems. The
stoichiometric LMO with the nominal t32ge1g occupancy of
Mn3+ ions is an insulator with strong Mott-Hubbard
correlations in a half-filled eg band [1]. An A-type
antiferromagnetic (AFM) ground state originates due to the
orbital ordering of eg-orbitals with ferromagnetic (FM) in-
plane and AFM out-of-plane exchange interactions.
Nevertheless, LMO can be easily transformed into an FM
metal, particularly in thin films [2] and superlattices of
LMO/SMO [3] and LMO/STO [4]. The ferromagnetism was
shown to be due to the change of: a) stoichiometric cationic
composition; b) optimal oxygen content as well as c) due to
epitaxial stabilization of a nonstoichiometric state in the
layers grown on SrTiO3 (STO) (100) substrates [2, 5]. The
―electron leakage‖ phenomenon, caused by the polar
discontinuity at the interfaces, was shown to control the
magnetotransport in superlattices [4, 6]. The main parameter,
influencing the direction of charge leakage and, therefore,
the magnetic properties, is the substrate-induced epitaxial
strain. The interest to LMO as a functional material was
recently stirred up by the demonstration of a metal-insulator Fig. 1. STM image of 10 nm LMO layer deposited on TiO2-terminated
transition at TMI >400 K in a heavy La-deficient films [7]. surface of STO(100) substrate.
An important question, concerning to electronic and A single heterojunction for an A1B1O3 layer, grown on the
structural reconstruction at the interfaces, is the atomic STO(100) substrate, can be modified by TiO2- or SrO-
structure of stacking planes. The LMO/SMO system termination of the substrate surface. In the case of
demonstrates exclusively the LaO-MnO2-SrO sequence of multilayered A1B1O3-A2B2O3 structures a conventional
atomic planes at the interface [8]. In contrast, the LMO/STO growth techniques produce two types of interfaces [9]. The
system reveals two types of interfaces due to different A- first layer starts from A1O-plane on TiO2-terminated surface
and B-site occupancies in the perovskite lattices. Namely, 1) STO(100) substrate and terminates by B 1O2-plane; the next
(LaO-MnO2)-(SrO-TiO2) (compactly MnO2-SrO)) and 2) layer repeats the alternation of AO- and BO2-planes. A
(MnO2-LaO)-(TiO2-SrO) (or LaO-TiO2) [9] interfaces were possibility to tailor the superlattices with single type of
observed. In this case one should expect different interface- interface by introducing an extra-plane was recently
induced properties [10]. An example of such different demonstrated for LMO/STO system [4]. The presence of
properties attributed to A1O-B2O2 and A2O-B1O2 interfaces

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

extra LaO-planes in manganite layers and TiO2-planes in deviation of La molar content from the ―right‖ La/Mn-ratio
titanate layers was confirmed by STEM combined with in the solution was used in the sequel as a measure of the La-
EELS analysis. deficiency. The La-deficiency of LMO layers was varied in
The aim of the presented work was to study the range 0-12%. The thickness of LMO films was d=6-30
magnetotransport properties of ultrathin LMO films with unit cells (u.c.) or d=2.5-12 nm.
thicknesses comparable to the thickness of single layers in LMO layers were deposited directly onto both TiO 2- and
SL‘s. To design the LMO-based layered structures with SrO-terminated substrates or onto the STO surface, buffered
optimized FM metallic behavior two approaches were by 2 u.c. of SMO. The top surface of LMO films have been
applied: 1) the La-deficiency was intentionally generated remained free or covered by 2 u.c. of the cap layer, e.g. STO
in the LMO layer and 2) ultrathin LMO films were or SMO. Electron transport measurements were performed
engineered by different interfaces. by standard 4-probe technique using commercial PPMS
from ―Quantum Design‖. Magnetization was measured by
II. EXPERIMENT AND RESULTES
means of commercial SQUID (MPMS, ―Quantum Design‖).
The samples were prepared by a metalorganic aerosol
The role of LaO-TiO2 interface was examined on series of
deposition (MAD) technique, elaborated earlier for the
samples with the same La-deficiency, =6 %, and thickness
preparation of complex oxide thin films and further
of LMO layer. The influence of LaO-TiO2 interfaces on the
developed for the deposition of ultrathin films and
electron transport as a function of temperature is shown in
superlattices [12]. Aerosols of organic solutions, containing
Fig. 2. We suppose that the growth of LMO on the TiO 2-
metal β- diketonates (e.g. La-, Sr-, Mn-acetylacetonates),
terminated STO(100) from a solution, containing both La
were sprayed onto a heated substrate. A film grows on the
and Mn precursors, occurs in the following way. It starts
substrate as a result of a heterogeneous pyrolysis reaction of
from LaO-plane, forming the LaO-TiO2 interface, and
the metalorganic component. Within the MAD technique
terminates with MnO2 plane completing perovskite
one can easily manipulate the precursor solutions, which
monolayer [9]. Thus, the LMO film with one (bottom) LaO-
contain either a single precursor for mono-oxide layers or a
TiO2 interface and free surface (top) was prepared after
mixture of two and more precursors to produce layers of
deposition of 26 perovskite unit cells of LMO. Such film
complex oxides. The monolayer accuracy was achieved by
demonstrates a metal-insulator (MI) transition at T MI=285K
accurate calibration of dosing units. Vacuum-free MAD
and metallic behavior at low temperatures (curve 1 Fig. 2). A
technique allowed us to interrupt deposition process and to
deposition of one monolayer of LaO, followed by 2 u.c. of
continue the preparation of the layered structure after
STO on the top surface of the LMO film has resulted in the
intermediate express measurements.
400 enhancement of TMI by 45 K and in the decrease of the
M, emu/cm3

resistance at TMI by 2 times (curve 2 Fig. 2). An LMO film

300
10
6
without LaO-TiO2 interfaces was prepared by the deposition
no LaO-TiO2
200 of one monolayer of SrO onto the TiO2-terminated
3 2
STO(100) prior to the deposition of LMO. In this case the
Resistance (

interfaces 100
5
1 manganite had to start the growth from the MnO2 plane.
10
100 150 200 250 300 LMO film with bottom SrO-MnO2 interface and free top
T,K surface shows a decreased T MI=210K and an insulating
behavior at low temperatures (curve 3 Fig. 2). Deposition of
10
4 single LaO-TiO2 4 2 u.c. of STO on the top of LaO-terminated manganite film
top interface 1
results in the formation of an LaO-TiO2 top interface, thus,
two LaO-TiO2 recovering the transport (curve 4 Fig. 2) to that described
3 2 interfaces above for the film with one LaO-TiO2 bottom interface.
10
150 200 250 300 350 We assume that optimized metallic behavior in LMO
engineered films is because each LaO-TiO2 interface creates
Temparature (K)
effective conductive channels close to (or inside) the LMO
Fig. 2. Evolution of transport properties of 10 nm LMO layers deposited on layer. Magnetization as a function of temperature (see inset
STO(100) substrates and equipped with: (1) bottom LaO-TiO2 interface; (2) to Fig. 2) reveals, however, an unexpected behavior: after
top and bottom LaO-TiO2 interfaces; (3) no LaO-TiO2 interface; (4) top adding the second LaO-TiO2 interface the Curie temperature
LaO-TiO2 interface. Insert: Magnetization as function of temperature. (TC) was increased up to 305 K (the film with one interface
shows TC=275 K). The increase of T C correlates with
STO(100) substrate was chosen due to the possibility to increase of TMI, but TC is consistently lower than T MI.
study the influence of both surface terminations. The Surprisingly, the saturation magnetization and magnetic
atomically smooth TiO2-terminated STO(100) with terrace hysteresis did not change after adding the second interface,
steps of one unit cell in height was obtained by treating the Ms~400 emu/cm3~2.5 μB/Mn. This value is larger than that
crystal surface with a pH-controlled NH4F-HF solution [13]. for undoped LMO [14] but it is significantly lower than
SrO-terminated surface was produced by deposition of SrO magnetization for optimal doped manganites, Ms~3.7 μB/Mn
monolaeyer (ML) on TiO2- terminated surface. The exact [15]. Relatively high residual resistivity, ρ10K=1.6·10-4 Ωcm,
oxygen stoichiometry in the prepared LaMnO3 layers was also indicates insufficient doping level.
assumed due to a high (atmosphere) gas pressure conditions Magnetic and transport properties of the samples with
[12].As the criteria of a stoichiometric La/Mn=1:1 relation different thickness and the same La deficiency of LMO
we used the insulating behavior of the film, unique for a layers (see Fig. 3) stay in line with the probably lowered
stoichiometric LMO, as well as smooth and flat surface doping level. The highest temperature of the metal-insulator
morphology (Fig. 1) with terraces inherited from STO. The transition TMI≈330 K was achieved in LMO with the

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

thickness 26 uc and La-deficiency, =6-8 %. The resistance 400

shows metallic behavior down to the lowest temperature. By 0H=1 kOe (a)
10 nm
decreasing the thicknesses of LMO layer a decrease of T MI
and an increase of the resistance was observed. The 300

M, emu/cm3
thickness dependence of the transport properties can be
rationalized within the ―electron leakage‖ from the interface 200 4 nm
into the LMO layer. The reduced oxidation state in the
sample is consistent with some degree of electron doping,
coming from the electron from the extra (LaO) plane. The 100
2.5 nm
depth of charge spreading is larger than 2 uc as calculated
for the insulating LMO [6]; it looks like charge is evenly 0
distributed among the tens of LMO unit cells [4]. By T, K 100 200 300
reducing the thickness of LMO, one extra-electron
distributed among smaller amount of LMO unit cells would T=10 K d=10 nm
give a stronger reduction of the averaged oxidation state.

M*10 (emu)
1
Such scenario suggests that LMO layers become
progressively less hole-doped as the thickness is reduced, i.e. d=4 nm

4
it is consistent with an increased electron leakage into LMO. 0
Finally, for samples thinner than as 3 nm (6-7 uc) no d=2.5 nm
metallic behavior was more observed regardless to the La
deficiency; note that 2.5 nm thick film still remains -1
ferromagnetic.
A further support for the above model comes from (b)
magnetization measurements. We observed a gradual -400 -200 0 200 400
decrease of MS with decreasing of the LMO thickness (see
0H (Oe)
Fig. 4a), that correlates both with the decrease of T C and TMI.
Magnetic hysteresis behavior also comes to agreement with Fig. 4. Magnetization as a function of temperature (a) and magnetic
histeresis (b) for the STO-LMO-STO structures with different thickness of
this model. The value of coercive field Hc ~30 Oe indicates LMO layers.
magnetic homogeneity of the 26 uc thick film. Apparently
(see Fig. 4b)), magnetic inhomogeneity increases and the
saturation magnetization decreases dramatically with
decreasing of the thickness, i.e. MS<1 μB/Mn for the 6 uc
thick film, that is typical for an undoped LMO [14]. From a
magnetic point of view only, the system looks like a weak
ferromagnet. However, the eg-hole is localized within a
certain regions with very few Mn-ions. The ground state is a
mixed state, composed from a disordered nm-size ―double-
exchange‖ metallic clusters and coexisting insulating
domains. Even for high magnetic fields the system with
magnetically aligned FM clusters do not reach the
percolation limit [16] even if they grow in size.

7
10
d=2.5 nm
6
10
Resistance (

5
10 4 nm

4 7 nm
10
11 nm
3
10

0 50 100 150 200 250 300 350 400

Temperature (K)
Fig. 5. Magnetization as a function of temperature (a) and resistance as
Fig. 3. Dependence of transport properties on temperature for STO-LMO- function of temperature (b) for: (1) STO-LMO(10 ML)-STO; (2) SMO-
STO structures with different LMO layer thickness. LMO(6 ML)-SMO; (3) SMO-LMO(10 ML)-SMO structures.

Inversion of the LaO-TiO2 interface to SrO-MnO2 by

introducing SrO extra-layer (see Fig. 2) leads to the MnO2 could improve the magnetotransport in LMO layer.
degradation of transport properties. A new design of SrO- According to the calculations [6] the Mn eg electrons leak
out from the LMO layer to the SMO one and change the
magnetism at the interface, while away from the interface,

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

the magnetism of the respective bulk materials is preserved.

Introduction of the 2 u.c. of SMO as the buffer and the cape [3] A. Bhattacharya, et al., "Metal-Insulator Transition and
layers allowed us to change the direction of the charge Its Relation to Magnetic Structure in
leakage and as a consequence to restore metallic behavior in (LaMnO3)2n/(SrMnO3)n Superlattices," Physical Review
very thin LMO films. Letters, vol. 100, p. 257203, 2008.
The resistance of SMO-LMO-SMO structure was found to [4] J. Garcia-Barriocanal, et al., "―Charge Leakage‖ at
be about 5 times lower than the resistance for STO-LMO- LaMnO3/SrTiO3 Interfaces," Advanced Materials, vol.
STO sample with the same thickness (10 u.c.) and La- 22, pp. 627-632, 2010.
deficiency (see Fig. 5(b)). LMO film confined by 2 SMO [5] P. Orgiani, et al., "Enhanced transport properties in
u.c. demonstrates metallic behavior down to the thickness of LaxMnO3 -  thin films epitaxially grown on SrTiO3
6 u.c. The saturation magnetization and T C of SMO-LMO(6 substrates: The profound impact of the oxygen content,"
u.c.)-SMO and STO-LMO(10 u.c.)-STO are very similar Applied Physics Letters, vol. 95, pp. 013510-3, 2009.
(Fig. 5(a)), but the thinning of LMO layer in any way leads [6] B. R. K. Nanda and S. Satpathy, "Polar catastrophe,
to rising of inhomogeneity that reflects in increased electron leakage, and magnetic ordering at the
resistance (curve 2 in Fig. 5(b)). It is worth to note that the LaMnO3/SrMnO3 interface," Physical Review B, vol.
upper limit of the layer thickness is absent in the case of La- 81, p. 224408, 2010.
deficient LMO with ferromagnetic metallic behavior. [7] P. Orgiani, et al., "Multiple double-exchange
mechanism by Mn2+ doping in manganite compounds,"
CONCLUSIONS
Physical Review B, vol. 82, p. 205122, 2010.
We have shown that tailoring of the interfaces can be very
[8] J. Verbeeck, et al., "SrTiO3(100)/(LaMnO3)m(SrMnO3)n
effective in modifying the magnetotransport properties of
layered heterostructures: A combined EELS and TEM
ultrathin LMO films. Combination of the doping effects due
study," Physical Review B, vol. 66, p. 184426, 2002.
to the La-deficiency with the interface-induced doping
[9] M. Varela, et al., "Oxide Interfaces Under the Electron
allowed us to preserve ferromagnetic metallic behavior in
Microscope," Microscopy and Microanalysis, vol. 14,
STO-LMO-STO structures with the thickness down to 10
pp. 1346-1347, 2008.
u.c. of LMO. Interface modification of LMO layers by the 2
[10] H. Zenia, et al., "Electronic and magnetic properties of
u.c. thick SMO bottom and top interfaces has led to a further
the (001) surface of hole-doped manganites," Physical
shrinkage of the metallic LMO layer thickness down to 6
Review B, vol. 71, p. 024416, 2005.
u.c. Engineering of the single type LaO-TiO2 interface in the
[11] D. H. A. B. J. Mannhart, H.Y. Hwang, A.J. Millis and
STO/LMO stacked perovskites can be performed within the
J.-M. Triscone, "Two-Dimensional Electron Gases at
MAD technique by deposition of an extra LaO plane. Thus,
Oxide Interfaces," MRS Bulletin, vol. 33, pp. 1027-
we show the possibility to change the natural growth
1034, 2008.
sequence, i.e. AO-BO2, along the <100> direction of the
[12] K. Gehrke, et al., "Interface controlled electronic
perovskite structure.
variations in correlated heterostructures," Physical
Review B, vol. 82, p. 113101, 2010.
REFERENCES [13] M. Kawasaki, et al., "Atomic Control of the SrTiO3
[1] A. Yamasaki, et al., "Pressure-Induced Metal-Insulator Crystal Surface," Science, vol. 266, pp. 1540-1542,
Transition in LaMnO3 Is Not of Mott-Hubbard Type," December 2, 1994 1994.
Physical Review Letters, vol. 96, p. 166401, 2006. [14] C. Adamo, et al., "Electrical and magnetic properties of
[2] A. Gupta, et al., "Growth and giant magnetoresistance (SrMnO3)n/(LaMnO3)2n superlattices," Applied Physics
properties of La-deficient LaxMnO3 - (0.67< x <1) Letters, vol. 92, pp. 112508-3, 2008.
films," Applied Physics Letters, vol. 67, pp. 3494-3496, [15] J. M. D. Coey, et al., "Mixed-valence manganites,"
1995. Advances in Physics, vol. 48, pp. 167 - 293, 1999.
[16] P. A. Algarabel, et al., "Peculiar ferromagnetic insulator
state in the low-hole-doped manganites," Physical
Review B, vol. 67, p. 134402, 2003.

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Nonlinear Transmission of Two Successive

Ultrashort Laser Pulses by a Thin
Semiconductor Film under Two-Photon
Generation of Biexcitons. Giant Oscillator
Strength Model
Igor BELOUSSOV1, Peter KHSDZHI1,2, Tatiana SHEMYAKOVA1, and Spiridon RUSU3
1
Institute of Applied Physics, Academy of Sciences of Moldova, Kishinev, Moldova
2
Dniester State University, Tiraspol, Moldova
3
Technical University of Moldova, Kishinev, Moldova
[email protected]

Abstract – The possibility was investigated to compress and to split laser pulses at their nonlinear optical
transmission through semiconductor films.

Index Terms – biexciton, exciton, thin semiconductor film, ultrashort laser pulse.

energy of a biexciton from the crystal ground state. A part of

† radiation is reflected by the front end of the film, another
I. INTRODUCTION
part enters the film and generates biexcitons from the crystal
In recent years the processes of interaction of resonance
ground state due to the process of two-photon absorption.
laser radiation with excitons and biexcitons in thin
The film thickness is of the order of the wavelength of
semiconductor films were studied in several works.
propagating radiation or greater. Therefore, owing to the
The thin-film approximation allows one to reduce the set
multiple re-reflections from the front and rear crystal ends a
of nonlinear partial differential equations for the
forward and a backward electromagnetic waves with the
electromagnetic field and the medium to a relatively simple
set of ordinary differential equations, which in some cases amplitudes E f  z , t  and Eb  z , t  , respectively, appear in
admits exact analytical solutions. the film. The amplitude of the forward wave on the rear end
Recent considerable advances in manufacturing of E f  L, t  defines the amplitude of the wave transmitted
dimensionally confined semiconductor structures stimulate
the investigations of nonlinear optical properties of through the film; the amplitude of the backward wave on the
semiconductor thin films. This research is of an obvious front end Eb  0, t  defines the amplitude of the reflected
practical interest owing to the promising applications of thin wave. The problem is to find the amplitudes of the
semiconductor films for the development of the systems of transmitted and reflected waves. Such condition of the
ultrafast optical processing of information. problem can be realized, for example, in CuCl or CuBr
In this work the results are presented of theoretical crystals, where the biexciton binding energy amounts to
investigations of the effects of nonstationary nonlinear ~30–40 meV, and the oscillator strength of two-photon
transmission of two successive ultrashort pulses of generation of biexcitons is gigantic.
resonance laser radiation, received from the same source,
through a thin semiconductor film under conditions when II. MAIN RESULTS
each of the pulses can induce a two-photon generation of We consider the case of ultrashort laser pulses such that
t p   biex and assume t p  1 ps . For this case, the condition
1
biexcitons from the crystal ground state. A similar problem
for the case of one pulse was considered in [1, 2].
3
Let ultrashort pulses of laser radiation with the envelopes t p  t f is satisfied for the film thickness L  10 cm . The
of the electric field strength Ein (t ) and the photon carrier results of numerical calculation of the set of equations
frequency  are normally incident on a thin semiconductor describing the transmission of ultrashort pulses through a
films with the thickness L in vacuum. It is assumed that the semiconductor film are shown in Figs. 1-4.
duration of each pulse t p considerably exceeds the photon For large delay times between the incident pulses t d , the
first pulse induces the polarization of media, which
time of flight through the film t f ( t p  t f ), and the sum completely disappears by the moment of incidence of the
energy of two photons is in resonance with the generation second pulse. Therefore, we can consider that there exist
envelopes of each of two independent transmitted (reflected)
†
This work is supported by the joint grant of the Academy of Sciences pulses generated by two incident pulses. A considerable
of Moldova (project 10.820.05.18/UF) and the Ministry of Education and variation of the envelope of transmitted (reflected) radiation
Science of Ukraine.

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occurs for 0  td  t p when the envelopes of incident pulses the intensity of the pulses increases. For the intensity
S  60MW / cm the transmission and reflection exhibit
2
partially overlap. For this case, the polarization of media
induced by the first pulse has not enough time to disappear two or several peaks (see Fig. 2). It is interesting that the
by the moment when the second pulse falls. In this case a amplitude of the additional peak of transmission increases
nonlinear interaction of polarizations from the both pulses with the increasing of the excitation level and for
S  60MW / cm it can already exceed the amplitude of the
2
occurs; owing to this, the shape of the transmitted (reflected)
pulse becomes more complicated. main peak. But for the case of reflection the amplitude of the
It can be also seen in Figs. 1-4 that the amplitude of additional peak is always smaller than the amplitude of the
transmitted (reflected) pulse decreases fast with the main peak.
increasing of the delay time between the incident pulses in For intensity S  100MW / cm the second transmission
2

the range of small delay times ( t d t p ); the pulse further peak considerably exceeds the first (main) peak by its
splits into two pulses, which propagate independently. amplitude, and the third peak arise (Fig. 3).
It follows from Fig. 1 that for low intensities of incident
2
radiation S 10MW / cm the envelope of the transmitted
(reflected) pulse even for zero delay between the incident
pulses practically repeats their shape.

S  100MW / cm .
2
Fig. 3. Same as in Fig.1 for

For intensity S  200MW / cm and relatively large

2
td the
second subpulse of transmission arise.
Fig. 1. Dependence of the normalized intensity of transmitted radiation When S further increases the number of additional
versus the dimensionless time t and delay time between the pulses td for transmission (reflection) peaks increases; their width
3
becomes considerably less than the width of the incident
the film thickness L  10 cm and intensity of the incident radiation pulses. The envelope of subpulses for transmission has the
S  10 MW / cm
2
in the conditions of exact resonance ( 2 m, shape of the incident pulse.

where m is the exciton formation energy).

S  200MW / cm .
2
S  60MW / cm . Fig. 4. Same as in Fig.1 for
2
Fig. 2. Same as in Fig. 1 for

The transmission of incident pulses through a

semiconductor film acquires additional peculiarities when

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III. CONCLUSION REFERENCES

Consequently, the thin semiconductor film substantially [1] I. Beloussov, P. Khadzhi, A. Corovai, and D. Markov,
transforms successive ultrashort pulses passed through it and Abstracts of International Conferences on Coherent and
changes both their intensity and shape. While using films Nonlinear Optics/Lasers, Applications and
with various thickness, changing the intensity of incident Technologies (Russia, Kazan, August 23-27, 2010).
pulses and the delay time between them one can obtain the [2] I. Beloussov, P. Khadzhi, A. Corovai, and D. Markov,
compression of the initial pulse or to split it into a sequence Abstracts of 5th International Conference on Materials
of two or several pulses with considerably less duration. Science and Condensed Matter Physics (Moldova,
Chisinau, September 13-17, 2010), p. 57.

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Quantum Oscillations of Conductivity in

Bismuth Wires
Elena CONDREA
Institute of Electronic Engineering and Nanotechnologies, Academy of Science of Moldova, Chisinau,
[email protected]
Abstrect – Measurements of the resistance of bismuth nanowires with several diameters and different quality
reveal oscillations on the dependence of resistance under uniaxial strain at T = 4.2 K. Amplitude of
oscillations is significant (38 %) at helium temperature and becomes smearing at T = 77 K. Observed
oscillations originate from quantum size effect.
A simple evaluation of period of oscillations allows us to identify the groups of carriers involved in transport.
Calculated periods of 42.2 and 25.9 nm satisfy approximatively the ratio 2:1 for two experimentally observed
sets of oscillations from light and heavy electrons.
Index Terms – nanowires, quantum size effect.

thickness are explained by the change of the transverse

I. INTRODUCTION quasi-momentum caused by composition variation in the Bi-
The emergence of the investigations concerned with Sb alloy. An other manifestation of the QSE [8] was
various nanostructures is motivated partially by the very observed while studying the thickness dependence of the
interesting thermoelectric and magnetotransport properties ratio of the electron and hole density of states measured
of bismuth nanowires (NWs) that make them potentially under electric field effect (EFE). The method allows a rather
useful for device applications. Theoretical calculations [1-3] precise determination of the film thickness period of the
predicted that Bi nanowires should have an enlarged oscillations, which is about 370 Å.
thermoelectric figure of merit, which results from the In most of the above-mentioned cases, QSE was shown as
quantum size effect, have induced extensive studies of Bi an oscillatory behavior of the resistance dependence on film
NWs. Under the quantum size effect (QSE), several thickness. As is pointed out in [9], a variation in the value of
fundamental macroscopic characteristic of solids exhibit an the band overlap should also produce an oscillatory behavior
anomalous dependence on reduced size. Therefore, for of the kinetic coefficients. The changes in band overlap in a
subsequent applications, a precise determination of the size- bulk Bi samples under deformation was described by Brandt
dependent parameters of investigated nanostructures is [15]. The influence of the deformation on the band overlap
required. If the decreased size of wires or films becomes changes was tested for bismuth films condensed on mica
comparable with the electron wavelength (d ~ λ), the substrates [10]. Observed non-monotonous behavior of the
transverse motion of carriers is quantized. Thus, the energy resistance in bismuth films under sagging deformation is in a
spectrum splits into subbands. When the discreteness of the good agreement with the concept of QSE.
energy subbands becomes significant, an oscillatory To our knowledge, up to now, most of the studies on
behavior of electron and hole density of states (DOS) as a quantum oscillations in transport properties of Bi
function of thickness is expected for metal films [3,4]. nanostructures are concerned with thin films. The conditions
Oscillations of DOS are due to variation in number of the of observation of the QSE on thickness dependences of the
subbands with diameter. According to the theoretical kinetic coefficients of thin wires are complicated by
considerations of the QSE [3,4,9] all the transport difficulties in the preparation of a series of samples with a
coefficients which depend on the DOS should oscillate as a small increment in thickness and identical characteristics of
function of sample thickness with the period: the bulk. Despite a lot of recently developed techniques for
Δd = h/2(2mt*EF)½ , (1), preparation of nanowires [1, 2, 16] the bulk characteristic
where mt* is the transverse effective masses, and EF is data from different experiments depend not only on sample
Fermi level. cross-sectional dimensions and crystallographic orientation,
The main experimental results in the investigations of the but also on sample quality and
QSE have been obtained for thin semimetal films. The first purity, shell/matrix material and annealing treatment. It is
quantum size oscillations in the resistivity, Hall coefficient, possible to observe the oscillations of kinetic parameters,
and magnetoresistance with a period of 400 Å were observed due to size-quantized energy spectrum on the individual
in thin bismuth films [5]. Investigations [6] of bismuth films cylindrical nanowire under certain external influence, for
in large range of thickness (200 - 3000 Å) revealed that the example, by impurity doping or deformation.
period of the resistance oscillations varied from 40 to 250 Å The aim of this study was to study transport coefficients
with sample thickness. The difference in the period was of individual bismuth nanowires under condition of QSE by
attributed to the differences in the carrier concentrations due applying uniaxial stress for tuning the electronic structure
to growth conditions. and inducing band overlap changes. According to the
Quantum oscillations in the resistance of bismuth- condition of QSE realization (d ~ λ), an oscillating behavior
antimony alloy films were registered under variation in both in transport coefficient of Bi samples is expected at
thickness and Sb concentration at a fixed thickness [7]. The diameters below 100 nm. One should note that uniaxial
concentration oscillations in a sample with constant strain in Bi NWs promotes the increases of band overlap

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between L-electron pockets and T-holes pocket at constant reproducible quantum oscillations on R(ε) were observed in
band gap, in contrast to its decrease under QSE. the thinner NWs with a diameter of 70 nm. The dependences
of resistance versus uniaxial strain R(ε) for Bi wires with the
diameters d ≥ 100 nm do not exhibits any oscillations and is
II. EXPERIMENTAL METHODS AND SAMPLES
similar to the one observed by us for thicker wires [13] and
Long Pyrex-coated Bi wires were fabricated using the
whiskers [11].
same improved variant of the Taylor method. This method,
Fig. 2 shows the temperature dependences of the
which is presently known as the glass-coated melt spinning
electrical resistance R(T) for Bi NWs with various
method, consists in the melting of a metal in a glass tube by
diameters. Observed R(T) dependences are consistent with
rf induction heating and drawing a glass capillary in which
previous results for Bi wires [14] and Bi nanowire arrays [1].
the molten metal is entrapped.
Curve 2 in Fig. 2 presents R(T) dependence for a 90 nm NW
The wire axis is at an angle of about 19 with the bisector after thermal treatment. History of the thermal treatment was
axis C1 in the bisector-trigonal plane C1C3. This orientation not simple. Various variants of thermal treatment were tested
is the same as that observed in Bi nanowire arrays by Z. and the optimal one was chosen. The NWs were annealed at
Zhang et al. [1]. Due to high elasticity of Pyrex capillaries, 180° C for 10 h under vacuum with slow cooling back to
the limit of elastic stretching of the glass-coated Bi wires room temperature. An evident increase of value of a residual
attains = 3.5 % (in comparison for Bi whiskers  = 2.0 % resistance ratio (RRR) for the 90 nm wire after thermal
[11] and for bulk Bi samples = 0.4 % [12]. Due to small treatment testified to an improved quality of annealed NWs.
dimensions of glass-coated NWs, it was not possible to This supports the idea that a semiconducting behavior of
apply mechanical loading directly to them. For the R(T) does not imply that a band gap opens even in the thin
measurements under uniaxial strain, the glass-coated wires wires, a negative TCR may be rather an evidence of large
with d = 70 – 150 nm and the length L 0 = 2.0 – 3.0 mm were defect density inside the as-prepared wires.
mounted on an elastic bronze ring in a special insert with If we attribute the presence of oscillations on R(ε) in Fig.
stretching device similar to the method, used for whiskers 1 to the manifestation of QSE, in addition to the main
[11]. The stretching was directed along the wire axis, i.e., condition d ~ λ for QSE occurrence [4], we should consider
close to the bisector axis C1. The measurements of resistance some important requirements such as a small washing out of
were performed using two-probe method. Resistance the discrete energy spectrum:
variation was noted as ∆R/R = (R - R0 )/ R0 where R0 is the h/ τ << ΔE , (2 )
value of resistance in non-deformed state. Strain variation and a small temperature smearing:
was noted as = (L - L 0 )/ L 0 where L0 is the length of the kT << ΔE , (3)
wire in non-deformed state. Electrical contacts to the wire
ends were made by Wood‘s alloy. Low dc currents (0.1 μA ≤ 0 50 100 150 200 250 300
I ≤ 1 μA) were used to make sure that the voltage of the 1,8 1,8

sample was a linear function of the applied current. 1

1,6 1,6
2
III. RESULTS AND DISCUSSION
1,4 1,4
The studies of the strain dependences of the resistance R(ε)
at 4.2 K for wires
R(T)/R(300K)

1,2 1,2

3
1,0 1,0

0,8 4 0,8
30
0,6 0,6
4.2K
5
0,4 0,4
R/R (%)

0 0 50 100 150 200 250 300

T (K)
77K
Fig. 2. Temperature dependence of resistance normalized to the resistance at
-30 300 K for as-prepared Bi NWs: (1) d = 90 nm, (3) d = 120 nm and thermal
annealed: (2) d = 90 nm, (4) d = 120 nm, (5) d = 150 nm.

0,0 0,8 1,6 2,4

Strain (%) where τ is the relaxation time, taking into account scattering
both in volume and on the surface; ΔE is the distance
between discrete energy subbands. Inequality (2) means a
Fig. 1. Relative variation of the resistance as a function of applied strain for high mobility and/or large free path length for carriers
90 nm Bi nanowire measured at 4.2 K and 77 K.
involved in transport. It seems that all the requirements for
with various diameters revealed the oscillating QSE are satisfied for annealed 90 nm wire at T = 4.2 K.
dependence of the resistance on applied deformation in wires The observed resistance oscillations were reproduced on
with a diameter of 90 nm subjected to thermal annealing all the wires with a diameter of 90 nm from the series of
(Fig.1). Since an oscillating behavior in samples subjected to thermal annealing. As one can see from
transport coefficient of Bi wires is expected at diameters Fig. 1, the R (ε) dependence at 4.2 K exhibits a modulating
below 100 nm, we can suppose that observed oscillations are profile consisting of two sets of oscillations with different
due to QSE. To our surprise, non-discernable and non- periods determined by different groups of carriers. First, we

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supposed that two different periods of oscillations are due to electron pockets. In terms of previous results on ETT with
contribution of electrons and holes to electrical conductivity. the vanishing of one electron pocket, the work of extension
It is known that difference in the periods of electron and hole of ε = 0.96 % should be on the order of the energy shift of
quantum oscillations results from the anisotropic properties electron pocket C with strain. Since the measurements were
of Bi. made in the elastic deformation range, we may use the value
A rough evaluation of possible periods of quantum of the elastic modulus for bulk Bi crystal along the bisector
oscillations in 90 nm bismuth wire was made by formula (1). direction; thus, it is possible to determine the tensile load
The value of effective transverse mass of heavy and light dependence P on the value of extension ε = ΔL/ L 0 which is
electrons was used from the model of the subband structure approximatively P = 0.38 GPa at ε = 0.96 %.
calculated in [1] for the Bi nanowire arrays with the same A rough estimation of value of the energy shift was made
crystal orientation, corresponding to [1011]. This is our case by using the values of shifting rate dE/dF of electron pockets
where three groups of carriers operate: heavy electrons from under anisotropic deformation along the bisector direction
two equivalent pockets A and B, light electrons from pockets for bulk Bi crystals calculated by authors in [17], which are:
C, and heavy T-holes. According to [1], as the diameter of dE/dF = 0.5 meV/kg for pocket C and dE/dF = - 0.6 meV/
Bi nanowire arrays decreases below 100 nm, the band kg for pockets A and B. In our case, the value of energy
overlap between light and heavy electron pockets and T-hole shift was determined at a strain of 0.96 %, where quantum
pocket decreases in the different ways, thus resulting in the oscillations with large period disappear. Calculated value is
splitting of the L-point band edge. In this model, the band dE ≈ 19 meV. Because of some involved calculational
edge energy of each subband is determined by the average uncertainties, the value of dE ≈ 19 meV is rather
transverse effective mass, approximated by the appropriate appreciative; nevertheless, it is reasonable of the same order
effective cyclotron mass. The values of effective masses with value of Fermi energy level and of the band overlap (16
calculated by authors of [1] are: m* = 0.00212m0 and m* = meV) for light electron pocket from the model of electronic
0.00372m0 for light and heavy electrons, respectively. band structure for 90 nm Bi NWs, advanced by authors of
Estimated periods for our 90 nm NW are: Δd 1 = 42.2 nm; [1].
Δd2= 25.9 nm and Δd3 = 16.0 nm for light and heavy
IV. CONCLUSIONS
electrons and holes, respectively.
Systematic measurements of the resistance of bismuth
Coming back to measured quantum oscillations of
nanowires with several diameters and different quality reveal
resistance (Fig.1) we note the period ratio of 2 : 1 for two set
oscillations on the dependence of resistance under uniaxial
of observed oscillations. Two of calculated periods 42.2 nm
strain at T = 4.2 K. Amplitude of oscillations is significant
and 25.9 nm satisfy approximatively the ratio 2 : 1. The
(38 %) at helium temperature and becomes smearing at T =
calculated value of 16.6 nm for hole period is overestimated
77 K. Observed oscillations originate from quantum size
as a result of using the value for hole transverse mass m* =
effect.
0.21m0 available for bulk Bi. The absence of quantum
The absence of quantum size oscillations in resistance
oscillations from holes can be caused by its small period and
dependence for 70 nm wires can be explained partially by
non-detectable amplitude versus background. Thus, we can
scarce number of light electrons responsible for oscillations
suppose that quantum oscillations with large amplitude and
with decreasing diameter [1] and partially by imperfection of
period of 42.2 nm occur from the light electrons with
the nanowires.
smallest effective mass, and quantum oscillations with weak
A simple evaluation of period of oscillations allows us to
amplitude and period of 25.9 nm occur from heavy electrons
identify the groups of carriers involved in transport.
from pockets A and B. A significant amplitude (38%) of
Calculated periods of 42.2 and 25.9 nm satisfy
resistance quantum oscillations with Δd1 = 42.2 nm is due to
approximatively the ratio 2:1 for two experimentally
the low quantum numbers of the subbands located below
observed sets of oscillations from light and heavy electrons.
Fermi energy level in the pocket C with light electrons. The
The importance of the quantum size effect manifestation
vanishing of these oscillations at the deformation higher than
in the resistance dependence on strain goes beyond studying
1% is suggestive of a change in the Fermi surface topology,
the structure of electron spectrum, it can also be applied to
known as an electronic topological transition (ETT) or
investigate the spectrum of phonons. With a view to
Lifshitz transition. As a result of our previous investigations
elucidate some aspects of the practical use of nanowires, we
[13] of the changes in the Fermi surface topology under
plan the further investigations under strain of the
stress by means of Shubnikov-de Haas oscillation
thermopower, which at low temperature may be due to the
measurements, we have found the upward shift of the light
diffusive or phonon drag mode of carrier interaction.
electron pocket C relative to the other two pockets A and B
up to its complete vanish at a high strain. Due to the
ACKNOWLEDGEMENTS
continuing increase in the band overlap between L-electron
This work was made possible by National Project no. 210
pockets (A and B) and T-hole pocket, quantum oscillations
PF under funding from CSSDT.
with a period of 25.9 nm are detected at a strain higher than
1 %.
REFERENCES
If we attribute the presence of the oscillations on R (ε) to
[1] Z. Zhang, X. Sun, M. S. Dresselhaus, J. Y. Ying and J.
the QSE manifestation, it is natural to make a brief analysis
Heremans Phys. Rev. B 61 4850 (2000)
of correlation between the value of uniaxial strain and the
[2] Y-M. Lin, X. Sun, and M. S. Dresselhaus Prys. Rev B
period of observed oscillations Δd in 90 nm wires. Though
62 4680 (2000)
the precise interrelation between applied uniaxial strain and
[3] V. B. Sandomirskii Zh. Eksp. Teor. Fiz. 52 158 (1967)
Δd is not known, we try to follow the influence of strain on
[Sov. Phys. JETP 25 101(1967)]
the Fermi level shifting through quantized subbands in

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[4] B. A. Tavger, V. Ya. Demikhovskii Uspekhi Fiz. Nauk Zh.Eksp. Teor. Fiz. 47 455 (1964)
96 61 (1968) [11] V. N. Lutskii Phys. Stat. Sol. A 1 199 (1970)
[Sov. Phys. Usp. (1969) 11 644] [12] T. W. Cornelius, M.E. Toinil Molares, R. Neumann,and
[5] Yu. F. Ogrin, V. N. Lutskii, and M. I. Elinson Zh. S. Karin J. Appl. Phys. 100 114307 (2006)
Eksp. i Teor. Fiz. Pis‘ma v Redaktsyu 3 114 (1966) [13] Yu. P. Gaidukov, N. P. Danilova and M. V. Shcherbina-
[Sov. Phys. JETP Letters 3 71 (1966)] Samoilova Zh. Eksp. Teor. Fiz. 77 2125 (1979)
[6] E. P. Fesenko Fiz. Tverd. Tela 11 2647 (1969) [Sov. Phys. JETP 50 1018 (1979)]
[Sov.Phys. Solid State 11 2135 (1970)] [14] O. P. Hansen, I. F. Mikhail, M. Yu. Lavrenyuk and N.
[7] E. I. Bukhshtab, Yu. V. Nikitin and Yu. F. Komnik Fiz. Ya. Minina J. Low Temp. Phys. 95 481 (1994)
Nizk. Temp. 3 755 (1977) [15] M. Gurvitch J. Low. Temp. Phys. 38 777 (1980)
[8] A. V. Butenko, Dm. Shvarts, V. B. Sandomirskii and [16] P. P. Bodiul, V. F. Garabazhiu, E. P. Condrea and A. A.
Y. Schlesinger Physica B 284-288 1942 (2000) Nikolaeva Czech J. Phys. 46 2417 (1996)
[9] E. F. Schulte Surf. Sci. 55 427(1976) [17] E. V. Bogdanov, M. Yu. Lavrenyuk and N. Ya. Minina
[10] N. B. Brandt, E. S. Itskevich and N. Ya. Minina Fiz. Tehn. Pol. 22 1348 (1988).

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Superposition of the luminescence spectra of

free and bound excitons in ZnP2-D48
Ion STAMOV, Lucretia NEMERENCO, Iurii IVANENCO, Nicolae SYRBU
Technical University of Moldova
[email protected]
Abstract – The luminescence spectra of ZnP2 tetragonal crystals doped Mn, Sn, Cd, Sb at 10 K emission lines
of bound excitons is detected. In the spectra non-phonon emission lines of bound and free excitons and their
phonon replicas is isolated. The emission lines by the levels of the axial center are described. The composition
of the luminescence of free and bound excitons at the axial center is investigated. In the region of phonon
replicas of free excitons observed enhancement of lines due to forbidden transitions involving the
recombination of excitons. A model of optic recombination transitions of the axial centre is proposed.

Index Terms – luminescence spectra, free and bound exciton, optical phonon, electron transitions, axial center

transitions is equal to 2.21 eV. Fig.1 shows

I. INTRODUCTION
8
photoluminescence spectra of specially nondoped and doped
Compound ZnP2- D4 indirect-gap semiconductors with with Mn crystals ZnP2 at 10 K in the short-wave region, i.e.
8 in the region adjoining the free exciton level. At the energy
band gap 2.21 eV at 10K. ZnP2- D4 crystals have a
2,2085 eV a weak peak of luminescence is found Eext L ,
pronounced birefringence, bright luminescence and a high
photosensitivity [1-3]. On the basis of these crystals active according to the edge absorption data it coincides with the
elements p-n structures, Schottky diodes, switches, optical radiation energy from the free exciton level. We explain
pulses are created and are promising materials for peculiarity x1 - x10 in the luminescence spectra by phonon
optoelectronic devices polarization. replicas of the free exciton recombination. The band xi is
behind the free exciton energy E gxlib = 2.2085 by the value of
II. RESULTS AND DISCUSSION.
optic phonons. In the luminescence spectra various optic
Optic spectra of absorption and luminescence are
phonons can take part [1]. The luminescence spectra with
measured in cryostat LTS-32C330 Workhorse-type Optical
many narrow lines bound excitons, in which different optical
with the help of double Raman spectrometer with the light
force 1:5 and dispersion of 5 A/mm. The crystals phonons were observed in the crystals ZnP 2 - D48 [1-3] and
ZnP2 - D48 have the structure described by the space group CdP2 - D48 [4].
D48 ( D44 ).The band gap ( Eg ) is determined by indirect

Fig.1. Luminescence spectra of undoped (a) and doped with Mn (b) crystals ZnP 2- D48 at 10K and the energy levels of the electron transitions of bound

excitons on axial center of Mn in the crystals ZnP2- D48 .

In the unit cell stacked 8 formula units, i.e. 24 atoms will discovered narrow lines E01-E05 and weaker lines x1-x10
go into unit cell, in the general case the number of phonon (fig.1, curve a). Emission bands of xi are phonon replicas of
branches is equal to 72. Availability of this quantity of free-exciton emission. These bands are observed
oscillation modes makes it possible to observe radiation of simultaneously with the narrow emission lines E01-E05 bound
free excitons with emission of many phonons. The excitons at the center of the impurity atoms Mn. Non-
luminescence spectra doped with Mn of crystals ZnP2- D4
8 phonon lines of radiation of bound exciton E 01(2,1951 eV),

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E02 (2,19440 eV), E03 (2,1928), E04 (2,19277) and E05 1

the level of free (Gext1) and bound E 0 (Gext2) excitons is
(2,18987) are seen as narrows lines. The bands xi are weaker
by hundreds times and they have halfwidth being practically equal to 13,3 meV, and optic phonons achieve the energy
by an order larger than the lines. These E01-E05 two types of value of 59.5 meV. Hence, exciton levels of bound (E 0) and
lines xi and E01-E05 of the radiative recombination are free exciton (Egx) satisfy the condition Ep1=Gext1-Gext2+Ep2.
observed simultaneously practically in one and the same Thus, the process of recombination radiation may occur
energy interval (fig.1). As it is known, in the unit cell of the simultaneously from two centres. The radiation caused by
8 annihilation of free excitons leads to appearance of a row of
crystal ZnP2 - D4 there are many atoms (N=24), this lib
bands (xi) in the longwave region from E ext (2,2085 eV) at
determining big quantity of oscillation modes of different
symmetry [1-3] in the wide energy range. At the temperature the energy distance being equal to the energy of optic
8 phonons.
10 K in the crystals ZnP2 - D4 the energy distance between

Fig.2. Fragments of the most intense luminescence lines ZnP2 - D48 crystals at 10 K, doped Mn (curve-e), Sn (curve-f), Cd (curve-a), Sb (curve a and b)

and luminescence spectra ZnP2 - D48 crystals at 10 K doped tin (Sn) and cadmium(Cd).

Electron transitions of the exciton bound on axial centre in energy distance between ()- determines the value of the
the ZnP2 are shows in the fig.1. We consider that narrow level splitting due to spin-orbit interaction (SO). In this
lines E 0  E 0 are due to phononless lines of exciton bound
1 5 model the value of splitting due to the spin-orbit interaction
is larger than the value of splitting due to the crystal field.
on axial centre [1-4]. The exciton consisting of the electron
The energy interval between - levels is equal to 2,2 meV.
with spin 1/2 and hole with spin 3/2 bound on the centre
The resulting intensity of the luminescence lines and their
with the axial symmetry forms (from the level J = 1) two
energy position shows that the spin-orbit splitting is greater
levels ( and ). Optic radiative transitions from the levels
than the splitting due to crystal field (fig. 2). In the transition
 and  (J = 1) are allowed and they determine phononless levels of bound excitons at the axial center should be
3 4
lines E 0 and E 0 . These lines are the most intense and they observed two intense emission lines as a permitted. These
disappear with the temperature growth (40 K). These lines lines should be detected in the short wave region.
are split by small value (~0,1 meV). The state with J = 2 Luminescence lines due to transitions from the levels from
under the action of the axial field is split into three levels , which transitions are forbidden by selection rules may occur
 and . Transitions from these levels are forbidden by the as weak intensity lines. The situation may change if the
selection rules. The phonon energy radiated by the crystal in phonon energy emitted by the crystal as a result of
the result of the free exciton annihilation in the luminescence annihilation of free excitons in the luminescence
spectra corresponds to the energy of radiation of the bound corresponds to the radiation energy of the forbidden
exciton forbidden transition. This leads to the resonance transition of a bound exciton. This can lead to resonant
excitation of the bound exciton forbidden states and to the excitation of forbidden states of the bound exciton and to the
removal of the ban and intensification of luminescence from lifting of the ban and increase the luminescence of
3 4 prohibited levels. The radiated energy of the phonon may
the forbidden levels. The radiation lines E 0 and E 0 are coincide with the energy position of the level of forbidden
determined by allowed transitions from the zones of states of bound exciton. At the free exciton annihilation
symmetry  and  correspondingly. These levels are split by lib
( E gx = 2,2085 eV) the phonon radiative band different from
the crystal axial field of the centre whereon the exciton is
lib
1 2
bound. The radiation lines E 0 and E 0 are split by 0,75 E gx at the energy distance 13,3 meV is observed. There is
meV and they are due to the levels  and  of the forbidden such a phonon of the symmetry E, it is radiated at the energy
state of the bound exciton. Spin-orbit interaction also leads 2,1951 eV. This radiative band coincides with the energy
1
to the state splitting and appearance of the level . The position of the level of bound exciton E 0 x (2,19515 eV)

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2 lib
and is close to E 0 x (2,19440 eV). E gx (2,2085 eV) - Egx
8
In the long wave region in the ZnP2 - D4 crystals Sb-
(13,3 meV) = Ei (2,1952 eV). Such a coincidence of energies doped there are two groups of lines that were previously
of phonon radiation resulting from the free exciton found in [1-3]. Narrow intense luminescence line A01
annihilation with the energy levels of bound excitons may 2
remove a ban of optic transitions from the levels of bound (2.1444 eV) and A0 (2.1442 eV) are non-phonon emission
exciton, which is put by rules of the bound exciton selection. lines of bound excitons to the axial center and are due to
The ZnP2 crystals doped with tin (Sn), cadmium (Cd) and transitions from levels Σ, Π (J = 1) in the ground state. These
antimony (Sb) also exhibit intense luminescence. In these 1
lines are split into 0.22 meV. Weak luminescence line B0
crystals narrow lines of radiation and more gentle
2 3
luminescence lines are observed. Figure 2A shows fragments (2.1422 eV), B0 (2.1417 eV) and B0 (2.1400 eV) are due
of the narrow luminescence lines, which are due non- to forbidden transitions from levels Σ, Π and Δ (J = 3 / 2) in
phonons excitons lines of emission bound these impurities. the ground state (fig.3). Emission bands a1, a2, ..., a18 are
The luminescence spectra were measured on crystals doped 1
with these impurities under the same experimental lines phonon replicas of the non-phonon emission lines A0
conditions. In addition to these luminescence lines are 2
and A0 . In these spectra, there is no lifting of the ban
observed their phonon replicas. The luminescence spectra
8 because of the involvement of phonons, so the luminescence
ZnP2 - D4 crystals at 10K doped with tin (Sn) and cadmium
line B01 , B02 and B03 are weak. In addition, the
(Cd) are shows in the fig.2B. In these spectra revealed non-
1 2 3
phonon excitons lines bound to the tin (Sn) atoms (Fo1, Fo2, luminescence line B0 , B0 and B0 located in the long wave
Fo3) and their phonon replicas f1, f2, f3, f4, f5. In these spectra
in the longwave region of the band f5 has a large number of region of A01 and A02 . Thus, in the band model of the
peaks, which in this figure are not shown. In crystals doped center spin-orbit splitting is less than the splitting due to
with cadmium discovered a group of intense narrow lines crystal field. Splitting of the states J = 1 and J = 3 / 2 defined
Do1, Do2, Do3, Do4 and weaker lines d1-dn (fig.2 shows only 1 1
by the energy spacing between levels A0 and B0 is equal to
the four lines).
Narrow and intense luminescence lines Do1, Do2, Do3, Do4 2.2 meV. Scheme of electronic transitions responsible for the
8 luminescence line (spectra) is shown in fig. 3. In the long
crystals ZnP2 - D4 doped cadmium also caused by excitons 1
wave region observed by us previously in [2, 3] lines B0
bound to the cadmium atom, which, as in previous cases, an
2
axial center. Line Do1, Do2, Do3, Do4 are non-phonon (2,0212 eV) and B0 (2,0210 eV) are non-pho luminescence
luminescence lines and the lines d1-dn - their phonon lines of bound excitons to different axial center.
replicas. The experimental results indicate that the
considered centers have identical parameters. Energy
interval Σ – Σ of the crystals doped with Mn (Е01 – Е03) III. CONCLUSION
equals 2.28 meV, Sn-doped (Fo1 - Fo3) is 2.0 eV and Cd- The luminescence spectra of crystals diphosphide zinc
doped interval Do1 –Do3 is 2.3 meV. As can be seen, the doped tetragonal Mn, Sn, Cd, Sb describes allowed and
splitting due to crystal field of the states of electron with forbidden recombination transitions in the model levels of
spin Je = 1 / 2 and a hole with spin Jh = 3 / 2 for the three the axial center. Superposition of the luminescence of free
considered centers (impurity atoms) is almost identical. and bound exciton increase emission lines due to forbidden
recombination transitions involving of excitons on the axial
center. Amplification with the levels of forbidden transitions
of bound excitons occurs at the coincidence of the phonon
energy with the energy of the forbidden transition of a bound
exciton.
REFERENCES
[1] N.N. Syrbu, Optoelectronic properties compounds A2B5,
td.Stiinca, Kishinev, 1983
[2] N.N.Syrbu, V.I.Morozova, G.I.Stratan, Phys. and
Technics of Semicond., vol. 23 (10), 1771 – 1777, 1989.
[3] N.N.Syrbu, V.I.Morozova, G.I. Stratan,
Sov.Phys.Semicond, vol 26 (1), pp. 42-46, Jan 1992,
Translated from Phys. and Technics of Semiconductors,
vol. 26 (1), pp. 74 – 82, 1992.
[4] R. Bindemann, H.Fisher, K.Kreher, N. N.Syrbu, Phys.
Fig.3. The luminescence spectra ZnP2 - D48 crystals at 10K doped with tin St. Sol. (b), vol. 69 (2), pp. K79 – K84, 1975,
(Sn)

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Exciton Spectra of AgAsS2 Crystals

Lucretsia NEMERENCO, Iurie IVANENCO
Technical University of Moldova
[email protected]
Abstract – Reflectivity and wavelength modulated reflectivity spectra of AgAsS2 crystals are investigated in the
region of exciton resonances. The exciton and energy band structure parameters were determined.

Index Terms – Reflectivity, modulated reflectivity spectra, energy band structure, exciton spectra

polarization are due to electronic transitions from the V1 and

I. INTRIDUCTION
V2 valence bands to the C1 and C2 conduction bands in the
AgAsS2 crystals belong to layered materials with different
center of the Brillouin zone. The energy values of 2,358 eV,
anisotropy degree of interatomic interaction forces. AgAsS2
2,402 eV, 2,358 eV and 2,402 eV define the minimal energy
compound crystallizes in a monoclinic lattice with С2/с – С2h6
intervals between V1-C1, V2-C1, V1-C2 and V2-C2 bands,
spatial group. The lattice parameters are as following: а -
respectively.
17.23, b = 7.78, с= 15.19Å, β- 101°12'. Unit cell contains 24
formula units (Z=24), while the primitive Bravias lattice
contains 12 units (Z=12). Smithite crystal structure belongs
to the Сс — Сs4 spatial group. In AgAsS2 crystals
interatomic interaction forces are divided into strong
intramolecular (intralayer) forces and weak intermolecular
(interlayer) forces. In these crystals, it was possible to
distinguish the splitting of vibrational modes caused by
intralayer and interlayer interaction and to define the
splitting of vibrational modes by the double Davydov
resonance. Effective Szigeti charge, dynamic effective Born
charge, cation and anion relative ionic charges were defined.
AgAsS2 crystals grown in ampoules by chemical vapor
transport method represent plates with mirror surface 2.5x1.0
cm2 with thickness of 300-400 µm. The surfaces of some
plates were parallel to the C axis. Reflection spectra and
wavelength modulated reflection spectra were measured by
the MDP-2 spectrometer. For low-temperature
measurements the samples were mounted on the cold station
of a LTS-22 C 330 optical cryogenic system. Fig.1. Transmittance spectra of AgAsS2 crystals at 300К with Е||с and Ес
polarization (crystal thickness of 78µm - curves р1,р2,р3; crystal thickness
II. EXPERIMENTAL TECHNIQUE AND RESULTS of 54µm -curve р4; crystal thickness of 4,5µm - curve р5).
The edge absorption edge of AgAsS2 crystals at room
Absorption spectra at 300K and 10K (spectra are
temperature for Е||с and Ес polarization is different. The discussed below) give evidence that the fundamental
absorption edge for Е||с and Ес polarization at photon bandgap is formed by direct allowed transitions. The exciton
energies energy E ≥ 2,3eV increases rapidly and crystals binding energy is small (12,3meV) and the excitons are
with thickness of few microns become opaque (fig. 1). dissociated at room temperature. The anisotropy of the
AgAsS2 absorption edges are shifted to higher energies with absorption edge at 2.3 eV is due to the presence of polarized
decreasing temperature. The temperature shift coefficient electronic transitions which take place in accordance with
=Е/Т for Е||с and Ес polarization is equal to 3,110-4 the selection rules for electronic transitions of С2h5 symmetry
eV/K. The ЕgA and ЕgВ absorption bands are observed at group crystals [1-2]. The transitions are split due to crystal
energies of 2,358eV and 2,402eV in the transmittance field. At the same time, there is a splitting due to the spin-
spectra of crystals with thickness d = 5,7 µm measured in orbit interaction.
Е||с polarization (fig. 1). For Ес polarization, the ЕgC and Low-temperature measurements showed that the
ЕgD absorption bands are observed at energies of 2,445eV fundamental bandgap is formed by direct allowed
and 2,510eV, respectively. The character of changes in the transitions. The fine structure of the wavelength modulated
spectra of edge transmittance (absorption) gives evidence optical reflection spectra was investigated in the
that the absorption edge is formed by direct allowed fundamental absorption edge region at the temperature of
transitions. The anisotropy of edge absorption is due to 10K. For the first time, the ground and excited states of four
direct polarized electronic transitions which take place in exciton series A, B, C and D were observed. Series A were
accordance with the selection rules for electronic transitions observed for Е||с polarization with the ground state n=1 at
of С2h6 symmetry group crystals. The four observed 10K at the energy of 2,3975eV and with the excited state
maximums of transmittance (absorption) spectra in the n=2 at the energy of 2,4075eV. The Rydberg constant is
region of the intrinsic absorption for Е||с and Ес equal to 13,3meV and the minimum bandgap is equal to

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2,4108eV. Exciton series B, C and D are situated in the room temperature. Consequently, the structure of the
short-wavelength interval. For exciton series D the minimum polarized electronic transitions can be discussed within the
bandgap is equal to 2,5792eV. The Rydberg constant is framework of the selection rules for electronic transitions
equal to 24,4meV. Therefore, the exciton binding energy is without taking into account the symmetry of exciton states.
small (13,3meV and 24,4meV), and they are dissociated at

Fig.2 Reflection spectra and wavelength modulated reflection spectra of AgAsS2 crystals in Е||с and Ес polarization at 10К.

The lines n=1 were observed in the reflection spectra of Rydberg constant determined from the energy position of the
AgAsS2 crystals at the temperature of 10K and Е||с lines n=1 and n=2 (fig.1) for these exciton series is equal to
polarization ( t = 2.417eV,  L = 2.418eV, see Fig.1). For 13,3meV. The energy continuum (Eg, n = ) is equal to
2.4108 eV. A maximum and minimum of reflection with a
this polarization type, the excitons of Г2¯(z) symmetry are
weak change in the intensity of the reflection (2%) are
active for crystals of C2h symmetry. The reflection spectra in
detected for Ес polarization in the reflection spectra at the
the region of the line n=1 has a usual exciton form with a
energies 2,439 – 2,440eV. Intensive features are revealed in
maximum and a minimum. These features are due to the
the wavelength modulated reflection spectra at the energies
presence of transverse and longitudinal excitons. Based on
2,4396eV, 2,4642eV and 2,4682eV which are due to the
these data the energy of longitudinal-transverse splitting of
states n=1, n=2 and n=3 of excitons with Г2¯(z) symmetry.
Г2¯(z) excitons was estimated to be equal to 1meV. In the
The Rydberg constant for these exciton series obtained from
spectral dependence of the wavelength modulated reflection
the calculation according to the energy position of the
(fig.2), the intensive lines were defined at the energy levels
ground and excited states is equal to 32,8meV. The energy
of 2,4175eV and 2,4275eV which are due to the states n=1
and n=2 of the hydrogen-like Г2¯(z) exciton series. The continuum (Eg, n = ) is equal to 2.4724 eV (fig.2).

TABLE 1. EXCITON PARAMETERS OF AGASS2 CRYSTALS

A(eV) B(eV) C(eV) D(eV) ∆cf(meV) ∆so(meV)
Exciton n=1 2.418 2.440 2.509 2,575 -0.002 151
state n=2 2.428 2.464 2.520 2,593
n=3 2,468 2,522 2,597
R 0.013 0.032 0.015 0,024
Eg 10K (n=∞) 2.431 2.472 2.450 2,529 -49.6 149
E(min.T) 300K 2,358 2,402 2,445 2,510

A maximum at 2,505eV (transverse exciton) and a C binding energy is equal to 14,6meV and the continuum
minimum at 2,508eV (longitudinal exciton, fig.3) are (Eg, n = ) is equal to 2,5235eV. A maximum and a
observed in Ес polarization. Longitudinal-transverse minimum of the reflection spectra are found at the energies
splitting of Г5 exciton is equal to 2,0meV. This hydrogen- of 2,566eV and 2,572eV in the short-wavelength region of
like series detected in the Ес polarization (conventionally the C-series for Ес polarization. In the wavelength
named C- Series), in accordance with the selection rules [1- modulated reflection spectra, the features are observed at the
3], can be formed by the states of orthoexciton with energies of 2,5752eV, 2,5932eV and 2,5970eV, which are
2Г1¯+Г2¯ symmetry. These states are forbidden in the due to the states n=1, n=2 and n=3 of excitons series D with
electric quadrupole approximation. The lines n=1, n=2 and 2Г1¯+Г2¯ symmetry, respectively. The Rydberg constant of
n=3 at the energies 2,5089eV, 2,5199eV, 2,5201eV, these exciton series is equal to 24,4meV from the calculation
respectively, are observed in the wavelength modulated of the lines n=1 and n=2 energy position. The continuum
reflection spectra. Taking into account the energy position of (Eg, n = ) of these series is equal to 2,5992eV.
the ground state n=1 and excited state n=2, the exciton series

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TABLE 2. EXCITON PARAMETERS AND ENERGY BAND PARAMETERS OBTAINED FROM THE CALCULATIONS OF THE OPTICAL
REFLECTION SPECTRA AND WAVELENGTH MODULATED REFLECTION SPECTRA OF AGASS2 CRYSTALS
E||c, 10K,  = 7.4 Ec, 10K,  = 7.26
Parameters A B C D
0, eV 2.411 2.439 2.506 2.566
LT, meV 1 1 2 4
, meV 0.2 0,2 0.16 0,5
M, m0 1,5
R, eV 0.013 0.032 0.015 0.024
, m0 0.054 0,129 0.06 0,093

mC , m0 0.1 0.1 0.1 0,1

mV , m0 0,12 0.44 0.14 1,4

In the region of exciton resonance, the reflection

coefficient is equal to 0,22-0,23 and d changes in the REFERENCES
interval 7,26-7,4. The value of the background dielectric
constant near the exciton resonance was used in calculations. [1] E.P.Zaretskaya, V.F.Gremenok, Yu.Rud,
With d = 7.4, the effective mass µ = ε b2R/RH equal to V.Yu.Rud,S.Schorr, Book of Abstrakts, 16th
0.054m0 was obtained for the most long-wavelength exciton, International Conf.on Ternary and Multinary
where R (0,013eV) is the Rydberg constant for Г2(z)- Compounds, Sept. 15-19, 2008, Berlin
[2] Chichibu S, Mizutani T, Murakami K, Shioda T,
exciton and RH 2 is the Rydberg energy of hydrogen atom
Kurafuji T, Nakanishi H, Niki S, Fons P J, and Yamada
(13,6eV). The Bohr radius (aB) of the S-State for Г2(z)- A J. 1998 Appl. Phys. 83, 3678
exciton is equal to 0.310-6 cm-1. With d = 7.4, the effective [3] Schuler S, Siebentritt S, Nishiwaki S, Rega N,
mass µ = εb2R/RH of B-excitons with Г2(z)-symmetry is Beckmann J, Brehme S, and Lux-Steiner M Ch 2004
equal to 0.129m0, the exciton binding energy being equal to Phys. Rev. B 69 045210
R =0.032eV. The Bohr radius (aB) of the S-State for Г4-
exciton is equal to 0,2110-6 cm-1 (table 2).

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Large Oscillator Strength Excitons in PbGa2S4

Crystals
PARVAN V., MIROVSCII V., MASNIC A.
Technical University of Moldova
[email protected]

Abstract – In PbGa2S4 crystals the exciton states with the energy of about 290 meV and high oscillator
strength (longitudinal – transversal dissipation of 75 meV) were observed. The ground states of the excitons
are not dissociated at the room temperature. At the temperature of 77 K and 8.6 K the ground (n=1) and
excited (n=2,3) states of two excitons series A and B are observed. The Bor radius for A excitons is about 70 Å
and for B excitons is about 10Å.

Index Terms – PbGa2S4 , excitons series, Bor radius for excitons, excitons with large binding energy and
oscillator strength, parameters of excitons

I. INTRODUCTION
Usually, the excitons are not observed in semiconductors at
room temperature due to low value of their exciton binding
energy. The efficiency of absorption and refraction at the
exciton resonance frequency is low due to the week exciton
strength and the high values of the exciton radius. According
to the literature data [1,2], two factors restrain the
implementation of semiconductors in optoelectronic devices:
(i) the low value of exciton binding energy and the
dissociation of excitons at room temperature, and (ii) the low
contribution of exciton states to the optical constants of
crystals (the low value of the exciton oscillator strength) due
to the high values of the exciton radius.
In this paper we present results of investigation of exciton
states in PbGa2S4 crystals with the ground state Bohr radius
of 70 Å and 10 Å. The excitons with the Bohr radius of 10 Å
are observed at both low and room temperatures. Apart from
that, excited n = 2 and n = 3 states are observed al low
temperature. The reflectivity spectra contours are calculated
and the main exciton parameters are determined. A model of
bands responsible for exciton transitions at К=0 is proposed.
Fig.1 Reflection spectra and wavelength-modulated reflection spectra of
II. EXPERIMENTAL DETAILS crystal PbGa2S4 in the polarization Е║с and Е┴с measured at 10K and
PbGa2S4 crystals are promising materials for photo- calculated by the dispersion relation contour of reflection spectra for
detectors sensitive in the UV region. These crystals has wide polarization Е║с
ban, with a band gap  3 еV. Exciton transition are detected The reflection spectra in the vicinity of these lines has
at room temperature. Reflection and transmission spectra traditionally form characteristic excitons with maximum and
were measured on JASCO-870 spectrometer, spectra at 10K minimum. Maximum of reflection spectra at 3,042eV is the
were measured on СДЛ-1 spectrometer in cryostat LTS-22 basic state n=1 and maximum at 3,094eV is the excited state
C330 Workhorse type Optikal. The comaund PbGa 2S4 n=2 of longwave exciton series A (series conventionally
24
crystallizes in rombic lattice with space group D2h with designated A). In the spectra form Fig.1 clearly stand out the
parameters а=20.706 Å, b=20.380Å, с=12.156 Å [7, 8]. minima of reflection spectra at 3,053eV. These features are
Edge absorption is due to direct allowed transition. For the due to the presence of transversal (maximum) and
longitudinal (minimum) of excitons. Based on these data
polarization Е||c and Ес the edge absorption split to 20-25
were estimated the energy of transverse-longitudinal
meV.Line spacing: single. Text organization: two columns.
splitting of the basic state of A-exciton ∆ωLT, which is equal
Column width: 8.3. Space between columns: 0.9 cm. Last
~11meV. In the right side of Fig.1 is presents the reflection
page columns must be equal in length. Header and footer:
spectra modulated by the wavelength at 10K of PbGa2S4
different for odd and even pages. In the reflection spectra of
crystals.In the polarizations Е║с and Е┴с in a modulated
PbGa2S4 crystals at the minimum of interband interval at
10K in the polarization Е║с and Е┴с were detected lines at reflectance spectra revealed the line n = 1 ( t = 3,043eV)
3,042eV ones and weaker line at 3,094eV. and n = 2 (3.096eV). In the region of exciton resonance
reflection coefficient is 0.24-0.25, and εd varies in the range
7.4-8.2. The calculations used the value of the background

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dielectric constant near the exciton resonance. When εd maximum of reflection spectra) of B-excitons for the
= 7.6 and 7.0 reduced effective mass of the A-exciton polarizations Е║с and Е┴с is equal with 50 and 52 meV.
µ = εb2R/RH = 0.352m0, where - RH 2 the energy of the Considering the energy position of the base and excited
states of B-excitons was defined Rydberg constant which is
Rydberg hydrogen atom (13.6 eV). Rydberg constant R, equal with 291 meV in the polarization Е║с and 292meV in
obtained from the calculations on lines n = 1 and n = 2 is the polarization Е┴с. Taking into account magnitude of
equal to 0.070 eV. The minimum gap width at 10 K is 3.112 background dielectric constant (7,6-7,0) was calculated the
eV. In the short-wavelength region of the exciton A series of B-exciton reduced mass μ , which is equal with 1,126 m0.
reflection spectra revealed intense peaks at an energy of Energy of continuum for B exciton series is equal with 3.617
3.326 eV for polarization Е║с and at an energy of 3.317 eV eV (Е║с) and 3.610 eV (Е┴с). The values obtained for the
for polarization Е┴с. These lines are due to the base state n = binding energy 291-292 meV for B-excitons in crystals
1 exciton of B series. In the short-wave region were detected PbGa2S4 are near a record for the crystals with a bandgap of
maxima at energies 3.544 eV and 3.584 eV, which are the 3 eV. Exciton energy exceeds 290 meV are observed in
excited states n = 2 and n = 3 in the exciton series. In the crystals [1]. In NaI crystals the Rydberg constant is equal
spectra clearly stand out a minimum of reflection at 3.382 with 300 meV in the KI crystal binding energy is equal with
eV and 3.408 eV. These minima are caused by the energy of 400 meV. In other alkali-halide crystals the binding energy
the longitudinal exciton of B series. is more. Excitons with the same binding energy is related to
the Frenkel exciton. [1].
Thus, the observed exciton states in a series of crystals
PbGa2S4 can be attributed to the Frenkel exciton, and it
should be noted that the crystals are PbGa2S4 narrower gap
than the crystals of KI and NaI. The difference in bandgap
crystals PbGa2S4 and KI (NaI) is equal to 2.3 eV.

Fig.3 The transmission spectra of PbGa2S4 crystals measured at 300K in the

polarizations Е║с (curve shifted vertically downwards by 0,5, Е┴с and in
unpolarized light (the thickness of the crystals 17 microns).

In Figure 3 shows the transmission spectra of PbGa2S4

crystals at 300K in a polarized and not polarized light. In the
transmission spectra revealed state n = 1 and n = 2 for A-
excitons, respectively, at energies 2.990 eV and 3.044 eV.

TABLE 1. PARAMETERS OF EXCITONS AND BANDS OBTAINED

Fig.2 The luminescence spectra of PbGa2S4 crystals at temperature 20K, FROM THE CALCULATIONS OF THE OPTICAL REFLECTION
70K, 100K and 200K and changes of the energy maxima of the SPECTRA AND WAVELENGTH-MODULATED REFLECTION SPECTRA
luminescence with temperature change in the crystal. OF PBGA2S4 CRYSTALS
In the photoluminescence spectra of the crystals PbGa2S4 E||c, 10K,  = 7.6 Ec, 10K,  = 7.0
Parameters
excited by argon laser line observed narrow emission lines A B A B
x1, x2, A1 and B1 at the energies 2.9312, 2.9771, 3.0534 0, eV 3.042 3.326 3.042 3.317
and 3.3613 eV, respectively. The nature of the lines x1 and LT, meV 11 50 11 52
x2 has the impurity character, with the temperature , meV 0.19 60 0.16 60
increases, their intensity decreases (especially peak-x2). t, Å 25 20 25 20
Increase in temperature leads to a shift in luminescence
M, m0 3 5 3 5
peaks in energy position (Fig. 2). Temperature gradient
R, eV 0.070 0.291 0.070 0.292
changes of emission maxima position for ω LB and ωLA within
the limits of experimental error coincide. Temperature , m0 0.352 1.134 0.352 1.134
gradient changes of the maxima energy position for x1 and  0.17 1.71 0.17 1.71
m C , m0
x2 differ (Fig. 2), which indicates extrinsic nature of these
peaks. Most likely, these peaks are due to bound excitons.
The energy position of lines A1 and B1 correspond to the mV , m0 2.83 3.29 2.83 3.29

energy of longitudinal excitons A and B. The estimated The difference in energy for base state n = 1 in the
value of the transverse-longitudinal splitting ∆ω LT (were
polarization Е║с and Е┴с does not exceed 20 meV. At the
taken the difference between the energy minimum and energy of 3.257 eV observed maximum of absorption due to

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transitions to the base state of transversal B-excitons. Taking while the 3 excitons are active in the E||c, (k||a, k||b)
into account the energy position of n = 1 and n = 2, Rydberg 
constant is equal to 90 meV. This value coincides with the polarization, and the 4 excitons are dipole-active in the
binding energy determined at 10K. Using the conditions E||a, (k|b, k|c) polarization.If one compares the obtained
1 1 1 experimental results with the exciton symmetries, one can
M  mV  mC and    were calculated the note that the long-wavelength A-excitons with 3 and 4
 
mV mC
effective mass of electrons and holes which are responsible (or 2 ) symmetry have similar parameters. The splitting of
for A and B series of excitons (Table 1). the ground exciton states does not exceed 20 meV. The
As seen from the table, the effective mass of electrons and symmetry of the B-excitons is the same as that of A-
holes are responsible for A and B exciton series are excitons. The energy position of the n = 1 state of B-excitons
different. These data indicate that the exciton series A is in the E||c and Ес polarizations also does not exceed 20
formed by a pair of zones V1 – C1 and Series B is formed by meV. On the basis of the selection rules and the obtained
a pair of zones V2 – C2. Effective Bohr radius aex are defined values of electron and hole effective masses, one can
by formulas of Bohr for hydrogen atom propose a following model of energy bands explaining the
аех = аВ  m0 /  exciton spectra: the A-exciton series is formed by the (V1-
 
C1) bands with Г 5  Г 5 symmetry, while the B-exciton
where aB the Bohr radius of hydrogen atom,  and -  
series is produced by the V2-С2) bands with Г 5  Г 5
dielectric constant and the reduced effective exciton mass. In
symmetry. According to this model, the both exciton series
discussed crystal PbGa2S4 exciton base state (n = 1) have
are produced in the center of the Brillouin zone as shown in
different radii of Bohr. For A-excitons aB is 70 Å, and for B-
Fig. 7. The C1 and C2 bands are probably degenerated in the
excitons in aB is 10 Å. Thus, we see two different exciton
with different Bohr radius. A series of excitons refer to center of the Brillouin zone, since the bandgaps for the Ес
Wannier-Mott excitons and B series can be considered the and Е||с polarizations obtained from exciton spectra coincide
Frenkel exciton. Exciton parameters are given in Table 1. in the limits of experimental errors.
We will analyze the energy band structure of PbGa2S4 III. CONCLUSION
crystals taking into account the exciton transitions discussed In conclusion, we note that the crystals were first
above. The wave functions of the valence and conduction discovered PbGa2S4 excitons with large binding energy and
bans of PbGa2S4 crystals are transformed according to the oscillator strength. These excitons contribute significantly to
irreducible representations 5 or 5 of the point symmetry the optical constants even at room temperature. On the basis
group D2h [23]. Therefore, one needs to consider the of such materials, you can create optoelectronic devices
selection rules of transitions from the ground crystal state  operating at room temperature, which action is based on
to the exciton К, Гех, j state, i. e. the conditions of physical principles of light interaction with excitons [2,3].
difference from zero of the matrix element of the transition
intK, ex, j, where K is the exciton wave vector, Гех REFERENCES
is the irreducible representation according to which the wave [1] R. Knox, Theory of excitons, (Mir, Moscow, 1966), 1
function of the exciton is transformed, j is the row, Гех is the st ed., p. 219.,Song,K.S.and Williams R.T.)1993).Self-
direct product of the irreducible representations l  h  Dl (i = trapped excitons.Springer-Verlag,Berlin
[2] L.V.Keldish Excitons in Semiconductor-Dielectric
0,1…) according to which the wave functions of electrons, anostructures/Phys.St.Sol.1997,Vol.164,N3
holes and their relative motion are transformed. The [3] V.S.Dneprovskii, E.A.Jucov, E.A.Malearov,
transitions occur under the action of the light. In the PbGa 2S4 S.G.Tihodeev, JETF,1998
crystals 2 excitons are dipole-active in the E||b, (k||a, k||c)
polarization,

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Effect of Time on the Properties of

Crystallization Agents: Ice-forming Aerosols
Efim ZASAVITSKY1, Valerii KANTSER1, Anatolii SIDORENKO1,
Ion GARABA2, Evghenii POTAPOV2, Nicolai KIM3
1
Institute of Electronic Engineering and Nanotechnologies “D.Ghitu”
of the Academy of Sciences of Moldova, [email protected]
2
Special Service for Active Influences on Hydrometeorological
Processes of Republic of Moldova,
3
Scientific Production Center “Meteoteh”, Russia
Abstract – The results of studies of the efficiency (yield) of pyrotechnic compositions used for the
prevention of hail in the Republic of Moldova as a function of storage time are described. The studies are
performed using an ingenious installation based on a small aerodynamic stand, which makes it possible to
control the efficiency of ice-formation of full-size generators in the on-line mode and to study the nucleation
activity of new reagents under dynamic conditions. It is shown that the efficiency of the pyrotechnic
compositions based on silver iodide (AgI) decreases depending on storage time. At the same time, the
decrease in yield for given standard storage conditions is on the order of 10% per year.

Index Terms – Ice-forming aerosol, silver iodide, AgI, aerodynamic stand

techniques and objectives of AIs [1].

I. INTRODUCTION
To date, we know a wide class of materials whose fine
The relevance of work on active impacts for the
aerosols can initiate the formation of ice crystals with a high
prevention of hail, the redistribution of precipitation, and the
probability. One of the most widely used reagents are those
thinning of fog and clouds does not give rise to doubts.
based on silver iodide (AgI). Ice-forming pyrotechnical
These works are carried out in many states. In the RM,
compositions based on silver iodide (AgI), which are used in
large-scale works on the protection of agricultural crops
antihail rockets for impacts on hail-hazardous clouds in the
from hail damage are carried out on a regular basis (in 2010
RM, yield more than 1013 g-1 of active ice-forming particles
the area of territories under protection was 1.4 mln ha);
at a temperature of the cloud (simulated) environment of -
thousands of antihail rockets are utilized for these purposes
10oC.
every year.
The theoretical foundation for describing the effects of
Along with cooling agents, ice-forming aerosols are
fine aerosols of ice-forming reagents based on the theory of
widely used as artificial means of crystallization in the
nucleation of ice on the surface of aerosol particles
practice of active influences on supercooled cloud
developed by H. Fletcher [2, 3].
environments. Ice-forming aerosols are fine particles of a
The use of pyrotechnic generators in different exposure
substance that, under given thermodynamic conditions in a
techniques requires reliable knowledge of their efficiency.
cloud, can act as nuclei (seed) for the formation and growth
Therefore, before using these tools in the active intervention,
of ice crystals.
it is necessary to experimentally prove their efficiency.
Ice-forming reagents are most commonly used owning to
We can state that the result of this impact on a potentially
a number of technical advantages, which result from the
hail-hazardous cloud with ice-forming reagents depends on
conditions of storage, delivery and dispersion in the zone of
many factors and, not least of all, on the yield of a particular
cloud seeding, etc. In the case of using these substances, the
generator, which depends on many factors: storage
method of active impacts is based on the formation of a
conditions, temperature, storage duration, etc. Thereby, the
necessary concentration of artificial ice crystals in the seeded
efficiency of pyrotechnic generators depends on observance
part of the cloud environment; that is, in a potentially hail-
of technological conditions of their manufacture as well as
hazardous cloud environment, it is necessary to form a
on the period and conditions of storage. Herein, a tendency
certain number of active ice-forming nuclei under given
of efficiency decreasing, sometimes by orders of magnitude,
conditions in the cloud and known conditions of introduction
can be observed [4].
of reagents into the atmosphere.
In this regard, laboratory technologies aimed at studying
Ice-forming reagents are effective means of artificial
the yield of generators are particularly relevant. To
crystallization of supercooled clouds and fog, which
implement an ideal case in which a technique for
determines their extensive use in the practice of active
determining the efficiency of means of crystallization most
influences (AIs) in many countries, including the Republic
fully takes into account different situations of impact on
of Moldova (RM). The ice-forming aerosol based on applied
supercooled clouds and various characteristics of generators
reagents is dispersed into cloudy atmosphere by means of
of ice-forming nuclei or crystals, we must provide the
special generators (rockets, pyrocartridges, ground-based
following conditions:
and airborne devices); their application is determined by

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• The efficiency of a generator should be studied using In the Eiffel chamber (d = 500 mm, L = 3 m), a device for
direct simulation over the entire set of parameters, both taking samples of ice-forming aerosol from the air flow is
parameters of the motion of the generator and the parameters placed. The general arrangement of the aerodynamic tube in
of the environment in which the generator operates; two project views is shown in Figs. 1 and 2. In the front part
• Any dilution and transfer of selected aerosol samples must of the aerodynamic tube, in front of the Eiffel chamber, an
not be accompanied by changes in temperature and access panel is arranged for the installation of full-size
humidity; generators of ice-forming aerosols and large fragments of
• The nucleation and growth of ice crystals must occur under samples of pyrotechnical compositions with reagents. The
the direct simulation of the basic parameters of the seeding flow velocity (m/s) in the HAT is determined by the method
zone: temperature, humidity, and the spectrum of droplet of measurement of gas dynamic pressure using a "Pitot
size distribution. tube."
The preference is given to aerodynamic tubes. Studies of
generators in aerodynamic tubes make it possible to acquire
reliable information on the efficiency of a particular
generator in strictly controlled measurement conditions.
II. THE TECHNIQUE FOR THE DETERMINATION OF
EFFICIENCY OF ICE-FORMING AEROSOL
GENERATORS AND EXPERIMENTAL DATA
The aerodynamic stand for the testing of full-size
generators of ice-forming aerosols is designed in the Institute
of Electronic Engineering and Nanotechnologies of the
Academy of Sciences of the RM with the participation of the
Special Service for Active Influences on
Hydrometeorological Processes of the RM.
This aerodynamic stand allows testing any type of
pyrotechnical generators of ice-forming aerosols, which are
used at present both in operations on protection of Fig. 1. A fragment of the HAT.
agricultural crops from hail damage and in operations
(experiments) on modification of precipitation.
It should be noted that the simulation of conditions of the
flight of a rocket using an aerodynamic stand is also caused
by the fact that the ice-forming activity of aerosols is
affected, to different extents, by many factors. One of them
is the ratio of the velocity of the generator to the velocity of
discharge of a gas-vapor stream from the nozzle of the
generator. In addition, the yield of active ice-forming
particles of AgI heavily and monotonically depends on this
parameter.
The main difficulty in these experiments is to form
particles, which are adequate to really used particles by their
physicochemical and, accordingly, ice-forming
characteristics. A practically significant parameter of
artificial crystallization, which is necessary to characterize
their performance under real conditions of impact, is the
yield of ice-forming particles in a temperature range of (-5 ’ Fig. 2. A fragment of the HAT with a system for sampling and
-15)oC. dilution of aerosol.
It should be noted that, despite the considerable number of
countries implementing projects on AIs, laboratories of this To ensure a correct representativeness of the aerosol
level are scarce in Europe (Russia, Bulgaria). sample in the aerodynamic tube, we carried out special
The aim of this work is to experimentally reveal the experiments to study the distribution of air velocity in the
dependence of the main parameter of rocket generators, i.e., tube. Figure 3 shows the results of the air velocity
yield, on external factors, i.e., temperature, time, storage distribution over cross section in the zone of the aerosol
conditions, etc., under laboratory conditions with a maximal generator at a flow rate in the working part of 30 m/s.
consistence of model conditions to real conditions of the It is evident that, for the used installation, the axis of
flight of a rocket in a potentially hazardous cloud upon symmetry in the horizontal direction almost coincides with
seeding with an ice-forming reagent. the cross-section center.
To simulate real conditions of the operation of generators, For better homogenization and mixing of the aerosol and
the technique was based on the use of a stand prepared of a the air, at a certain distance behind the generator, we
small horizontal aerodynamic tube (HAT) designed and installed a special unit, i.e., turbulator intended for the
constructed at the Institute of Electronic Engineering and intensive stirring of the aerosol plume in order to obtain a
Nanotechnologies, Academy of Science of Moldova. uniform aerosol concentration over the cross section at the
The diameter of the HAT d = 330 mm; the length L = 9 m. sampling point. The estimation of the uniformity of the
distribution of aerosol concentration over the cross section

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

showed that the ratio of the concentration at the center to the fog, variation in its density, and formation of ice
concentration at any point of the cross section varies within crystals.
10%. Supercooled fog in the chamber is created by the injection
of hot vapor, which condenses to form water aerosol with a
modal diameter of droplets of about 4 m.
+
24 Given the linear dimensions of the chamber, the vertical
temperature gradient in the chamber does not exceed 0.02
0
23 -
deg/cm; the horizontal gradient, 0.005 deg/cm.
The initial water content of fog depends on the duration of
¯
the introduction of vapor; it was 0.4-3.0 g/m3.
22
The accuracy of temperature measurement in the
chamber working volume is ±0.1oC.
v, m/s

21 For the experiment (measurement) temperature, we take

the temperature settled in the chamber working volume after
20 the formation of fog in it, before the introduction of the
aerosol sample.
19 The lifetime of vapor fog in the chamber for an initial
water content of 1’2 g/m3 is 2’3 min.
18 Fog in the cloud chamber is generated by the
-16 -12 -8 -4 0 4 8 12 16 condensation of a hot water vapor being introduced into a
cooled volume.
L, cm The activation of samples of ice-forming aerosol is carried
out in the chamber at specified temperature levels up to Т = -
+
Fig. 3. Distribution of air velocity in the cross section of the
aerodynamic tube 20oC.
Ice crystals that are formed on introduced nuclei grow to
The system of sampling and dilution allows representative sedimentation sizes and are recorded at the bottom of the
chamber using a thermostat. The quantity of the
sampling of the aerosol generated0 by a generator in the air microthermostats is determined by objectives of the specific
flow of the HAT. The intake is placed in the Eiffel chamber.
- pipe exposed at the center
The intake consists of a stainless experiment. According to the number of crystals formed,
of the tube with holes directed toward the flow, a piping knowing the characteristics of the equipment and
system, and a syringe. Since the difference between consumption data for the generator, we can calculate the
¯
atmospheric pressure and dynamic pressure is usually no yield of nuclei. It should be noted that the time of the
more than 1%, the transfer of the sample from the tract of manifestation of ice-forming nuclei depends on temperature;
the aerodynamic tube into a mixing chamber is carried out in addition, the kinetic constant decreases with decreasing
isothermally and with a constant humidity. temperature, and the time of the manifestation of a given
To prevent the suppression of the activity of ice-forming fraction of nuclei increases and is about 3 min at -5oC.
particles due to the effect of "re-seeding", it is necessary to The duration of one measurement (experiment) using the
obtain an optimum concentration of crystals in the mixing aerodynamic stand, which consists in the measurement of
chamber, which would provide a statistically significant the yield of active ice-forming particles, is 30-40 min at a
result of the experiment. In order to reduce the aerosol given temperature.
concentration, the sample had previously been dissolved in a For the determination of the yield of active ice-forming
cube with a volume of 1000 and 125 l, respectively (Figs. 1, particles according to this technique, it is necessary to take
2). into account a number of factors, the disregard of which can
The nucleation and growth of ice crystals occurs in a significantly distort results:
supercooled fog produced in the working volume of the  presence of significant temperature gradients in the
mixing chamber. In the capacity of a mixing chamber in the chamber working volume;
stand under discussion, we used an ILKA KTLK-1250  inhomogeneity of water content of supercooled fog;
climate chamber with a working volume of 1200 l  run-to-run reproducibility of fog parameters;
manufactured in the German Democratic Republic. In  local supersaturation of water vapor upon the
accordance with the objectives of the experiments, the introduction of aerosol in the chamber;
camera was modified as follows.  coagulation of aerosol particles in the process of
 Access holes were made in the door for the placing formation and introduction into the chamber, their
and removal of microthermostats. precipitation on chamber walls, injector, and feeding
 A system for introducing a measured sample of the hoses.
active aerosol into the working volume was The estimation of accidental errors of measurements
prepared. showed that the error of a single measurement is ±15% in a
 A fan to mix the air to reduce temperature gradients temperature range of -10 to 20oC and ±30% at the fog
was installed in the working volume. temperature of -5oC. As the temperature decreases, the error
 A temperature and humidity sensor was installed. is reduced. The total systematic error is ± 3% and can be
 In the upper part of the cloud chamber, a lighting ignored in the calculations.
unit was installed; it generated a beam of light for Based on the designed aerodynamic stand and developed
the visual observation of the process of formation of procedure of testing of ice-forming pyrotechnic

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

compositions, we carried out experiments on the of crystallization means on the basis of silver iodide AgI, we
determination of the practical yield of active particles of a analyzed the yield of really used generators of rockets of the
pyrotechnic composition for different series of antihail "Alazan" type as a functions of external factors. This
rockets, which were produced in different years and used for technique makes it possible to perform a direct simulation of
active impacts on hail-forming processes by the Special the formation of aerosols and their interaction with the
Service for Active Influences on Hydrometeorological supercooled cloud environment, which gives the possibility
Processes of the Republic of Moldova in the respective years to obtain adequate information about the efficiency of the
(Fig. 4). generator in a real process of exposure. The technique is
1E13
based on a direct aerodynamic modeling of the motion of a
real generator in the air in an aerodynamic tube. It is shown
that the efficiency of the pyrotechnic compositions based on
silver iodide (AgI) decreases depending on storage time. The
decrease in yield for given standard storage conditions is on
1E12 the order of 10% per year.
The technique is protected by an author's certificate. To
N (g-1)

date, it has been used for the practical testing of generators

of ice-forming aerosols based on Alazan' and Loza rockets
Theor. used in our country. The developed technique and devices
1E11 01-06, Nr97 make it possible to systematically study the yield of mass-
8-07,Nr109 produced generators of rockets that are used in the practice
2-07,Nr199 of active influences (Alazan', Loza).
30-07,Nr1639 Thus, the totality of the studies is a solution to the
4-08,Nr46 important scientific and technical problem, i.e., the rapid
-5 -6 -7 -8 -9 -10 -11 determination of the yield of real generators used in
0 Moldova in the practice of active influences on supercooled
Temperature, C cloud environments to prevent hail. The results of these
Fig. 4. Temperature dependence of the yield of active particles of a studies based on the experimentally measured value of yield
pyrotechnic composition of antihail rockets. give the possibility to correctly calculate the minimum
number of rockets required for the processing of a
Analysis of Fig. 4 shows that, in general, the behavior of potentially hail-hazardous cloud.
temperature dependence remains the same. However, REFERENCES
depending on the year of manufacture of the rocket (the [1] A. S. Dennis Weather Modification by Cloud Seeding.
rocket's storage time at deposit), an interesting relationship is Academic Press, 1980.
observed: the "older" the pyrotechnic composition, the lower [2] N. H. Fletcher ―Size effect in heterogeneous nucleation‖
its yield. On the basis of general considerations, this J.Chem.Phys., vol.29, pp. 572-576, 1958.
dependence of the generator yield is clear. Under the [3] N. H. Fletcher The physics of rainclouds. Cambrige,
influence of external factors (temperature, time, storage University Press, 1962.
conditions, etc.), irreversible changes take place in a [4] E. I. Zotov, N. I. Zotova, T. D. Nikorich, and E. I.
pyrotechnic composition and lead to the experimentally Potapov, ―The influence of gas impurities on ice-
observed decrease in yield of the generator of antihail forming activity of pyrotechnic compositions with 2%
rockets. content of AgI (in Russian)‖ – Chisinau, Collection
«Active influence on atmospheric processes in
III. CONCLUSION Moldova‖, issue 3, pp. 86-90, 1992.
Based on the technique and devices that were developed [5] E. A. Zasavitsky ―The aerodynamic stand for research
and introduced into practice for studying the efficiency of ice-forming characteristics of reagents‖ Moldavian
Journal of the Physical Sciences, vol 9(2), pp.237-242,
2010.

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Detection in the Contacts With Bismuth-

Antimony Alloy: Numerical Modeling of the
Contact Area Role
Iacov KERNER
Institute of Electronic Engineering and Nanotechnologies “D. Gitsu”
Academy of Sciences of Moldova
[email protected]

Abstract: Diode detectors (DD) are widely used in electronic information and communication systems. The
use of diodes with Schottky barrier gave a possibility to master radiowaves of high frequencies (above 1
GHz). These diodes use the quick-acting metal-semiconductor contacts.
The further improvement of their parameters was achieved due to fall of the working temperature (T). This
direction was named cryogenic electronics or briefly cryoelectronics, it allows to raise the nonlinearity of the
current-voltage dependences (CVD) and current responsivity (CR).
In this paper the numerical modeling of the electrical potential distribution and current passing in the
contacts of normal metal with semiconductor alloy bismuth-antimony (Bi-Sb) with different contact area was
made. There were analyzed possibilities to create the diode detectors based on these contacts and working at
liquid helium temperature 4.2 K. The dependences of the current responsivity, the voltage responsivity (VR)
and the noise equivalent power (NEP) on the signal frequency (f) were analyzed. The obtained results were
compared with literature data. Both DD working at temperature of liquid nitrogen (T = 77.4 K) and liquid
helium (T= 4.2 K) were considered.
The comparison with existent literature data shows the proposed DD can be 10100 times better. The
physical reasons of these advantages were discussed too. It is shown that unique properties of Bi-Sb alloys
and especially of Bi0.88Sb0.12 alloy make these alloys to be the very perspective materials for cryoelectronics.
Therefore these DD are perspective for cryogenic electronics and there is an actual problem to elaborate
them.
Key words- detection, Schottky diodes.

I. INTRODUCTION
The diode detectors play an important role in radio technics CR ≈ 40 A/W, VR ≈ 106 V/W and NEP ≈ 810-15 W/ Hz
and electronics. The use of high frequencies (above 1 GHz) at T = 77.4 K and f = 10 GHz. At the same
stimulated the careful study of diodes with Schottky barrier. temperature and f = 30 GHz these DD may have CR ≈ 15
These diodes use the quick-acting metal-semiconductor A/W, VR ≈ 3.5105 V/W and NEP ≈ 210-14
contacts [1]. W/ Hz .
The further improvement of their parameters was achieved On the other hand often there is an oxidation of
due to fall of the working temperature. This direction was semiconductor in HTSC-semiconductor contacts, because
named cryoelectronics [2], it allows to raise the oxygen is an integral part of HTSC. Also cooling to the
nonlinearity of the current-voltage dependences and current liquid nitrogen temperature 77.4 K may be insufficient to
responsivity. The thermal noise power decreases too. For obtain the good DD parameters. In this situation, taking into
example there were elaborated DD based on the contacts Pb- account the rapid development of cryogenics, the study of
pGaAs [3, 4]. At the signal frequency f = 9 GHz and T= 4.2 DD based on the contacts traditional superconductor –
K these diodes had CR ≈ 500 A/W and noise equivalent semiconductor seems to be actual problem. Usually these
power 510-15 W/ Hz . Also the deep cooling allows DD work at liquid helium temperatures (T ≤ 4.2 K). In this
using the materials with little energy gap width but high article there are discussed DD based on the contacts of
mobility of electrons, such as solid solutions Bi-Sb [2, 5]. normal metal with semiconductor solid solution Bi-Sb. We
After the discovery of the high temperature superconductors tried to analyze the contact area role in this DD.
(HTSC) the possibilities to use HTSC in cryoelectronics II. RESULTS AND DISCUSSION
were studied too. At the liquid nitrogen temperature T = 77 The contacts of semiconductor solid solution Bi0.88Sb0.12
K and signal frequency f = 37.5 GHz the corresponding with normal metal were considered. The normal metal may
structures revealed the voltage responsivity 3000 V/W [6]. be aluminum at T ≥ 1.2 K and silver or gold at lower
The further studies [7] allowed to create the structures with temperatures. Materials properties were taken from [9-11].
VR=5000 V/W and noise equivalent power NEP = 210-12 Results of calculations are shown in figures (figs.) 1-3. In all
W/ Hz at the signal frequency f=31 GHz and figures the logarithmic scale for X-axes is used. An
exponential form is often used for numbers of axes.
temperature T = 77 K. According to our publication [8] the
Figs. 1 - 3 show that current and voltage responsivities
diode detectors based on the contacts HTSC-InSb may have
decrease and NEP increases at the frequencies more 3 GHz.

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At these frequencies the negative role of the barrier capacity (ii) High mobility of electrons, which reduces ohm
is revealed and it begins to shunt the nonlinear contact resistance and improves frequencies properties.
resistance. On the other hand at high frequencies the contact (iii) Little barrier capacity, due to little barriers heights
capacity resistance becomes compared with ohm spreading and small effective masses of electrons, which also improves
resistance. The current redistribution occurs, it leads to frequencies properties.
reduction of the rectified current and DD parameters become
worse. 1,00E-14
The round flat contacts with contact area 100, 10 and 1 µ2
were studied. Taking into account the little surface area these
contacts may be considered as point contacts [1].In this case

NEP, W/Hz 1/2

1,00E-15
the barrier capacity is proportional to S, where S is the 1
contact area, and ohm spreading resistance is proportional to 2
S -1/2 [1]. In this situation, when the contact area decreases, 3
1,00E-16
the capacity resistance rises faster then the ohm spreading
resistance. Therefore the redistribution of applied variable
voltage occurs, the contact voltage grows and DD
parameters become well (see curves 1, 2, 3 in fig. 1). When 1,00E-17
the contact area reduces the contact differential resistance 0,3 1 3 10 30 100
rises and voltage responsivity rises too. On the other hand f, GHz
noise current falls and noise equivalent power falls too (see
figs. 2 and 3). Fig. 3. The calculated noise equivalent power dependence on the signal
frequency. The legend inscriptions and other data are similar to those in fig.
For comparison our results [12] for contacts HTSC- 1. T = 4.2 K.
semiconductor with contact area 100 µ2 are presented in figs.
4, 5.
100
1000 90
900 80
800 70
Si
CR, A/W

700 60
50 InSb
CR, A/W

600 1
500 2 40 GaAs
400 3 30
300 20
200 10
100 0
0 0,3 1 3 10 30 100
0,3 1 3 10 30 100 f, GHz
f, GHz
Fig. 4. The calculated current responsivity dependence on the signal
frequency for contacts HTSC-semiconductor (the semiconductor substance
Fig. 1. The calculated current responsivity dependence on the signal
is shown in legend inscriptions). T = 77.4 K.
frequency in the contacts with Bi0.88Sb0.12 . The legend inscriptions 1, 2 and
3 correspond to the contact area 100, 10 and 1 µ2. T = 4.2 K.
1.00E-10

1,00E+09
1.00E-11
NEP, W/Hz 1/2

1,00E+08 1.00E-12 Si
1 InSb
VR, V/W

1,00E+07 2 1.00E-13 GaAs

3
1.00E-14
1,00E+06

1.00E-15
1,00E+05 0.3 1 3 10 30 100
0,3 1 3 10 30 100 f, GHz
f, GHz
Fig. 5. The calculated noise equivalent power dependence on the signal
frequency for contacts HTSC-semiconductor. The legend inscriptions and
Fig. 2. The calculated voltage responsivity dependence on the signal other data are similar to those in fig. 4. T = 77.4 K.
frequency. The legend inscriptions and other data are similar to those in fig.
1. T = 4.2 K.
These unique properties of Bi-Sb alloys and especially of
The main advantages of Bi-Sb are next:
Bi0.88Sb0.12 alloy make these alloys to be the very perspective
(i) Little barriers heights due to narrow energy gap. This
materials for cryoelectronics.
fact provides a big CVD nonlinearity and big current
responsivity.

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Taking into account results [3, 4, 6-8] we may conclude that Magnetics, vol. MAG-13, no. 1, 1977, pp.221-227.
contacts with Bi-Sb allow improving considerably DD [5] V.G. Alekseeva, T.M. Lifshits, E.G. Chirkova, A.Ia.
parameters. On one hand they are much more effective than Shul'man, Bi1-xSbx is a new semiconductor material,
contacts HTSC-superconductor [6-8]. On the other hand they Radio technics and Electronics (in Russian), vol. 23, no.
are better than contacts with GaAs [3, 4] working at liquid 9, 1978, pp.1926-1938.
helium temperature. [6] V.A. Kulikov, L.V. Matveets, A.Iu. Serebryakov et al,.
The detecting properties of the superconducting thin
III. CONCLUSION
film micro bridges from YBa2Cu3O7-x , Pis‘ma v JTF
The comparison with [3, 4] data shows that in the
(Letters in Journal of Technical Physics – in
proposed DD current responsivity can be 2 times more and
Russian), vol. 15, no. 20, 1989, pp. 74-77.
noise equivalent power can be 100 times less than the ones
[7] L.S. Kuz`min, V. N. Ohrimenko, E. S. Soldatov, A. N.
in existing DD (at the same temperature and signal
Tavhelidze, The detecting properties of the YBaCuO
frequency). Also they may have very high voltage
films micro bridges. (1990) Sverhprovodimost`
responsivity.
(Superconductivity– in Russian), vol. 3, no.11, 1990,
The contact area reduction may sufficiently improve the
pp. 2650-2660.
frequencies properties, noise equivalent power and
[8] Ia.I. Kerner, HTSC-Si and HTSC-InSb contacts for
especially voltage responsivity.
diode detectors: comparison of characteristics.
This fact draws the conclusion the contacts with Bi-Sb
Moldavian Journal of the Physical Sciences, vol. 5, no.
are perspective to elaborate them.
3-4, 2006, pp. 360-365.
REFERENCES [9] D.V. Gitsu, I.M. Holban, V.G. Kantser, F.M. Munteanu,
[1] V.I. Striha, E.V. Buzaneva, I.A. Radzievsky, Transport phenomena in bismuth and its alloys (in
Semiconductor devices with Schotttky barrier. Physics, Russian), Kishinev, Stiinta,1983.
technology, application (in Russian). M., Sov. Radio, [10] Ch. Kittel, Introduction to Solid State Physics (in
1974. Russian), M., Nauka, 1978.
[2] V.N. Alfeev Superconductors, semiconductors and [11] Tables of the physical values. Reference book (in
paraelectrics in cryoelectronics (in Russian), M., Sov. Russian), Edited by academician I.K. Kikoin, M.,
Radio, 1979. Atomizdat,1976.
[3] M. Mc Call, M.F. Millea, A.H. Silver, The [12] Ia.I. Kerner, Contacts of HTSC with different
superconductor-semiconductor Schottky barrier diode semiconductors for diode detectors: comparison of
detecto, Applied Physics Letters, vol. 23, no. 5, 1973, characteristics, Proceeding of the 3-rd Internatinal
pp. 263-264. Conference ―Telecommunications,Electronics and
[4] M. Mc Call, M.F. Millea, A.H. Silver et al., The super Informatics‖, Chişinău, Moldova, May 20-23, 2010,
Schottky microwave mixer, IEEE Transactions on vol. 1, Chişinău, UTM, 2010, pp. 268-273.

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Optical Properties of Amorphous As-Se Thin

Films
D.V.HAREA, M.S.IOVU, V.G.BENEA, E.P.COLOMEICO, I.A.COJOCARU
Institute of Applied Physics, Academy of Sciences of Moldova,
[email protected]

Abstract – Photostructural transformations in amorphous films of chalcogenide glasses (ChG) under light
irradiation present scientific and practical interests. From scientific point of view, because the composition of
ChG determine the kind of structural units and the mean coordination number, in the present work the
amorphous films of the chalcogenide systems As100-xSex (x=40÷98) and As40Se60:Sny (y=0÷10.0 at.% Sn) were
studied. The experimental investigation of the transmission spectra, photodarkening relaxation and
holographic characteristics of the amorphous films under study, including the thickness dependence are
presented. The dependences of the refractive index under light irradiation and heat treatment were revealed.
It was established that the more sensitive to light irradiation are the amorphous films of As 60Se40 and
As50Se50, which exhibit big modifications of the refractive index ( (n n)  0.394 )

Keywords –: Amorphous chalcogenide films, optical absorbtion, refractive index, photoinduced phenomena

and =540 nm, P=0.75 mW) were used as a source of light

exposure. The experimental set-up included a laser, a digital
I. INTRODUCTION
build-in PC-card PCI-1713A for data acquisition connected
Optical properties and photoinduced phenomena in
with the Si-photodetector. Special software was elaborated
chalcogenide glasses are very attractive for many
for automatic measurements.
applications in photonics and optoelectronics (inorganic
photoresists, registration media for optical and holographic
information, passive and active elements for integrated III. RESULTS AND DISCUSSION
optics, all-optical switching, imaging devices, vapor sensors, The optical transmission spectra for amorphous AsxSe100-x
etc.) [1-3]. The arsenic selenide amorphous films usually (L~1,3 µm) was investigated at room temperature (as-
became darkened under action of light from the region of deposited, heat treated in vacuum at Ttreat=120 oC during 1
fundamental optical absorption hEg and so-called hour and exposed with light E=50000 Lx during 1 hour).
photodarkening effect takes place. Increasing of the optical Increasing of the As content As100-xSex system shift the
absorption is accompanied by the red shift of the absorption absorption edge in the red region of the spectra. The band
edge and increasing of the refractive index. In this paper the gap value for amorphous As40Se60 thin films, determined
effect of the composition in the glassy systems As100-xSex from the absorption spectra is Eg=1.82 eV. This is in good
(x=4098) and As40Se60:Sny (y=0’10.0 at.% Sn) on the agreement with the experimental data presented in [4],
optical properties and on the degree of photostructural according which the optical band-gap values decrease from
transformations are presented. The kinetics of Eg=1,95 eV for As8Se92 up to Eg=1,83 eV for As36Se64.
photodarkening and the dynamics of optical registration
process of micro-holograms in -As100-xSex thin films also
were investigated. On the base of the observed changes of
the refractive index in both As100-xSex and As40Se60:Sn glassy
systems was established the higher sensitive to light
exposure compounds. It was shown that the more sensitive
to photostructural transformations under light exposure are
the non-stoichiometric As50Se50 and As60Se40 amorphous
films, and decrease with increasing of Se content in the
As100-xSex glasses.

II. EXPERIMENTAL
The glasses As100-xSex (x=4098) and As40Se60:Sny
(y=0’10.0 at.% Sn) were synthesized from the elements of Fig.1. The shift of the absorption edge (, curve 1) and the degree
6N (As, Se, Sn) purity by conventional melting technique. of modification of the refractive index (n, curve 2) under the light
The amorphous As100-xSex and As40Se60:Sny thin films of irradiation for different film composition of the glassy system As100-
different thickness (L=0.2’5.0 m) were prepared by ―flash‖ xSex.

thermal evaporation in vacuum onto the glass substrates kept The displacement of the absorption edge under light
at Tsubs=100 oC. exposure and heat treatment for all amorphous As100-xSex
To initiate photostructural transformations in thin film films is accompanied by the respective modifications of the
samples a continuous He-Ne lasers (=630 nm, P=0.6 mW refractive index n. For calculation of the optical constants

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the Programme PARAV-V1.0 was used [5]. The degree of

the displacement of the absorption edge in the red region 4.5
1
depends on the composition of the amorphous film, intensity

Refractive index
and time of exposure, and heat treatment. Influence of the 4.0 2

light exposure at the level of transmission T=20 % is

manifested by the shift of the absorption edge =920 nm 3.5
3
which correspond to the amorphous As60Se40, and decrease
3.0
with increasing of Se content up to =2’5 nm for As5Se95
and As10Se90 (Fig.1). 2.5
Increasing of Sn concentration in amorphous 0.0 0.5 1.0 1.5 2.0
As40Se60 thin films shifts the absorption edge in the red Sn concentration in As2Se3
region of the spectra. Concentration of Sn in amorphous
Fig.4. Dependence of the refractive index n vs. Sn concentration in
As40Se60 thin films increases the refractive index n (Fig.2). as-deposited amorphous As40Se60:Sny thin films calculated at
different wavelengths , nm:

4.5 1 – 715, 2 – 735, 3 – 800.

Photodarkening relaxation was measured during
Refractive index

4.0 illumination for as-deposited amorphous As100-xSex

(x=4098). The relaxation of the relative optical
3.5 transmission T(t)/T(0) of the amorphous As100-xSex films is
4 shown in Fig.5. Increasing of Se in the As100-xSex system
3.0
2
suppressed the photodarkening effect and x=72’98 is absent
3 or is very small. The relaxation of photodarckening is
2.5 1
described by the stretched exponential function
700 750 800 850
Wavelength (nm) T(t)/T(0)=A0+Aexp[-(t-t0)/τ] (1-α). Here t is the exposure time,
τ is the apparent time constant, A characterizes the exponent
Fig.2. Dispersive curves of the refractive index n for amorphous amplitude, t0 and A0 are the initial co-ordinates, and α is the
As40Se60 (1), As40Se60:Sn0.5 (2), As40Se60:Sn1.0 (3), and dispersion parameter (0<<1).
As40Se60:Sn2.0 (4) thin films.
The dependence of the relaxation time  and of the
For x=2.0 at. % of Sn the refractive index n=3.5 at =800 dispersion parameter  for as-deposited (UN) and annealed
nm. Fig.3 represents the influence the light exposure and (AN) films is shown in Fig.6. The dispersion parameter α is
heat treatment on the degree of modification of the refractive close to α =0.3 for almost all UN As100-xSex (x=40’60), and
index n for amorphous As40Se60:Sn1.0 thin films. In these non-monotonously is changed with composition.
cases, the light exposure as well as the heat treatment
increases the refractive index n. 100

80 1
Transmittance (%)

60

40
2

20 3

0
0 1000 2000 3000 4000
Time (s)

Fig.5. Photodarkening kinetics (T/T0) of as-deposited amorphous

As28Se72 (1), As40Se60 (2), and As50Se50 (3) films vs. exposure time
t. Excitation wavelength exc=0.63 m.
Fig.3. Dispersive curves of the refractive index n for amorphous
As40Se60:Sn1.0 thin films: 1 – as-deposited, 2 – as-deposited and
In our experimental conditions, for the AN films the lower
light exposed, 3 – heat treated, 4 – heat treated and exposed. value of the dispersion parameter 0.3 is for the As45Se55
composition and increase up to 0.6’0.65 for the As40Se60
Fig.4 shows the dependence of the refractive index n on
Sn concentration in as-deposited amorphous As40Se60:Snx and As60Se40. Such behaviour of the dispersion parameter 
with composition may be associated with the structure of the
thin films calculated at different wavelengths .
investigated glasses. According to [6], for the glassy system
As100-xSex the composition x=0.45 took the maximum value
of the glass transition temperature Tg.

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The maximum of the diffraction efficiency is reached at

800 0.8
 - UN 10-15 min of the exposure and after that for the
 - UN 0.7 compositions richer in Se the saturation take place. For the
600  - AN compositions richer in As atoms the kinetics of the
 - AN 0.6
diffraction efficiency represents a curve with maximum or a
400 0.5 sinusoidal (not shown in the Fig.9).
 (s)


0.4
Prolonged time exposure decreases the diffraction
200 efficiency after the maximum. At the same time we have
0.3 demonstrated that doping of amorphous As40Se60 doped with
0
0.2 Sn allow to rich saturation on the curve of growth of the
40 45 50 55 60
diffraction efficiency in dependence with the exposure dose
Concentration of Se (at.%) in AsxSe100-x [9]. This effect we have explained by the specific of
structure of the tin doped films.
Fig.6. The dependence of the parameters  and  of the stretched The holographic sensitivity of the amorphous films and
exponential for the as-deposited (UN) and annealed (AN) the diffraction efficiency of the hologram have decreases
amorphous As100-xSex thin films.
with increasing of the selenium content in As100-xSex glassy
The relaxation of the relative optical transmission system (Fig.10, curve 1).
T(t)/T(0) of the amorphous As60Se40 films of different

Diffraction Efficiency & n/n

thickness is shown in Fig.7. The experimental data show that
for the thicker films the photodarkening is stronger, and
almost is absent for the films with thickness about L0.2-0.3 0.4
µm. The influence of the thickness on the photodarkening
effect also was demonstrated for the amorphous As2S3 and
0.2
As2Se3 films [7], and for As2Se3 pure and doped with Dy and 2
Pr films [8]. Fig.9 shows the kinetics of growth of the
1
diffraction efficiency for amorphous As100-xSex thin films 0.0
during exposure as result of interference of two He-Ne laser
40 50 60 70 80 90
beams (=0.63 µm) with a power of W=30 mW. The
Se content in As100-xSex
intensity of the first interference maximum was recorded in
the transmittance mode.
Fig.10. The dependence of the diffraction efficiency (curve 1) and
the degree of modification of the refractive index n/n (curve 2) vs.
100 Se concentration in the As100-xSex glassy system.
1

80 The measured value of the diffraction efficiency for

Transmittance (%)

different amorphous films of the As100-xSex glassy system are

60 in good correlation with the degree of modifications of the
2
refractive index n/n under the light exposure (Fig.10, curve
40 2).
The thickness dependence of the diffraction efficiency for
20 3
amorphous As60Se40 films also was investigated. Increasing
4
of thickness from L=0.27 µm up to L=4.07 µm also lead to
0
0 1000 2000 3000 4000 rising of diffraction efficiency with decreasing of the
Time (s) recording time.

Fig.8. The dependence of transmission versus exposure time for IV. CONCLUSION
amorphous As60Se40 films of different thickness L, m 1-0.27; 2-0.69, Photostructural transformations in amorphous As100-xSex
3-2.04, 4-4.07. (x=40’98) and As40Se60:Sny (y=0’5.0 at.% Sn) films were
investigated. The changes of the refractive index under light
irradiation and heat treatment calculated from the
Diffraction Efficiency (a.u.)

0.5 4
transmission spectra exhibits composition dependence due to
0.4 the difference of the existing structural units. The more
sensitive to light irradiation are the amorphous films of
0.3 As60Se40 and As50Se50, which exhibit big modifications of
0.2 the refractive index ( (n n)  0.394 ) and high holographic
3
0.1 parameters. Metal impurities effectively reduce the
2
1
photodarkening, and the degree of reduction becomes
0.0 stronger as the impurity concentration is increased. Changes
0 2 4 6 8 10 12 in the optical transmission of the investigated amorphous
Time (min)
films under illumination may be described by a stretched
Fig.9. The kinetics of growth of the diffraction efficiency vs. exponential with the dispersive parameter 0.41.0.
exposure time for amorphous As40Se60 (curve 1), As45Se55 (curve The composition dependence of the transmission spectra,
2), As50Se50 (curve 3), and As60Se40 (curve 4) thin films. photodarkening characteristics, and kinetics of recording

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process of holographic information in the films of the glassy AKNOWLEDGEMENTS

system As100-xSex (x=4098) was investigated. It was For calculation of the optical constants the Programme
established, that the higher sensitivity to light exposure PARAV-V1.0 was used (www.chalcogenide.eu.org).
exhibit the non-stoichiometric As50Se50, As55Se45, and
As60Se40 amorphous films, and decrease with increasing of REFERENCES
Se content in the As100-xSex glass. The experimental results [1] M.Popescu, A.Andriesh, V.Chiumach, M.Iovu,
are interpreted in terms of structural optical polymerization S.Shutov, and D.Tsiuleanu. The Physics of
process, which includes the transformation of As4Se4 and Se2 Chalcogenide Glasses, Ed. Stiintifica Bucharest -
structural units in homogenius AsSe3/2 network. I.E.P.Stiinta, Chisinau, 1996 (In Romanian).
The photodarkening phenomenon in chalcogenide glass [2] A.Kovalskiy. M.Vlcek, H.Jain, A.Fiserova, C.M.Waits,
films under illumination has no plain explanation up to now J. of Non-Cryst. Solids 352, 589 (2006).
in spite of detailed investigation and a series of models [3] Mihail Iovu & Maria Iovu, Chalcogenide glass photonic
advanced for interpretation of it. The red shift of the devices, In: Proceedings of 33 American Romanian
absorption edge indicating the narrowing of the optical gap Academy of Sciences and Arts, 02-07 June 2009, Sibiu,
of the film at photodarkening, is believed to be due to Romania.
broadening of the valence band, the top of which is formed [4] P.Nagels, Romanian Reports in Physics 51, 209 (1999).
mainly by states of lone-pare electrons of the chalcogen [5] A.Ganjoo, R.Golovchak, J. of Optoelectronics and
atom. According to the model for photodarkening in a- Advanced Materials 10, 1328 (2008).
As2Se(S)3 [10], the photoexcited charge carriers in extended [6] S.Mamedov, D.G.Georgiev, Tao Qu, P.Boolchand, J. of
states are considered as responsible for photodarkening. Phys.: Condens. Matter 15, 2397 (2003).
Unlike to the previous conceptions this takes into account [7] K.Hayashi, N.J.Mitsuishi, J. of Non-Cryst. Solids
the layered cluster structure of a chalcogenide glass. During 299&302, 949 (2002).
exposure the layer is negatively charged due to capture of [8] M.S.Iovu, S.D.Shutov, P.Boolchand, E.P.Colomeico,
photoexcited electrons, and repulsive forces are built V.G.Ciorba, S.M.Iovu, M.Popescu, J. of Optoel. and
between the layers. These forces cause enlargement of the Adv. Materials 4, 857 (2002).
interlayer distance (leading to photoexpansion) and slip [9] A.I.Buzdugan, M.S.Iovu, A.A.Popescu, P.G.Cherbari,
motion along the layers. This latter process alters interaction Balkan Phys. Letters 1, 7 (1993).
of lone-pair electrons between the layers leading to [10] A. Ganjoo, N. Yoshida and K.Shimakawa. Recent
photodarkening effect. Research Developments in Applied Physics, ed.
M.Kawasaki, N. Ashgritz and R. Anthony (Research
Signpost, Trivandrum, 2, 129 (1999).

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Morphology and Luminescence Properties of

ZnO layers produced by Magnetron Spattering
Emil RUSU1, Irina GHIŢU1, Vladimir PRILEPOV2, Victor ZALAMAI3, Veaceslav URSAKI3
1
Institute of Electronic Engineering and Nanotechnologies, Academy of Sciences of Moldova,
Academy str. 3/3, Chisinau MD-2028, Republic of Moldova, e-mail: [email protected]
2
State University of Moldova, Mateevici str. 60, Chisinau MD-2009, Moldova
3
Institute of Applied Physics of the Academy of Sciences of Moldova, Academy str. 5, Chisinau MD-
2028, Moldova

Abstract – We show that the morphology and the luminescence properties of ZnO layers produced by
magnetron sputtering can be controlled by technological parameters of sputtering, particularly by the ratio
of argon to oxygen gases in the gas flow during the growth process. Smooth and flat layers were produced
with a high Ar/O ratio, while porous layers with various morphologies were obtained with a low Ar/O ratio.
The layers produced with O/Ar ration equal to 10 exhibit extremely high near-bandgap luminescence
intensity even higher in comparison with bulk ZnO single crystals. The free carrier density estimated from
the analysis of photoluminescence spectra is also very high in these samples suggesting that these
technological conditions promote both optical and electrical activation of the doping Al impurity. The
samples grown with high Ar/O ratios exhibit strong visible emission which is controlled by the technological
conditions.

Index Terms – ZnO, magnetron sputtering, morphology, luminescence, excitonic emission, deep centers.

sputtering is a technique which allows one to produce both

I. INTRODUCTION nanostructured and flat layers, in being at the same time less
ZnO demonstrates increasing fundamental interest and expensive than MOCVD and MBE technologies.
technological applications due to its wide and direct band In this work, we investigate the morphology and the
gap (3.37 eV at room temperature), large exciton binding photoluminescence (PL) properties of ZnO layers produced
energy (60 meV), large bond strength (with a cohesive by magnetron stuttering in order to establish their
energy of 1.89 eV), and large mechanical stability (with a dependence upon the technological conditions of growth.
melting point of about 2200 K) [1], it being of a particular
II. SAMPLE PREPARATION AND EXPERIMENTAL
interest for optoelectronic and photonic devices [2-4].
DETAILS
In recent years, with the development of different growth
Magnetron sputtering of ZnO films was performed in an
techniques, gallium nitride (GaN) has become the most
installation assembled on the basis of a VUP-5 instrument. A
important building block for LEDs operating in the green to
control sample was placed in the stuttering chamber near the
ultraviolet light range [5-7]. ZnO and GaN are analogous
Si, SiO2/Si, or ITO-on-glass basic support for monitoring the
materials with many similar properties. ZnO has an
deposition process via measuring the resistivity of the layer
advantage over GaN, due to the availability of high quality
deposited on the control sample. A 99,99 % purity Zn plate
ZnO substrates, while there is a lack of GaN substrates. This
with a diameter of 40 mm and thickness of 5 mm doped with
makes possible the preparation of ZnO based homojunction
2% wt of Al was used as target. The temperature of both the
in addition to heterojunctions.
control and the basic supports was maintained at a
A multitude of synthesis methods, such as various wet
temperature from the interval 200 – 220 oC, while the
chemical methods [8-12], sol-gel methods [13,14], metal
magnetron power was W=360 V x 100 mA. The Si support
organic chemical vapour deposition (MOCVD) [15-17],
was treated in a 30% Na2S2O3x5H2O solution before the
molecular beam epitaxy (MBE) [18,19], electrochemical
sputtering process for improving the adhesion of the
deposition [20-22], metal-catalyzed vapour-liquid-solid
deposited ZnO layer.
(VLS) growth [3,23], and thermal chemical vapour transport
A mixture of Ar+O was used as working gas. The ratio of
and condensation method without metal catalysts [24-28]
Ar/O in the gas flow was changed and air was introduced in
have been employed for the fabrication of ZnO layers.
the grouth chamber for a certain period of time during the
Such methods as chemical, electrochemical, sol-gel,
sputtering process in order to controll morphology and the
VLS, and chemical vapour transport and condensation
raditive properties of the deposted ZnO film. The samples
growth are cost effective. However, they basically lead to
were annealed in air during 30 min at 450 oC after the
the production of nanostructured layers, such as wires, rods,
deposition process.
ribbons, belts, tubes, discs, tetrapods, combs, rings, springs,
A VEGA TESCAN TS 5130 MM scanning electron
propeller arrays, etc, it being hard to produce smooth and flat
microscope (SEM) was used for morphological
layers with these techniques. Smooth and flat films are
characterization of the samples.
highly desired in homojunction and heterojunctions. Smooth
Photoluminescence was excited by 325 nm line of a He-
surfaces can be obtained with MOCVD and MBE methods.
Cd Melles Griot laser and was analyzed through a double
However, these technologies are quite expensive. Magnetron

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spectrometer at low temperature (10 K). The resolution was emissions can be observed with a peak position varying in a
better than 0.5 meV. The samples were mounted on the cold wide wavelength range from 450 to 830 nm.
station of a LTS-22-C-330 cryostat.

Fig. 1. SEM image of ZnO layers produced by magnetron sputtering in Fig. 2. Enlarged SEM view of ZnO layers produced by magnetron
processes with different ratio of argon to oxygen gases in the gas flow sputtering in processes with different ratio of argon to oxygen gases in the
during the growth process as follows: Ar:O = 10:1 (a); Ar:O = 1:1 (b); Ar:O gas flow during the growth process as follows: Ar:O = 10:1 (a); Ar:O = 1:1
= 1:10 (c). (b); Ar:O = 1:10 (c).

III. RESULTS AND DISCUTIONS Since the defect-related emissions are known to be sensitive
Wide-gap oxide semiconductors are attractive materials to technological conditions of sample preparation, one can
as phosphors if they exhibit visible emissions arising from expect that the luminescence spectrum from ZnO samples in
defect levels in the bandgap. Apart from the near-band-edge the visible range as well as the morphology of layers can be
ultraviolet emission at approximately 380 nm, ZnO is also controlled by the technological parameters of magnetron
known to exhibit a complex luminescence behavior in the sputtering.
visible wavelength region [29,30]. Visible deep-level The investigation of the morphology as well as the
radiative properties of ZnO layers grown by magnetron

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sputtering demonstrated that they are determined by the oxygen content leads to the creation of spectacularly twisted
technological conditions such as the pressure of gases in the microstructures (Fig. 1c) which prove to be porous at a more
growth chamber, the concentration of oxygen, as well as by accurate analysis (Fig. 2c). The length of the microstructures
the substrate used. It was found that the introduction of air in produced with an Ar:O ratio of 1:10 on an ITO-on-glass
the grouth chamber for a period of time longer than 30 min substrate vary in the range of 4 to 20 m with a diameter of
during the sputtering process leads to the oxidation of the 1 – 4 m.
target. This oxidation, in turn, affects the magnetron power Apart from morphology, the ratio of argon to oxygen
and creates instabilities in plasma maitaining. The velosity gases in the gas flow during the growth process strongly
of gas flows into the chamber is set to a value assuring the influences the radiative properties of the produced ZnO
maintainance of a constant pressure, and therefore a stability layers. The smooth films produced with a high Ar/O ratio
of the created plasma. exhibit weak luminescence suggesting an amorphous nature
of the film. Annealing of samples in air during 30 min at 450
o
C after the deposition process leads to increasing
luminescene intensity due to the crystalization [curve (a) in
Fig. 3].
Several visible PL bands are observed in the luminescence
spectrum in addition to the near band-edge emission. The
visible emission from the sample produced with the Ar/O
ratio equal to 10 (Fig. 3) consists of three bands located
around 1.85 eV, 2.37 eV, and 2.67 eV at both 10 K and room
temperature. The near-band-edge luminescence at 10 K is
dominated by two bands at 3.61 and 3.71 eV related to the
recombination of donor bound excitons (D0X) (Fig. 4).

Fig. 4. Near band-edge PL spectra of the samples (a) and (b).

The D0X bands at 3.61 eV and 3.71 eV correspond to the

previously observed I1 and I6 bands, the I6 band being
associated with the Al impurity [31]. Apart from the D 0X
Fig. 3. PL spectra of ZnO layers produced by magnetron sputtering in bands, a PL band is observed at 3.314 eV accompanied by
processes with different ratio of argon to oxygen gases in the gas flow LO phonon replicas, it being previously attributed to the
during the growth process as follows: Ar:O = 10:1 (a); Ar:O = 1:1 (b); Ar:O
= 1:10 (c). The samples were annealed in air during 30 min at 450 oC after
donor-acceptor pair recombination (DA) [32]. At room
the deposition process temperature, the near-band-edge luminescence represents a
band due to the recombination of free excitons at 3.30 eV
The morphology of the produced ZnO layers was found with a LO phonon replica.
to be determined first of all by the ratio of argon to oxygen As concerns the visible luminescence, taking into account
gases in the gas flow during the growth process. High values the n-type of the produced material, one can suggest that
of the Ar/O ratio result in the production of smooth and flat assignment of these PL bands to the electron transitions from
ZnO films with the morphology illustrated in Fig. 1a for a a deep donor level to the valence band (D-h-type
film produced with the Ar/O ratio equal to 10. The increase recombination) is very improbable [33]. Most probably,
of the oxygen content into the gas flow leads to the these PL bands are due to electronic transitions from the
production of porous layers as shown in Fig. 1b and 1c. conduction band to acceptor levels (e-A-type
When the Ar:O ratio is 1:1, the obtained ZnO layer consists recombination). The red band at 1.85 eV is supposed to be
of microcrystallites as shown in Fig. 1b. The size of these associated with a deep unidentified acceptor with the energy
crystallites determined from the enlarged view presented in level situated close to the middle of the bandgap [34]. The
Fig. 2b is around 200 – 500 nm. Further increase of the PL bands in the spectral interval of 2.3 – 2.7 eV are most

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probably due to different defect complexes involving the VZn semiconductor zinc oxide‖, Opt. Mater., vol. 30, pp.
acceptor center. The isolated zinc vacancy is expected to 292-310, 2007.
have charge −2 in n-type ZnO where its formation is more [2] S. Choopun, H, Tabata, K. Kawai, ―Self-assembly ZnO
favorable. The transition level between the −1 and −2 charge nanorods by pulsed laser deposition under argon
states of VZn occurs at 0.8 eV above the valence band [34]. atmosphere‖, J. Cryst. Growth, vol. 274, pp. 167-172,
Thus, one may expect transitions from the conduction band 2005.
to the VZn acceptor at around 2.6 eV in n-type ZnO. Other PL [3] M. Huang, S. Mao, H. Feick, H. Yan, Y. Wu, H. Kind,
bands observe in this spectral range can be attributed to E. Weber, R. Russo, P. Yang, ―Room-Temperature
complex defects involving the VZn center such as zinc Ultraviolet Nanowire Nanolasers‖, Science, vol. 292,
vacancies and zinc antisites (VZn−ZnO) [35], zinc vacancies pp. 1897-1899, 2001.
and oxygen vacancies [36,37], or more complex defect [4] R. Hauschild, H. Kalt, ―Guided modes in ZnO
clusters [38]. nanorods‖, Appl. Phys. Lett. 89, pp. 123107, 2006.
The increase of the oxygen content in the Ar/O ratio to 1:1 [5] Y. Y. Naoi, K. Ikeda, T. Hama, K. Ono, R. Choi, T.
leads to the emergence of a PL band centered at 2.50 eV Fukumoto, K. Nishino, S. Sakai, S. M. Lee, M. Koike,
instead of bands at 2.37 eV and 2.67 eV which suggest the ―Blue light emitting diode fabricated on a-plane GaN
reconfiguration of the defect complexes (Fig. 3). Apart from film over r-sapphire substrate and on a-plane bulk GaN
that, the near-band-edge luminescence is intensified by an substrate‖, Phys. Status Solidi c, vol. 4, pp. 2810–2813,
order of magnitude, the D0X band related to the Al impurity 2007.
becoming highly predominant (Fig. 4) suggesting an [6] Z. Zhong, F. Qian , D. Wang, C. M. Lieber, ―Synthesis
efficient optical activation of this impurity. of p-Type Gallium Nitride Nanowires for Electronic and
Further increase of the oxygen content leads to a Photonic Nanodevices‖, Nano Lett., vol. 3, pp. 343-346,
spectacular increase of the near-band-edge luminescence 2003.
intensity by additional several orders of magnitude with a [7] F. A. Ponce, D. P. Bour, ―Nitride-based semiconductors
concomitant broadening of the near-band-edge luminescence for blue and green light-emitting devices‖, Nature, vol.
band. A characteristic feature of this PL band is the 386, pp. 351-359, 1997.
broadening toward the Stokes part of the emission. The [8] J. Zhang, L. D. Sun, J. L. Yin, H. L. Su, C. S. Liao, C.
width of this PL band is 58 meV at 10 K and 115 meV at H. Yan, ―Control of ZnO Morphology via a Simple
room temperature. It was previously shown that most Solution Route‖, Chem. Mater., vol. 14, pp. 4172-4177,
probably this PL band is due to direct transitions of electrons 2002.
from the conduction band tails to valence band tails [39]. [9] B. Liu B. H. C. Zeng, „Hydrothermal Synthesis of ZnO
The broadening of the PL band involved can be accounted Nanorods in the Diameter Regime of 50 nm‖, J. Am.
for by the broadening of the band edges due to potential Chem. Soc., vol. 125, pp. 4430-4431, 2003.
fluctuations induced by the high concentration of intrinsic [10] H. L. Cao, X. F. Qian, Q. Gong, W. M. Du, X. D. Ma,
defects or impurities. This model has been applied to Z. K. Zhu, ―Shape- and size-controlled synthesis of
correlate the width of the PL band to the free carrier nanometre ZnO from a simple solution route at room
concentration in highly doped ZnO samples [39]. By using temperature‖, Nanotechnology, vol. 17, pp. 3632-2636,
the established dependence, one can estimate that the 2006.
electron concentration in the sample produced with the Ar:O [11] S. T. Shishiyanu, O. I. Lupan, E. V. Monaico, V. V.
ratio of 1:10 is 4.01019 cm-3 at T = 10 K, and 1.51020 cm-3 Ursaki, T. S. Shishiyanu, I. M. Tiginyanu,
at room temperature. These data suggest that increasing the ―Photoluminescence of chemical bath deposited ZnO:Al
oxygen content in the Ar/O ratio during the magnetron films treated by rapid thermal annealing‖, Thin Solid
sputtering promotes the optical and electrical activation of Films, vol. 488, pp. 15-19, 2005.
the doping Al impurity. [12] V.V. Ursaki, O.I. Lupan, L. Chow, I.M. Tiginyanu,
V.V. Zalamai, ―Rapid thermal annealing induced
change of the mechanism of multiphonon resonant
IV. CONCLUSION Raman scattering from ZnO nanorods‖, Solid State
The results of this study demonstrate that the morphology Communications, vol. 143, pp. 437-441, 2007.
and the luminescence properties of ZnO layers can be [13] G. Westin, A. Ekstrand, M. Nygren, R. Österlund, P.
controlled by technological parameters of magnetron Merkelbach, ―Preparation of ZnO-based varistors by the
sputtering. High values of the ratio of argon to oxygen gases sol–gel technique‖, J. Mater. Chem., vol. 4, pp. 615-
in the gas flow during the growth process lead to the 621, 1994.
production of smooth and flat layers with nearly identical [14] S.-Y. Chu, T.-M. Yan, S.-L. Chen, ―Characteristics of
intensity of the near-band-edge and visible luminescence, sol-gel synthesis of ZnO-based powders‖, J. Mater. Sci.
while the layers obtained with low values of this ratio are Lett., vol. 19, pp. 349-352, 2000.
porous and exhibit extremely high near-bandgap [15] W. I. Park, D. H. Kim, S. W. Jung, G. C. Yi,
luminescence intensity. ―Metalorganic vapor-phase epitaxial growth of
vertically well-aligned ZnO nanorods‖, Appl. Phys.
ACKNOWLEDGMENTS Lett., vol. 80, pp. 4232-4235, 2002.
This work was supported by the Academy of Sciences of [16] Y. J. Zeng, Z. Z. Z. Ye, W. Z. Xu, L. P. Zhu, B. H.
Moldova under Contract No. 10.820.05.20/RoF. Zhao, ―Well-aligned ZnO nanowires grown on Si
REFERENCES substrate via metal–organic chemical vapor deposition‖,
[1] S. Tuzemen, E. Gur, ―Principal issues in producing new Appl. Surf. Sci., vol. 250, pp. 280-283, 2005.
ultraviolet light emitters based on transparent

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

[17] A. Burlacu, V. V. Ursaki, V. A. Skuratov, D. Lincot, T. [29] Stratan, A. Burlacu, I. M. Tiginyanu, ―Optical
Pauporte, E. V. Rusu, I. M. Tiginyanu, ―The impact of characterization of hierachical ZnO structures grown with a
morphology upon the radiation hardness of ZnO layers‖, simplified vapour transport method‖, Nanotechnology,
Nanotechnology, vol. 19, 215714, 2008. vol. 18, 215705 (2007).
[18] El-Shaer, A. Che Mofor, A. Bakin, M. Kreye, A. Waag, [30] K. Vanheusden, C. H. Seager, W. L. Warren, D. R.
―High-quality ZnO layers grown by MBE on sapphire‖, Tallant, J. A. Voigt, ―Correlation between
Superlattices and Microstructures, pp. 265-271, 2005. photoluminescence and oxygen vacancies in ZnO
[19] H. Kato, M. Sano, K. Miyamoto, T. Yao, B.-P. Zhang, phosphors ―Appl. Phys. Lett., vol. 68, pp. 403-405,
K. Wakatsuki, Y. Segawa, ―MBE growth of Zn-polar 1996.
ZnO on MOCVD-ZnO templates‖, Phys. Status Solidi [31] R. M. Nyffenegger, B. Craft, M. Shaaban, S. Gorer, G.
(b), vol. 241, pp. 2825–2829, 2004. Erley, R. M. Penner, ―A Hybrid Electrochemical/
[20] T. Pauporté, D. Lincot, ―Heteroepitaxial Chemical Synthesis of Zinc Oxide Nanoparticles and
electrodeposition of zinc oxide films on gallium Optically Intrinsic Thin Films‖, Chem. Mater., vol. 10,
nitride‖, Appl. Phys. Lett., vol. 75, pp. 3817-3820, pp. 1120-1129,1998.
1999. [32] Meyer B K et al., ―Bound exciton and donor–acceptor
[21] M. J. Zheng, L. D. Zhang, G. H. Li, W. Z. Shen, pair recombinations in ZnO‖, Phys. Stat. Sol. (b), vol.
―Fabrication and optical properties of large-scale 241, pp. 231-260, 2004.
uniform zinc oxide nanowire arrays by one-step [33] V.V. Ursaki, I.M. Tiginyanu, V.V. Zalamai, V.M.
electrochemical deposition technique‖, Chem. Phys. Masalov, E.N. Samarov, G.A. Emelcenko, F. Briones,
Lett., vol. 363, pp. 123-128, 2002. ―Photoluminescence of ZnO layers grown on opals by
[22] O. Lupan, T. Pauporte, B. Viana, I. M. Tiginyanu, V. V. chemical deposition from zinc nitrate solution‖,
Ursaki, and R. Cortes, Epitaxial Electrodeposition of Semiconductor Science and Technology, vol. 19, pp.
ZnO Nanowire Arrays on p-GaN for Efficient UV- 851-854, 2004.
Light-Emitting Diode Fabrication, ACS J. Appl. [34] M. A. Reshchikov, R. Y. Korotkov, ―Analysis of the
Materilas and Interfaces, 2, No. 7, 2083–2090 (2010). temperature and excitation intensity dependencies of
[23] S. Y. Li, C. Y. Lee, T. Y. Tseng, ―Copper-catalyzed photoluminescence in undoped GaN films‖, Phys. Rev.
ZnO nanowires on silicon (1 0 0) grown by vapor– B, vol. 64, 115205, 2001.
liquid–solid process‖, J. Cryst. Growth., vol. 247, pp. [35] U. Ozgur, Ya. I. Alivov, C. Liu, A. Teke, M. A.
357-362, 2003. Reshchikov, S. Doğan, V. Avrutin, S.-J. Cho, H.
[24] P. X. Gao, Z. L. Wang, ―Nanoarchitectures of Morkoç, ―A comprehensive review of ZnO materials
semiconducting and piezoelectric zinc oxide‖, J. Appl. and devices‖, J. Appl. Phys., vol. 98, 041301, 2005.
Phys. 97, 044304, 2005. [36] Z. Q. Chen, K. Betsuyaku, A. Kawasuso, ―Vacancy defects in
[25] F. Xu, K. Yu, G. Li, Q. Li, Z. Zhu, ―Synthesis and field electron-irradiated ZnO studied by Doppler broadening
emission of four kinds of ZnO nanostructures: of annihilation radiation‖, Phys. Rev., vol. B 77,
nanosleeve-fishes, radial nanowire arrays, nanocombs 113204, 2008.
and nanoflowers‖, Nanotechnology, vol. 17, 2855- [37] S. A. Studenikin, M. Cocivera, ―Time-resolved
2859, 2006. luminescence and photoconductivity of polycrystalline
[26] C. Li, G. Fang, F. Su, G. Li, X. Wu, X. Zhao, ZnO films, J. Appl. Phys., vol. 91, pp. 5060-5064, 2002.
‖Synthesis and photoluminescence properties of [38] J. Zhong, A. H. Kitai, P. Mascher, W. Puff, ―The influence of
vertically aligned ZnO nanorod–nanowall junction processing conditions on point defects and
arrays on a ZnO-coated silicon substrate‖, luminescence centers in ZnO‖, J. Electrochem. Soc.,
Nanotechnology, vol. 17, 3740-3744, 2006. vol. 140, pp. 3644-3649, 1993.
[27] Y. H. Yang, B Wang, G. W. Yang, ―Growth [39] Y. Dong, F. Tuomisto, B. G. Svensson, A. Yu. Kuznetsov, L. J.
mechanisms of one-dimensional zinc oxide hierarchical Brillson,‖Vacancy defect and defect cluster energetics in
structures‖, Nanotechnology, vol. 17, 5556-5560, ion-implanted ZnO‖, Phys. Rev. B, vol. 81, 081201(R),
2006. 2010.
[28] V. V. Ursaki, E. V. Rusu, A. Sarua, M. Kuball, G. I. [40] V.V. Zalamai, V.V. Ursaki, E. Rusu, P. Arabadji, I.M.
Tiginyanu, L. Sirbu, ―Photoluminescence and resonant
Raman scattering in highly conductive ZnO layers‖,
Appl. Phys. Lett., vol. 84, pp. 5168-5170, 2004.

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Effective Laser Luminescence of

Nanocomposites Eu(TTA)2(Ph3PO)2NO3-
Polyvinylpyrrolidone
V.I. VERLANA, M.S. IOVUA, S.A. BUZURNIUCA, Yu.H. NISTORA, I. CULEACA, C.I. TURTAB,
V.E. ZUBAREVAB, L.A. MALAHOVC
a
Institute of Applied Physics, Academy of Sciences of Moldova.
b
Institute of Chemistry of the Academy of Sciences of Moldova
c
Institute of Mathematics of Academy of Sciences of Moldova. [email protected]

Abstract –Thin films (1-10 µm thickness) of nanocomposites (NC) based on organic coordinated compound
(OCC) Eu(TTA)2(Ph3PO)2NO3 (where TTA is thenoyltrifluoroacetonate (C8H5F3O2S), Ph3PO -
triphenylphosphine (C6H5PO) and polymer – polyvinylpyrrolidone ((C6H9NO)n) (PVP)) were obtained by
chemical methods and with different molar ratios into organic polymer matrix. NC have been characterized
by measurements of optical transmission, excitation spectra of photoluminescence (PL) and
photoluminescence of NC at different concentrations of Eu(TTA)2(Ph3PO)2NO3 in NC. In the optical
transmission of NC, the characteristic parameters of NC such as threshold absorbance, dependence on the
concentration of the organic coordinated compound in NC, etc., have been determined The displacement of
threshold absorption to infrared is observed with increasing of the concentration of the coordination material
in NC. The excitation spectrum of photoluminescence of NC led the range from 200 to 400 nm energy at
which takes place the photoluminescence in NC. The PL of nanocomposites was detected as specific for
internal transitions 4f → 4f of the Eu3+ ion 5D0 → 7Fi (i = 0,1,2,3 and 4) centred at 537, 578, 615, 632,649, 690
and 705 nm, respectively at T=300 K. The dominant PL is in the position to 615 nm and the halfwidth is less
than 10 nm and it is attributed to the transition 5D0 → 7F2. The comparison of PL of NC with organic
coordinated compounds at equal ultraviolet exciting show the increasing of the external efficiency of NC
luminescence. In nanocomposites, the effect of energy transfer from polymer matrix to coordinated molecule
with subsequent transfer of them to Eu+3 ion have been identified. It was proposed some applications of given
nanocomposites in optoelectronics and medicine.

Key words – nanocomposites, rare earth ion, photoluminescence, polymer, energy transfer, laser emission

luminescence bands less than 10 nm in the visible and near-

infrared regions of spectrum at different excitations are of
I. INTRODUCTION
special interest.
Nanocomposites (NC) based on polymers and coordinate
Advantage of application of coordinated compounds of rare
complex organic compounds of rare earth metals are
earth ions with β-diketonates and ligands in nanocomposites is
excellent materials for a new generation of light emitting
based on the so-called "antenna" effect, or the transfer of
devices with high efficiency due to strong luminescence,
excitation energy from outside of the system of Eu3+ ion
easy colour tuneable, temperature insensitivity, and high
towards their energy levels. The population of upper energy
stability. Luminous properties of the complex coordinated
levels with subsequent transition to ground states is increased
compounds and nanocomposites on their basis can be a
in this case. The intermolecular energy transfer to the Eu3+ ion
subject of different applications in medicine, solar cells
takes place via the levels of ligands and their surroundings.
devices on the flexible substrates, optical signal
In prevous paper we report the investigations of the NC
amplification, etc. For the visible spectrum, more frequently
from copolymer butylmetacrylate and styrene in ratio of 1:1
are used the compounds with Europium (Eu3+) and Terbium
in whose matrix Eu(TTA)3H2O, Eu(TTA)3Phen and
(Tb3+) ions. Improving of their luminescence properties
Eu(DBM)3Phen were introduced [1-4]. For all investigated
depends on the type of ligands using for surrounding of the
materials with NC, photoluminescence levels caused by
rare earth ions. Photoactive complexes of organic
4f→4f transitions of Eu were identified. The most intensive
compounds of lanthanides may be used, as an example, like
luminescence band was centered at 615 nm and halfwidth ca
the trivalent ion of Europium chelated with β-diketonates, or
10 nm in all studied cases.
the cyclic ligands of carboxylate when the coordination
number of Eu3+ varies in the range from 6 to 9. Future II. METHODOLOGY
researches should be oriented towards achieving coordinated The synthesis of organic coordinated compound of
surrounding of the ion of Eu3+ in order to improve bis(thenoyltrifluoroacetonato) bis(triphenyl-phosphine
luminescence efficiency, and to obtain a final stable oxide)(mononitrate) europium (III) (Eu(TTA)2(Ph3PO)2NO3)
compound for various practical applications. The was carried out after the scheme described in [5,6] for
fundamental studies of the spectroscopy photophysic of rare analogue compounds. An amount of 4 mmol (0.44 g) of β-
earth metals and applications of the technology connected diketone and 2 mmol (0.56 g) of neutral ligand were
with effective luminescence with the halfwidth of the dissolved in 10 ml. of hot 96% ethanol, and 2 ml. of 1N

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sodium hydroxide were added. The mixture was stirred, Eu(TTA)2(Ph3PO)2NO3.

while 1 mmol of Europium nitrate in 5 ml. of water was On Fig.5a,5b,5c the spectra of photoluminescence of NC
added dropwise. A type of light cream precipitate formed Eu(TTA)2(Ph3PO)2NO3-PVP under excitation by N2 laser are
immediately. The precipitate was filtered off, washed with presented. The detected fluorescence bands correspond to
ethanol, dried thoroughly in air, and the solid of the complex the radiative transitions between the energy levels of the
was obtained. Yield was (0.85 g ) : Europium ions centred at 537, 578, 615 (611, 613, 617, 620),
For C52H38F6EuNO9P2S2 calcd, %: C = 51.49; H = 3.16; N 650 and 702 nm, and can be attributed to the spin forbidden
= 1.15; S = 5.28. 4f → 4f transitions 5D0 → 7Fi (i = 0,1,2,3 and 4),
Found, %: C = 51.49; H = 3.48; N = 0.95; S = 5.14. respectively. The most effective luminescence has the
The formula of the structure of OCC maximum at 615 nm at temperature 293 K which is about 20
bis(thenoyltrifluoroacetonato)bis(triphenylphosphine oxide) times higher than others, and its halfwidth is less than 10
(mononitrate)Europium(III) C52H38F6EuNO9P2S2 is shown nm.
on Fig.1. The optimal concentrations of Eu(TTA)2(Ph3PO)2NO3 in
Nanocomposites PVP/Eu(TTA)2(Ph3PO)2NO3 were nanocomposite were found in the range of 6 – 11% (Fig.6).
prepared from chemical solutions of separate components by There is an almost monotonous increase of intensity of
detailed method of preparation which will be described photoluminescence up to some 6 % of the OCC
separately later [7]. Polyvinylpyrrolidone ((C6H9NO)n was concentration in NC, and this feature is characteristic for all
used as the polymer with an average molecular weight 1 300 thin film samples at room temperature. The main feature of
000 g∙mol-1, white to light yellow, hygroscopic, amorphous these characteristics is a quite low signal of
powder (purchased from Aldrich Chemical Company). The photoluminescence in liquid solution samples, while thin
Europium complex Eu(TTA)2(Ph3PO)2NO3 was successfully film samples exhibits a significant grow of the intensity of
incorporated with different molar ratios into organic polymer photoluminescence.
matrix of PVP via sol–gel process. Drop- and spin-coated
IV. DISCUSSION
thin films on optical glass and quartz substrates were
The measuring of PL spectra determine the effective
obtained. The dried layers with thickness around 1-10 µm
transfer of energy from polymer matrix PVP to energy levels
turn out to be transparent in visible range of spectrum.
LUMO chelates of the complex Eu(TTA)2(Ph3PO)2NO3 and
The microscopic investigations of the morphology of the
subsequent energy transfer to the energetic levels of Eu3+
NC surface on a microscope MII-4 show that the dimensions
ion. HOMO and LUMO of complex Eu(TTA)2(Ph3PO)2NO3
of Eu(TTA)2(Ph3PO)2NO3 particles, incorporated in the
are found to be situated between levels S and T of polymer,
polymer matrix are invisible and hence are less than 100 nm.
and this case is similar to the doping case of semiconductor
Photoluminescence spectra have been measured using a set-
into its forbidden band with particularities of they
up based on MDR-23 monochromator connected to PC. NC
dimensions.
excited with N2-laser (λ = 0.337 μm) or Deuterium lamp
By comparing the PL of Eu(TTA)2(Ph3PO)2NO3 complex
have generated some sharp emission bands in the spectral
with PL of NC, the enhancing of the efficiency for
range of 300 – 800 nm. For optical transmission
photoemission in NC was observed. The enhancing can be
investigations a Specord UV/VIS (300’800 nm) CARL
explained by the coordination ability of the organic
ZEISS Jena unit was used. Absorption and luminescence
counterpart of the host structure of polymer, which is strong
properties of powder of Europium complex and NC were
enough to stabilise the position of chelates in
measured on each step of technology.
Eu(TTA)2(Ph3PO)2NO3 neighborhood after incorporation
III. EXPERIMENTAL RESULTS process.
Fig.2a,b shows the surface images of the NC films at The emission spectra of PVP/Eu(TTA)2(Ph3PO)2NO3 NC
different concentration of Eu(TTA)2(Ph3PO)2NO3 in the and Eu(TTA)2(Ph3PO)2NO3 powder was studied and
nanocomposites under white (Fig. 2a) and UV illumination analyzed. The emission spectra of NC were similar to that of
(Fig. 2b). The photos also reveal that Eu(TTA)2(Ph3PO)2NO3 corresponding Eu(TTA)3Phen complex [2], and the halfwidths
complex are dispersed in PVP homogenously without any of the strongest bands of PL were found to be less than 10 nm,
phase separation. but in this case the PVP/Eu(TTA)2(Ph3PO)2NO3 have most
Transmission spectra T(λ) of thin layers of NC on quartz high fluorescence intensity and color purity. Nanocomposites
substrates in the ultraviolet (UV) show clearly 3 absorption display a bright and narrow Eu3+ ion emission, which is due to
bands with maximums at 3.8, 4.5 and 4.8 eV, and with the so-called ―antenna‖ effect, defined as a light conversion
increasing of the OCC concentration in NC they grow until process via an absorption energy transfer-emission sequence
complete darkening in UV range. The sharp absorption involving distinct absorption by a polymer and ligand and their
threshold (Fig.3,4) is presented for all concentrations of energy transfer to Eu3+ ions and later their emission.
coordinated compounds of OCC in NC in the range of 370 - The experimental data of photoluminescence can be
380 nm of spectrum. The absorption spectra (α(λ)) are explained from the viewpoint of the surrounding
calculated from the transmission spectra T(λ) by the formula environment where the Eu3+ ion resides. PVP and OCC
α(λ) = - lnT/d (where d is the thickness of NC, α – absorption significantly affected the strength of the hypersensitive
coefficient). The energies of forbidden bands of NС (ΔENL= transitions (5D0 → 7Fi (i = 0,1,2,3 and 4) for Eu3+) of the
LUMO – HOMO, were HOMO is energy of high occupied complexes and the maximum of PL intensity at 613 nm.
molecular orbital and LUMO – low unoccupied molecular For the Europium complex, the intensity of the
orbital) obtained from 80 % of absorption threshold of T (λ) transitions of 5D0 → 7Fi (i = 0,1,2,3 and 4) increases in the
are in the range 3.14 - 3.16 eV. Forbidden band ΔENL = LUMO nanocomposite with grows the concentration of OCC in NC.
– HOMO= 3.15 eV are referred to coordinated compounds of When Eu(TTA)2(Ph3PO)2NO3 complexes were incorporated

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

into PVP, the complexes exhibited disorder. Under the Sciences of Moldova (Project 06.408.012F).
influence of the electric field of the surrounding ligands, the
REFERENCES
distortion of the symmetry around the lanthanide ion by the
[1] M. S. Iovu, A. M. Andriesh, S. A. Buzurniuc, V. I.
capping PVP due to the polarization of Eu3+, which increases
Verlan, M. I. Caraman, V. E. Zubarev. Luminescence
the probability for electric dipole allowed transitions. The
properties of Eu3+/thenoyltrifluoroacetonate
influence of PVP on the coordinated environment of Europium
composites. J. of Optoel. and Advan. Mater, 10, iss.4,
ions changes the energy-transfer probabilities of electric-dipole
841(2008).
transitions, accounting for the increase in luminescent intensity
[2] A. Andriesh, S. Buzurniuc, V. Verlan, M.I. Caraman, S.
of 615 nm peak of NC.
Robu, N. Barbă. Fluorescent properties of
The difference of the photoluminescence of Eu complex in
nanocomposite organic luminophore compound –
different nanocomposites can be interpreted as follows: when
polymer. J. of Optoel. and Advan. Mater., 10,
Eu complexes are introduced into the PVP, the molecular
353(2008).
motion is restricted and the stretching and bond vibration are
[3] M.S. Iovu, A.M. Andriesh, S.A. Buzurniuc, V.I. Verlan,
weakened by the PVP, both of which decrease the non-
C.I. Turta, V.E. Zubareva, M.I. Caraman. New
radiative transition. These results show that the
photoluminophore nanocomposite based on organic
nanocomposites could provide a relatively stable
compound with Eu3+ ions and copolymer styrene-
environment for lanthanide complexes and improve their
butylmethacrilate. J. of Non-Crystalline Solids, v.355,
luminescence properties.
p.1890(2009).
We suppose that the interaction of macromolecular
[4] M. S. Iovu, S. A. Buzurniuc, V. I. Verlan, I. P. Culeac,
ligands at high concentrations of Eu3+ ion leads to partial
and Yu. H. Nistor. New composite materials for
formation of coordinated unsaturated complexes and ionic
optoelectronic applications. Advan. Topics in Optoel,
aggregates, leading to the quenching of luminescence. From
Microel. and Nanotechn. IV. Ed. by Paul Schiopu,
these positions, the resulting polymer composites open the
Cornel Panait, George Caruntu, Andrian Manea Proc.
most promising way to neutralize the coordinated complexes
SPIE, 7297, (2009) 729703.
and to obtain structurally homogeneous materials with
[5] Melby L.R., Rose N.J., Abramson E., Caris J.C.
desired properties. From the spectra of NC (Fig. 5a,b), we
Synthesis and Fluorescence of Some Trivalent
can also suppose a low local symmetry of ligand field of ion
Lanthanide Complexes. J. Am. Chem. Soc. 86,
Eu3+ observed line transition 5D0 →7F0, which is interdicted
5117(1964).
under the high symmetry of the luminescence centre. The
[6] Batyreva V.A., German A.I. Serebrenicov V.V.
intensity of the transition 5D0 →7F0 is comparable with
Synthesis of rare earth compounds, Part 2, Tomsk
intensities of 5D0 →7F1, indicating also a significant
(Russia), ed. by university of Tomsk, 121(1986).
asymmetry around of rare-earth ions. The presence of
[7] Iovu Mihail, Verlan Victor, Buzurniuc Svetlana,
splitting of the transition line 5D0 →7F1 on three components
Zubareva Vera, Turtă Constantin. Process for obtaining
and of the transition line 5D0 7
F2 on five components
of luminophore composite based on polymer and
indicates the absence of axial symmetry of the inner
organic coordinated compound. Patent filed with the
coordination sphere of central ion Eu3+.
Agency AGPI of Moldova Republic. Number and date
V. CONCLUSION of deposit: S 2010 0087 at 2010-05-11.
The nanocomposites PVP/Eu(TTA)2(Ph3PO)2NO3 were
obtained by the method of chemical solutions.
From transmission spectra of NC measured in range 200
to 800 nm we have identified the absorption bands with
maximums centred at 3.8, 4.5 and 4.8 eV in the UV, and the
threshold of absorption forbidden band ΔENL = 3.15 eV was F3C
estimated. It is shifted slightly in the IR direction of the
O [O-P-Ph3]2
spectrum with increasing the percentage of
Eu(TTA)2(Ph3PO)2NO3 concentration in NC.
The photoluminescence spectra of NC was attributed to
Eu
the internal of transition of Eu3+ ion 5D0 →7Fi (i = 0,1,2,3 O
and 4) centred at 537, 578, 615 (611, 613, 617, 620), 650 NO3
and 702 nm. The halfwidth of PL band at 615 nm is less than
10 nm, which indicates that the nanocomposite exhibits high
fluorescence intensity and colour purity. S
The positive influence of PVP matrix on the coordinative 2
environment of Eu3+ ions was determined. A possible
method of raising the fluorescence of NC
PVP/Eu(TTA)2(Ph3PO)2NO3 is energy transfer from polymer Fig.1. Formula of the structure of
bis(thenoyltrifluoroacetonato)bis(triphenylphosphine
PVP levels and from levels of ligand to internal levels of oxide)(mononitrate)Europium(III) C52H38F6EuNO9P2S2.
Eu3+ ion. It was demonstrated the amplification of PL in the
NC compared with organic complex compound special.
ACKNOWLEDGMENTS
This work was supported by the Supreme Council for
Science and Technological Development of the Academy of

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2.5

2.0

2
1 - 1% 5
3
1.5 2 - 3%
4

D , a.u.
3 - 6%
4 - 9% 1

1/2
1.0 5 - 11%

Eg = 3.15 eV
0.5

0.0
a 2.6 2.8 3.0 3.2 3.4 3.6 3.8
h, eV

Fig.4. The optical density transmission spectra of samples of thin layers of

NC on glass substrates for different concentration of Eu(TTA)2(Ph3PO)2NO3
in PVP at room temperature (T=293 K).

3000

6% of Eu(TTA)2(Ph3PO)2NO3 in PVP
2500

2000
I, a.u.

1500

b 1000
Fig.2. Samples of thin layers of NC illuminated with visible (a) and UV
light (b).
500

0
100 500 550 600 650 700 750

90
, nm
80
Fig.5a
70
Transmision, a.u.

60 1 6% of Eu(TTA)2(Ph3PO)2NO3 in PVP
2500
50
1 - 1%
2
40 2 - 3% 2000
3 - 6%
30 4 - 9% 5
1500
5 - 11%
I, a.u.

20
3
1000
10 4
0
500
2.6 2.8 3.0 3.2 3.4 3.6 3.8
h, eV
0
450 500 550 600 650 700 750
Fig.3. The transmission spectra of samples of thin layers of NC on glass , nm
substrates for different concentration of Eu(TTA)2(Ph3PO)2NO3 in PVP at
room temperature (T=293 K). Fig.5b

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

2500
2600
6% of Eu(TTA)2(Ph3PO)2NO3 in PVP

Imax of photoluminescence, a.u.

2400

2000
2200

2000
1500
1800
I, a.u.

Eu(TTA)2(Ph3PO)2NO3 - PVP
1600
1000 d=4.5 m
1400

1200
500
0 2 4 6 8 10 12
x, %
0
600 605 610 615 620 625 630 635

, nm Fig.6. The maximum of intensity of photoluminescence at 615 nm of thin

layers of NC versus of concentration x of Eu(TTA)2(Ph3PO)2NO3 in NC.

Fig.5c
Fig.5. The photoluminescence spectrum of thin layer of NC
PVP/Eu(TTA)2(Ph3PO)2NO3 10 wt.% of concentration of complex
Eu(TTA)2(Ph3PO)2NO3 in NC: a,b – whole spectrum, c – detailed spectrum
of main maximum at room temperature (T=293 K).

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Nanoporous Zinc Oxide Films Prepared by

Magnetron Sputtering
L. GHIMPU, O. LUPAN, L. POPESCU, I.M. TIGINYANU
Laboratory of Nanotechnology, IEEIT, Academy of Sciences of Moldova
National Center for Materials Study and Testing, T.U.M.
Technical University of Moldova
[email protected]

Abstract – In this paper we demonstrate an inexpensive approach for the fabrication of nanoporous zinc
oxide films by using magnetron sputtering. Study of the structural properties proves the crystallographic
perfection of porous nanostructures and the possibility of its controlling by adjusting the technological
parameters in the growth process. The XRD pattern of nanoporous ZnO films exhibits high intensity of the
peaks relative to the background signal which is indicative of the ZnO hexagonal phase and a good
crystallinity of the samples grown by magnetron sputtering.

Index Terms – ZnO, nanoporous, films, magnetron sputtering.

for implementation in sensors. There are many types of

I. INTRODUCTION biosensors for use in physiological environments. Of these,
Over the last decade, nanostructured materials have those based on potentiometric measurement technique
received much greater attention because of their new (there, where current flow is not necessary during the
properties promising for various applications [1-6]. Control measurement) using zinc oxide, are interesting and
of size and morphology of materials is of interest to necessary, because current flow could damage biological
researchers dealing with the design of functional devices; systems and environments. Zinc oxide is biocompatible,
especially taking into account that optical and electronic biosafe and, moreover, it is a semiconductor with photonic
properties of nanometer sized materials depends upon the properties potentially usable for biophotonics. It is important
dimensions and shape [1,7]. to note that, along with UV, it emits in the visible region
Exploration of zinc oxide has proven its piezoelectric [13-15]. In addition, ZnO has an excellent electrochemical
properties, which led to its application in electronics, in activity and good properties of electron transport. Nanowire
particular in thin layers for devices with surface acoustic arrays or nanoporous films found application dye-solar cells
waves [8]. Currently the research of zinc oxide as a as well [13-15]. Most importantly, in the nanostructured
semiconductor material exhibits a new period of intense form zinc oxide can be grown on any substrates, either
development. Over the last years, remarkable results have crystalline or amorphous, and at various temperatures,
been published in the most prestigious international journals. including the possibility to grow it at relatively low
Increased interest in ZnO as an optical material has been temperatures, even at the temperature as low as 300 K. In
unleashed on p-type conductivity with ferromagnetic this work, we will present the magnetron sputtering of zinc
properties, and manufacture of field effect transistors in thin oxide nanoporous films. Its structural, morphological and
layers. A major driving force for research of zinc oxide as a vibrational properties are shown and discussed in details.
semiconductor material is its prospective use as a wide-band
semiconductor for light emitting devices and solar cells [4- II. EXPERIMENTAL PART AND DISCUSSIONS
6]. Note that the exciton binding energy of 60 meV is bigger Basic parameters of the magnetron sputtering method are
than the effective thermal energy at 300 K (26 meV). the voltage and discharge current power, specific power on
These characteristics make ZnO promising in a variety of the cathode, the gas pressure in the working chamber and
fields, along with electronics and optoelectronics. Further magnetic induction. The main advantages of this method
development of efficient systems for drug delivery for health consist in high speed of layers deposition and reproducibility
care needs new sensible and selective biosensors [9-10]. accuracy of the composition of the deposited layers. The
ZnO nanoparticles have been used in many applications in condensation rate of the magnetron sputtering depends on
our daily life, such as drug carriers and cosmetics [11]. the power of the discharge current and gas pressure in the
However, although inhalation of ultrafine ZnO particles at working chamber. Thus, using this method we succeeded to
relatively high dose (500 mg/m3) for 2 hours did not induce grow ZnO layers in the atmosphere of argon by applying a
acute systemic effects in humans, inhalation of ZnO fumes constant current (DC) and radio-frequency (RF) AC. A disc
in an occupational setting can cause metal fume fever of 99.99 % pure zinc served as target.
(fatigue, chills, fever, myalgias, cough, dyspnea, Pure porous-Zn was deposited over SnO2 thin films of size
leukocytosis, metallic taste, and salivation) [12]. Generally, 1.5 cm2 on glass substrates by direct current (DC) magnetron
nanostructures with high surface to volume ratio exhibit high sputtering. Preliminary, the substrates were cleaned for 2-3
sensitivity to adsorbed molecules and therefore are suitable hours in the mixed solution of chromium (7gK2Cr2O7-10ml

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

H2O-100ml H2SO4) at room temperature. The argon (Ar) nanostrucured films are represented. As one can see from the
working gas pressure was regulated in such a way to table, the chemical compozition shows 41.44 % of zinc and
maintain a constant vacuum pressure of 5 × 10−3 Torr. The 57.27 % of oxygen.
DC current used was 0.12-0.15 A, and the deposition time A section of ZnO structure morphology is represented in
was 9-22 min. The substrate was kept at a constant Figure 2. It is clearly seen that the zinc oxide layer is porous
temperature around 210oC. Several sets of samples have and is quite homogenous over the whole surface of the
been prepared in this way. Afterwards, these nanolayers samples.
grown on tin oxide/glass substrate were introduced into a
reactor and annealed at a temperature of 481 oC for 45
minutes in an oxygen atmosphere; gas flow was
approximately -100 ml/min.
The phase structure of the deposited films was studied
using Rigaku X-ray diffractometer (XRD) (CuK radiation
(=1.54178 Å)) and optimized operating conditions of 30
mA and 40 kV at a scanning rate of 0.04/s in the 2 range
of 24-90. The XRD pattern of doped nanoporous ZnO films
is shown in Figure 1. All tin oxide substrate peaks are
marked and are assigned to SnO2 according to PDF 00-041-
1445 card.

Fig. 1. XRD pattern of nanoporous ZnO grown by magnetron at 5C on tin

oxide/glass substrate. Substrate peaks are marked as SnO2.

The diffraction peaks in the pattern can be indexed to

hexagonal wurtzite structured ZnO [space group:
P63mc(186); a=0.3249 nm, c=0.5206nm] and diffraction
results are in agreement with JCPDS 036-1451 card for ZnO
[16]. The intensity of the peaks relative to the background
signal demonstrates high purity of the ZnO hexagonal phase
of the products and a very good crystallinity of the samples
[17-19] grown by magnetron sputtering. The characteristic
peaks of impurities was not observed, which is indicative of
a single phase hexagonal ZnO. The nanocrystallites are
oriented along the (101) indicated by the highest intensity
peak [16].
The morphology and chemical composition of the
nanostructured films of ZnO were studied using a TESCAN
Scanning Electron Microscope (SEM) equipped with an
Oxford Instruments INCA Energy Dispersive X-ray (EDX)
system. The EDX analysis of the produced structures
demonstrates a relative stoichiometric ZnO composition
(within a precision of 1 at.%). The composition was Fig. 2. a) EDX images of nanoporous ZnO; b,c) SEM images of
characterized by Energy Dispersion X-ray Spectrometer nanoporous zinc oxide films grown by magnetron sputtering on tin
(EDX). oxide/glass substrate: top and cross-sectional views, respectively. Scale
In the Figure 2a the results of EDX analysis of the bars are 5 µm and 10 μm, respectively.
The room temperature Raman scattering was studied with

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a Confocal Laser Raman System in the backscattering REFERENCES

geometry under the excitation by a laser. Raman [1] Z. L. Wang, ―Zinc oxide nanostructures: growth,
investigations (see Fig. 3) provide information about the properties and applications,‖ J. Phys.: Condens. Matter.,
material quality, the phase and purity, allowing one to vol. 16, pp. R829–R858, 2004.
understand vibrational properties and phonon interaction [2] R. Baron, F. W. Campbell, I. Streeter, L. Xiao, R. G.
with the free carriers [15,17]. The group for ZnO is C 6 v , and Compton, Int. J. Electrochem. Sci. 3, pp. 556, 2008.
[3] O. Lupan, G.A. Emelchenko, V.V. Ursaki, G. Chai,
12 degrees of freedom exist since there are four atoms per A.N. Redkin, A.N. Gruzintsev, I.M. Tiginyanu, L.
primitive cell. There are nine optical phonon modes and Chow, L.K. Ono, B. Roldan Cuenya, H. Heinrich, E.E.
three acoustic phonon modes. Phonon modes E2 (low and Yakimov, ―Synthesis and characterization of ZnO
high frequency), A1 [(TO)-transverse optical and (LO)- nanowires for nanosensor applications,‖ Materials
longitudinal optical] and E1 (TO and LO) are expected, all Research Bulletin, vol 45(8), pp. 1026-1032, August
being Raman and infrared active [17,20]. According to 2010.
group theory, the optical modes at the  point of the [4] O. Lupan, L. Chow, G. Chai, A. Schulte, S. Park, O.
Brillouin zone can be expressed by [20]: Lopatiuk-Tirpak, L. Chernyak, H. Heinrich,
―Biopolymer-assisted self-assembly of ZnO
opt  1A1  2B1  1E1  2E2 nanoarchitectures from nanorods,‖ Superlattices and
Microstructures, vol. 43(4), pp. 292-302, April 2008.
A1(z), E1(x), E1(y) and E2 are Raman active modes, except [5] O. Lupan, Th. Pauporté, B. Viana, I. M. Tiginyanu, V.
the silent mode B1. Figure 3 shows the Raman spectrum V. Ursaki and R. Cortés, ―Epitaxial Electrodeposition of
measured in backscattering geometry in the nanoporous ZnO ZnO Nanowire Arrays on p-GaN for Efficient UV-
grown by magnetron sputtering on TO substrate. The E2 Light-Emitting Diode Fabrication,‖ ACS Appl. Mater.
optical mode corresponds to dominant peaks at 100 cm-1 and Interfaces, 2010, 2 (7), pp 2083–2090, July, 2010.
438 cm-1, which are commonly detected in the wurtzite [6] O. Lupan, T. Pauporté and B. Viana, ―Low-Temperature
structure of ZnO [20]. The Raman spectrum of the ZnO Growth of ZnO Nanowire Arrays on p-Silicon (111) for
films demonstrates a high quality of the wurtzite crystal Visible-Light-Emitting Diode Fabrication,‖ J. Phys.
structure in the produced material. Chem. C, 2010, 114 (35), pp 14781–14785, August
2010.
[7] A. Bayandori Moghaddam, M. Kazemzad, M. R. Nabid,
H. H. Dabaghi, Int. J. Electrochem. Sci. 3, pp. 291,
2008.
[8] D. J. Milliron, S. M. Hughes, Y. Cui, L. Manna, J. Li,
L.-W. Wang, A. P. Alivisatos, Nature 430, pp. 190,
2004.
[9] D. C. Look, Mater. Sci. Eng. B 80, pp. 383, 2001.
[10] Vavrinsky E., Flyckyngerova, S.Gaspierik,
P.Skriniarova, J.Novotny, et all. Micro-nano-
structuralized interfaces of conductive and transparent
thin film microelectrodes for biomedical application.
App.Scien. in Biomedical and Communication
Technologies, 2009, ISABEL, 2009, 2nd International
Sympozium.
[11] Haijun Zhanga, Baoan Chena, Hui Jiang, Cailan Wang,
Huangpin Wang and Xuemei Wang. A strategy for ZnO
nanorod mediater multi-mode cancer treatment.
Fig. 3. Raman spectrum for nanoporous zinc oxide films grown on tin Biomaterials Volume 32, Issue 7, pp.1906-1914, 2011.
oxide/glass substrate. [12] W. S. Beckett, D. F. Chalupa, A. Pauly-Brown, D. M.
Speers, J. C. Stewart, M. W. Frampton, M. J. Utell, Li-
III. CONCLUSION Shan Huang, C. Cox, W. Zareba and G. Oberdörster,
Novel nanoporous ZnO films were synthesized by American Journal of Respiratory and Critical Care
magnetron sputtering. The obtained results of the ZnO Medicine 171, pp. 1129, 2005.
structure morphology and the XRD data prove the possibility [13] J. Zhou, N. S. Xu, Z. L. Wang, Adv. Mater. 18, pp.
to control the properties in a controlled fashion. Wurtzite 2432, 2006.
crystal structure corresponds to a single hexagonal phase of [14] O. Lupan, V.M. Guérin, I.M. Tiginyanu, V.V. Ursaki,
ZnO, where the nanocrystallites are oriented along the (101) L. Chow, H. Heinrich, T. Pauporté, ―Well-aligned
axis. This study allows one to conclude that these layers are arrays of vertically oriented ZnO nanowires
useful for DSSC solar cells and light emitting devices. electrodeposited on ITO-coated glass and their
integration in dye sensitized solar cells‖, Journal of
Photochemistry and Photobiology A: Chemistry, vol.
ACKNOWLEDGMENTS 211(1), pp. 65-73, March 2010.
Financial support by Supreme Council for Science and [15] I. M. Tiginyanu, O. Lupan, V. V. Ursaki, L. Chow, M.
Technological Development of the Academy of Sciences of Enachi, ―Nanostructures of Metal Oxides.‖
Moldova are acknowledged.

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Comprehensive Semiconductor Science & Technology, [18] L. Chow, O. Lupan, Guangyu Chai, ―FIB fabrication of
Chapter 3.11, pp. 396-479, 2011. ZnO nanotetrapod and cross-sensor,‖ Physica Status
[16] XRD. American Society for Testing and Material. Solidi (b), vol. 247(7), pp. 1628–1632, July 2010.
Powder Diffraction Files; Joint Committee on Powder [19] O. Lupan, L. Chow, G. Chai, H. Heinrich, ―Fabrication
Diffraction Standards: Swarthmore, PA, pp.3-888. Joint and characterization of Zn–ZnO core–shell
Committee on Powder Diffraction Standards, Powder microspheres from nanorods,‖ Chemical Physics
Diffraction File PDF# 021-1250. Letters, vol. 465(4-6), pp. 249-253, November 2008.
[17] O. Lupan, L. Chow, G. Chai, B. Roldan, A. Naitabdi, A. [20] O. Lupan, V.V. Ursaki, G. Chai, L. Chow, G.A.
Schulte, H. Heinrich, ―Nanofabrication and Emelchenko, I.M. Tiginyanu, A.N. Gruzintsev, A.N.
characterization of ZnO nanorod arrays and branched Redkin, ―Selective hydrogen gas nanosensor using
microrods by aqueous solution route and rapid thermal individual ZnO nanowire with fast response at room
processing,‖ Materials Science and Engineering: B, vol. temperature,‖ Sensors and Actuators B: Chemical, vol.
145(1-3), pp. 57-66, December 2007. 144(1), pp. 56-66, January 2010.

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Interband Optical Transitions in the Region of

Excitonic Resonance in In0.3Ga0.7As/GaAs
Quantum Wells
Eli KAPON1, Alexandru MEREUŢA1, Andrei DOROGAN2, Nicolae DRAGUTAN2,Tatiana VIERU2,
Nicolae SYRBU2, Victor ZALAMAI3
1
Swiss Federal Institute of Technology in Lausanne, Lausanne, Switzerland
2
Technical University of Moldova, Kishinev, Moldova
3
Institute of Applied Physics, Kishinev, Republic of Moldova
[email protected]

Abstract – Reflection spectra of In0.3Ga0.7As layers with 8nm thickness with quantum wells limited by GaAs
barrier layer with 100nm thickness (bottom) and 9nm (upper) had been measured at S and P polarizations in
the interval of photon energies 0.6 – 1.6eV at an incident angle near the normal one (4.5о) and Brewster angle
(76 о). Thin absorption lines 0.9021eV, 1.0161eV, 1.1302eV, 1.1973eV, 1.2766eV conditioned by the transitions
hh1-e1(1s), lh1-e1(1s), hh2-e2(1s), lh2e-2(1s), hh3-3(1s) and lh3-3e(1s) had been revealed. The intensity of
absorption lines changes in the limits 10 – 70%.
Index Terms – quantum wells, optical properties, exciton, resonance.

coefficient is the change of the nonradiative decay Г with the

effective nonradiative decay in the respective expression
I. INTRODUCTION
The study of semiconductor heterostructures with eff    inh , where inh is the broadening parameter.
quantum points and wells are of big interest if talking about Figure 1 shows the reflection spectra of In0.3Ga0.7As/GaAs
revealing fundamental electronic states of excitonic with quantum wells at 300K and incident angles 7о and 76о
polaritons in quantum points and wells. At the same time, it (Brewster angle) for S-S (A) and P-P (B) lightwaves‘
has to be highlighted, that basing on quantum well structures polarization. The experimental rays‘ path is presented in the
are developed opto- and micro-electronic devices of new insertions a and b. The reflection minimums b1- b6, which
generation [1-3]. Injection lasers based on quantum points have and increasing half with in case of Brewster angle, are
that prove a high temperature stability of threshold current present at S-S polarization at a 7о incident angle. The same
density Jth, low value of Jth and continuous generation at minimums are present in reflection spectra at P-P
room temperature with 3W output power are created at the polarization at a 7о incident angle.
moment.
II. EXPERIMENTAL DATA AND DISCUSSIONS
The optical reflection has been measured on JASCO-680
spectrometer at 300K and s and p polarizations, at different
light angles incident on the surface of the heterojunction
with quantum wells.
The reflection spectra R   r   , among the
2

photoluminescence analysis, is the simplest method of

characterization of heterostructures with quantum wells.
The inferior surface of the structure was polished
till a mirror state in order to study transparency spectra
T    t   . It is necessary to measure R and T to
2

determine the absorption of structures with quantum wells,

and to determine the A  values.
A   1  R   RT  . (1)
It is known, that not the idealness of the structure Fig. 1 Reflection spectra of GaAs /In0.3Ga0.7As/GaAs structure with
influences the optical reflection and absorption spectra, quantum wells at 300K and incident light angle 7о and 76о (Brewster angle)
broadening the exciton resonance frequency in for S-S (А) and P-P (Вpolarizations of lightwaves. The experimental rays‘
path is presented in the insertions a and b.
heterostructures. The inhomogeneity can lead to a
smooth coordinate dependence of ω0 in the quantum well The minimums а1- а6 are revealed in the reflection
plane or in the volume of the supperlattice, which leads to a spectra at an incident angle equal to the Brewster one (76о),
broadening of the absorption and reflection lines. The i.e. they are shifted. The shifting value for all reflection
simplest and most effective method of accounting the minima is approx equal. The measurement amplitude of
inhomogeneous broadening while calculating the reflection reflection spectra (max – min) is also twice decreased for

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this polarization. bidimensional wave vector is excited, i.e. with K x  K y  0 .

Figure 2 shows the scheme of the periodical structure, A detailed analysis of the reflection and transparency
consisted of In0.3Ga0.7As layers with 8nm thickness with coefficients of quantum well heterostructures is presented in
quantum wells divided by GaAs barrier layers with 9nm
thickness and the electronic transitions from the ground the work [1], where the reflection rQW has the expression:
excitonic states in quantum wells. The reflection spectra i0
presented in figure 3 are measured at an incident angle of 7о rQW  (4)
 0    i  0 
and the transparency spectra at a normal light angle incident
to the GaAs/In0.3Ga0.7As/GaAs heterostructure surface with 0*  0  r100 sin 2 0  0 (1  r10 cos 2 ) (5)
quantum wells.  and 0 are the resonance frequency and the radiative
*
0
As the measurements were done at a spectrometer with
high resolution, it can be noted that the minimums‘ energy decay of the exciton, renormalized taking into account the
of reflection spectra completely coincide with the energetic exciton interaction with the lightwave, induced by this
position of the maxima in the absorption spectra. The exciton and reflected from the external surface.
reflection geometry is presented in figure 1, b. The plane
monochromatic wave Er, t   E0 exp  it  ikr  falls on the
In0.3Ga0.7As quantum well, positioned between two identical
GaAs barriers, which are characterized by real permittivity
 b . The lightwave vector is linked with the frequency
correlation ω k   c   b , where c – light speed in vacuum.

Fig. 3 Reflection and transparency spectra of GaAs/In0.3Ga0.7As/GaAs

heterojunctions with quantum wells.

Fig. 2 Periodical structure consisted of two In 0.3Ga0.7As layers with 8nm

The dependence of the reflection coefficient was
thickness with quantum wells, divided by GaAs barrier layers with 9nm established after some transformations [1] on the reflection
thickness and the electronic transitions from the excitonic states in quantum and absorption coefficients:
wells.

In case of normal incident light, when the lightwave (6)

vector k is parallel to the main structure axis z, the lightwave (7)
amplitude E 0 lays in the interface plane x, y  . As the where
system possesses axial symmetry in reference of k to z axis, (8)
the electrical vectors of the incident, reflected and passed (9)
lightwaves are parallel to each other and scalar amplitudes
According to the Fresnel formulas, in case of normal
Е0, Еr and Еt can be used instead of vector amplitudes. The
incident light:
amplitude reflection and absorption coefficients are:
r  E r E0 , t  Et E 0 (2) (10)
In case of energy dissipation absence inside the quantum
The A and B coefficients can obtain different sign values,
well the law of energy conservation lays on these
and, separately, become null, depending on the distance
coefficients:
between the well center and the external surface. If A  0 ,
r  t 1
2 2
(3)
B  0 the resonance contour is consisted of a maximum
In case of normal incident light the exciton with a null

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  0* and minimum at   0* . If B  0 , the spectra has The best correlation between calculated and
experimental spectra was obtained at a decay factor   0 ,
one maximum ( A  0 ) or one minimum ( A  0 ) [1, 2].
0  (20  2)meV , and background dielectric permittivity
 b  10 and the longitudinal-transversal permeability
 LT  80meV . The exciton lifetime is
 0  20   2  10
1 11
s  10 ps . The thin absorption and
reflection lines and the theoretically obtained parameters can
prove the quality of the structure with quantum wells.

REFERENCES
[1] E. L. Ivchenko, Optical spectroscopy of semiconductor
nanostructures (Alpha Science International, Harrow,
UK, 2005).
[2] L. E. Vorobjev, E. L. Ivchenko, D. A. Firsov, V. A.
Shalygin, Optical nanostructures properties., Edited by
V. I. Iljina and A. Ja. Shika, Edition ―Science‖, Sankt-
Petersburg, 2001.
Fig.4 Experimental reflection spectra and the ground excitonic state [3] N. N. Syrbu and V. V. Ursaki, Book, Exciton
contours in quantum wells of GaAs /In0,3Ga0,7As/GaAs heterojunctions Quasiparticles: Theory, Dynamics and Applications,
calculated by the dispersion correlations.
Editors: Randy M. Bergin, (Nova Science Publisher.
The calculations of the reflection spectra of the ground Inc., USA, 2010).
excitonic states in quantum wells are made basing on the
dispersion correlations which is based on multi oscillatory
model [3].

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Multi-gated Field Emitters for a Micro-column

Hidenori MIMURA1, Akifumi KOIKE1, Toru AOKI1, Yoichiro NEO1, Tomoya YOSHIDA2, and
Masayoshi NAGAO2
1
Research Institute of Electronics, Shizuoka University, Hamamatsu, 432-8011, Japan
2
National Institute of Advanced Industrial Science and Technology, Tsukuba, 305-8568, Japan
[email protected]

Abstract – We have developed a multi-gated field emitter (FE) such as a quadruple-gated FE with a three-
stacked electrode lens and a quintuple-gated FE with a four-stacked electrode lens. Both the FEs can focus
the electron beam. However, the quintuple-gated FE has a stronger electron convergence than the quadruple-
gated FE, and a beam crossover is clearly observed for the quintuple-gated FE.

Index Terms – beam crossover, electron beam, focusing, micro-column, multi-gated field emitter

After the deposition of SiO2 and Nb films, a photoresist is

I. INTRODUCTION spin coated on the Nb film. The thickness of the photoresist
A field emitter array (FEA) with a focusing electrode is an on top of the mountain structure becomes thinner than that
attractive device for applications, such as a scanning electron on the flat surface. (d) Therefore, the Nb electrode at the tip
microscope and electron beam lithography and so on. As the is selectively etched by the following RIE step without
FEAs with a focusing electrode, double-gated FEAs have precise lithography. The electrode height can be controlled
been proposed. However, the double-gated FEA has a by the etching time and is adjusted to be the same as that of
problem that the emission current decreases under the strong the emitter tip. The first Nb electrode acts as an extraction
focusing conditions. This is due to the lowered field gate electrode. (e) In the quadruple-gated FE, three
enhancement at the emitter tip caused by the low potential of additional electrodes, which form an electrostatic lens, are
a vicinal focusing electrode. [1] To solve such the problem, stacked by repeating the steps from (b) to (d) three times. In
we have reported the other approach that uses the focusing the quintuple-gated FE, four additional electrodes, which
electrode located below the extraction gate electrode in a form an electrostatic lens, are stacked in the similar way. (f)
volcano structure. [2, 3] However, we observed that some Finally, the emitter tip is opened by the buffered
electrons cannot penetrate the potential barrier formed by the hydrofluoric acid (BHF).
focusing electrode potential under strong focusing Figures 2 (a) and (b) show cross sectional SEM images of
conditions. These electrons go back to the extraction gate the quadruple-gated FE and quintuple-gated FE,
electrode. To overcome these problems simultaneously (field respectively. In the both FEs, the first Nb electrode acts as
enhancement and potential barrier), an electrostatic lens an extraction gate electrode. In the quadruple-gated FE, the
using a multistacked-electrode should be integrated at the G1 and G2 among the three-stacked electrostatic lens are set
emitter tip, and at least three additional electrodes are at the same voltage. In the quintuple-gated FE, G1 and G4
necessary. The first electrode (near the emitter tip) is used to among the four-stacked electrostatic lens are set at the same
maintain the potential at the emitter tip; therefore, a voltage voltage. G2 and G3 (G2,3) are connected through a contact
higher than the extraction gate voltage is applied. The hole, and are set at the same voltage. Therefore, both the
second electrode is used to focus the electron beam; three-stacked and four-stacked electrostatic lenses form an
therefore, a voltage lower than the extraction gate voltage is eizel lens.
applied. The third electrode is used to inhibit the generation Figure 3 shows the top-view micrograph of the quadruple-
of a potential barrier on the electron trajectory; therefore, a gated FE. The dotted line in the micrograph shows that the
voltage higher than the second electrode voltage is applied. electrode holes from accurate concentric circles with the
In this paper, we have developed a multi-gated field emitter tip as a center pole. This is due to the full self-
emitter (FE) with a four-stacked gate electrode, and a FE aligned process. The alignment of electrode holes is very
with a five-stacked gate electrode, that is, quadruple-gated important for the electrostatic lens to avoid an aberration.
FE with a three-stacked electrode lens and quintuple-gated
FE with a four-stacked electrode lens. III. ELECTRON EMISSION CHARACTERISTICS
The electron emission from both the quadruple-gated FE
II. FABRICTION OF THE MULTI-GATED FIELD and quintuple-gated FE were measured in a high-vacuum
EMITTERS chamber at a pressure of 1 x 10 -7 Pa. Figures 4 (a) and (b)
The fabrication process for the multi-gated FEs is show extraction-gate-voltage (Gex) versus anode-current
schematically shown in Fig. 1. (a) An emitter cone is formed characteristics of the quadruple-gated FE and quintuple-
from single crystalline Si by reactive ion etching (RIE) using gated FE, respectively. An anode phosphor screen biased at
a SiO2 dot as an etching mask. The apex radius of the tip is 1 kV was located 1 mm above the FE substrate. For the
5-10 nm. (b) A SiO2 insulating layer is deposited by plasma- simple anode-current characteristics, the all potentials of the
enhanced chemical vapor deposition (PE-CVD) using electrostatic lens were set equal to that of the extraction gate
tetraethoxysilane (TEOS) gas followed by Nb deposition. (c) electrode, as schematically shown in the insert of Figs. 4 (a)

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and (b). In the quadruple-gated FE, emission started at 20 V than that of the quadruple-gated FE.
and reached 3 A at an extraction voltage of 60 V, while in
IV. CONCLUSION
the quintuple-gated FE, emission started at 30 V and reached
We have successfully fabricated a multi-gated FE such as
100 nA at an extraction voltage of 60 V. In the quintuple-
quadruple-gated FE with a three-stacked electrode lens and a
gated FE, more electrons entered the gate electrodes in
quintuple-gated FE with a four-stacked electrode lens. The
nonfocusing condition, because the lens size is larger than
fabrication process uses an etch-back technique. In our
that of the quadruple -gated FE.
method, gate hole opening is a self-aligned process;
Figure 5 shows the beam spots measured from the anode
therefore, the axes of electrode holes are well aligned
phosphor screen images for the quadruple-gated FE and
without precise lithography. Both the quadruple-gated FE
quintuple-gated FE. In the quadruple-gated FE, the voltages
and quintuple-gated FE can focus the electron beam.
of Gex, G1 and G3 were fixed at 50, 100, and 100 V,
However, lens function for the quintuple-gated FE is
respectively. The voltage of G2 was changed from 100 V
stronger than that of the quadruple-gated FE, and a beam
(nonfocusing condition) to -20 V (focusing condition). In the
crossover is formed for the quintuple-gated FE. The multi-
quintuple-gated FE, the voltages of Gex, G1, and G4 were
gated FE is a promising device for a micro-column for a
fixed at 50, 100, and 100 V, respectively. The voltage of
scanning electron microscope and electron beam
G2,3 was changed from 100 V (nonfocusing condition) to -
lithography.
10 (focusing condition). Figure 5 also shows the phosphor
images at G2,3 = 100, 10, and -10 V for the quintuple-gated
FE. For the quadruple-gated FE, the beam spot REFERENCES
monotonously decreases as the G2 voltage decreases from [1] Y. Yamaoka, S. Kanemaru, and J. Itoh, Jpn. J. Appl.
100 to -30 V. On the other hand, for the quintuple-gated FE, Phys. 35, pp.6626, 1996.
the beam spot decreases as the G2,3 voltage decreases from [2] Y. Neo, T. Soda, M. Takeda, M. Nagao, T. Yoshida, C.
100 to 10 V, but then the beam spot increases as the G2,3 Yasumuro, S. Kanemaru, T. Sakai, K. Hagiwara, N.
voltage go from 10 to -10 V. This indicates that a beam Saito, T. Aoki, and H. Mimura, Appl. Phys. Express 1,
crossover (a beam focal point) is formed between the anode pp.053001, 2008.
and the field emitter. Since the field emitter and anode are 1 [3] T. Soda, M. Nagao, C. Yasumuro, S. Kanemaru, T.
mm apart and the crossover is formed immediately in front Sakai, N. Saito, Y. Neo, T. Aoki, and H. Mimura, Jpn. J.
of the field emitter, the beam spot size shown in Fig. 5 are Appl. Phys. 47, pp.5252, 2008.
not exact size, and real beam size of the crossover is
expected less than 50 nm. The results in Fig. 5 also show
that the lens function for the quintuple-gated FE is stronger

Fig. 1 Fabrication process for the quadruple-gated FE with a three-

stacked electrode lens.

Fig. 2. Top-view SEM image of the quadruple-gated FE.

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Gex

(a) (b)
Fig. 3 Cross-sectional SEM images of the quadruple-gated FE (a) and the quintuple-gated FE.

(a) (b)
Fig. 4 Emission characteristics of the quadruple-gated FE (a) and the quintuple-gated FE (b).

Quadruple-gated FE

Quintuple-gated FE

Beam crossover

Fig. 5 Beam spots measured from phosphor screen images for the quadruple-gated FE (a) and the quintuple-gated FE (b). Solid and dashed lines are
the least-square estimations for the quadruple-gated FE and the quintuple-gated FE, respectively.

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Nano Metrology Aspects of Design, Simulation,

Fabrication, Testing , Reliability and Failure
Analysis of Wafer Fused VCSEL
Vladimir IAKOVLEV, LPN EPFL

Abstract – In this paper are presented several application aspects of nano metrology tools in characterization
and fabrication of high performance long wavelength wafer fused VCSELs as well as for failure analysis.
As long wavelength VCSELs are emerging as attractive light-sources for replacing DFB lasers in power
consumption sensitive applications, the main challenges in developing the cost and time efficient nano
metrology tools for supporting processing and characterization are discussed.

Index Terms – Long-wavelength, VCSELs, wafer fusion, VCSEL technology, failure analysis, nanometrology

industrial fabrication process demonstrates the possibility of

I. INTRODUCTION
wavelength inventory selection in the range 40 nm on the
Long wavelength (LW) vertical cavity surface emitting
same 2-inch VCSEL wafer. The first documented reliability
lasers (VCSELs) emitting in the 1300 and 1550 nm band
data obtained on wafer-fused VCSELs processed in the
with single mode (SM) output power in excess of 1mW in a
industrial wafer fab of a leading optical component
wide temperature range up to 85°C, high speed modulation
manufacturer in Europe. Results show that VCSELs
capabilities and accurate emission wavelength setting
fabricated with the wafer-fusion technique and displaying
present interest in broad band optical communications, and
high performance level, meet Telcordia generic requirement
sensing . Compared with standard distributed feedback
standards. Finally, the first results of implementing state
(DFB) edge-emitting lasers, VCSELs offer advantages of
of the art nanometrology tools for failure analysis as well as
the main challenges in decreasing the cost and duration of
full range on ongoing failure analysis are briefly discussed.
II. VCSEL DESIGN AND SIMULATIONS
The VCSEL device structure comprises an InP-based 5/2
λ-active cavity that is fused on both sides to undoped
AlGaAs/GaAs DBRs, as schematically depicted on Figure 1.
The active cavity includes an InAlGaAs/InP multi-QW
Fig. 1. Schematic cross section of the wafer fused 1310 nm VCSEL region with 4-6 compressively strained quantum wells and a
symmetric far-field emission pattern, low power p++/n++ InAlGaAs tunnel junction.‖
consumption and continuous wavelength tuning with Figure 2 presents transverse gain and mode profiles of this
current. State of the art longwavelength VCSELs with design at different temperatures that were obtained by
increased single mode output power have a hybrid structure numerical solving of a fully coupled 2-dimentionsional set of
combining GaAs/AlGaAs or dielectric distributed Bragg elctro-opto-thermal equations [4].
reflectors (DBRs) for high reflectivity with InP/InAlGaAs
quantum well (QW) active regions for high optical gain at
elevated temperatures. In addition, employing tunnel
junctions has allowed intra-cavity contacting with low-
absorption DBRs, a crucial ingredient for reaching high
single mode power and high modulation speed. Among all
leading LW-VCSEL technologies, localized wafer fusion
offers the greatest flexibility in selecting the emission
wavelength while the utilized GaAs/AlGaAs DBRs provide
the best thermal conductivity . Consequently, the wafer
fusion approach yielded 1300 and 1500 nm VCSELs with
state of the art performances [1,2]. In this paper we describe
the design, fabrication process and characterization results of Fig. 2. Lateral gain and optical field distributions from the center of the
tunnel junction . Ro represent the edge of a TJ mesa with diameter of 6 um
wafer fused 1310 and 1550 nm single-mode VCSELs with
lower power consumption as compared with corresponding As one can observe the fundamental mode is predominant
DFB edge-emitting lasers at the same output power level of and the gain and mode profiles spread by about 1-1.5 μm
1mW and operation speed above 5 Gb/s . The capability of outside the active region defined by the tunnel junction
cavity adjustment for setting the emission wavelength in a mesa. The optical confinement is due to a lateral refractive
specified position of the CWDM grid, on the full wafer-scale index variation that corresponds to a difference in the optical

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paths of about 7 nm for the light propagating through the the VCSELs structure. Double fused VCSEL wafers are
tunnel junction mesa and adjacent re-grown InP. produced systematically without any voids at both fused
III. FABRICATION AND TESTING 1
The InP-based active cavity and GaAs-based DBRs are
grown by low pressure metal-organic vapor phase deposition
(LP-MOVPE) on 2 (100) wafers [3] . A mesa-structure of 6-
7 μm in diameter formed in the tunnel junction that is
regrown with n-type InP serves for carrier and photon
confinement.
Electrical contacting is performed by top and bottom 2
intra-cavity n-InP layers. This contacting scheme allows a b
using un-doped top and bottom DBR mirrors. InGaAsP
cavity adjustment layers that are located on both sides of the
active cavity serve for precise adjustment of the emission
wavelength.
Figure 4 depicts images of tunnel junction mesas at
different stages of the fabrication process: a- initial mesas
etched in the tunnel junction, b,c after regrowth, before first
c d
fusion step, d, e-after the first fusion step. As one can Fig. 3. (a) Peak lambda map, (b) peak intensity map (c) spectrum in point
observe from Figure 4, after re-growth mesas have elliptical 1 and (d) spectrum in point 2.
shape and a size that is 2-2.5 times larger compared with
initial mesas that have a round shape ( please note that the interfaces, with a high surface quality over the full 2-inch
image size and picture resolution are not enough to give all wafer.One of the big advantage of vertical cavity surface
the details, Figure 4 should be considered only for concept emitting laser technology is the possibility to perform full
description). This occurs due to predominant lateral wafer test without cutting the wafer is parts. In Figure 3 it
overgrowth with a tendency to planarization occurring is presented the pictures of wafer map performed
during regrowth by MOVPE. Consequently, the optical immediately after removing substrate form top DBR side.
mode, that extends by about 1.5 μm outside the active region One can clearly see 4 different wavelength regions, the
defined by the mesa etched in the tunnel junction (Figure 4) shortest wavelength is in region denoted by 1 in Figure 3a
is well within the edges of the re-grown region that will help and the longest is in region denoted by 2. The PL spectra
in selection of the fundamental mode. The elliptical shape of are presented in Figure 3c and d respectively: In Figure 3b
the regrown mesa provides a way for discrimination of it is presented the map of peak intensity. As one can see,
polarization modes. Before the first fusion process, the top the highest intensity it is observed in region 1, the lowest
InGaAsP cavity-adjustment layer is selectively etched on it is observed in region 2. One of the challenges in the
one half of the wafer. The oblique line on Figure.2,c future work in developing nano metrology tools for
represents the border between two regions on the wafer with
different cavity lengths.
During the fusion process, InP-based and GaAs-based 2-
inch wafers are brought into contact at 600°C in vacuum,
and by applying a pressure of 7000 N for 30 min in an
industrial custom-built wafer bonding machine. At these
values of temperature and pressure, both wafers undergo a
slight plastic deformation resulting in a uniform contacting
on a nanometer scale. As a result, covalent bonds are
formed between InP-based and GaAs-based wafers. After a b c d e
cooling down the stack that includes InAlGaAs/InP- Fig. 4. Images of TJ mesas: a - initially etched 7 µm mesas, b,c-
AlGaAs/GaAs half-cavity with InP and GaAs substrates on regrown mesas before fusion, d, e - after fusion.
respective sides is bowed. This bowing with a radius of
supporting
curvature of about 1 m occurs because of different values of
fabrication technology of longwavelength VCSELs is to
thermal expansion coefficients of GaAs-based wafers with
find the necessary vertical design and processing flow
lattice parameter of 5.6535Å and InP-based wafers with
that will allow correlation between PL map data and
lattice parameter of 5.86875Å, (5.8x10-6 /K for GaAs and
device performance.
4.8x10-6 /K for InP). After selectively etching the InP
The processing of the double-fused VCSEL wafer is
substrate the remaining GaAs substrate containing the fused
performed in a standard way. It includes reactive ion etching
stack re-gains its planarity.
of the top DBR, selective chemical etching steps in the
In the second fusion step a second DBR is fused to the
InAlGaAs/InP active cavity region, dielectric deposition, dry
InP-based active cavity in the same conditions as during the
etching steps and e-beam deposition of metals for contacts
first fusion. The difference is that the fused stack is not
and electroplating for bond-pads (Figure 5). After wafer
bowed any more. SEM and TEM images ( that will be
qualification by performing on-wafer continuous work (CW)
presented elsewhere) shows that the misfit dislocations
and high frequency (HF) tests, the wafer is thinned and
resulting from the lattice mismatch of GaAs and InP are
scribed into individual chips. Figure 6 depicts a typical
confined at the fused interface and do not propagate inside
VCSEL chip that is mounted on a sub-mount and electrically

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contacted with Au wires by ball-bonding will be the goal of a long lasting project and will be
The 1310 nm range VCSELs fabricated by wafer fusion described in a dedicated publications. The reason to
technique exhibit excellent performance in terms of spectral present the experimental results depicted in Figure 8-11 is
and power emission in the temperature range up to 100°C as to describe the initial phase of work in selecting the
well as modulation response up to 10Gb/s [5,6] . minimum necessary tools and characterization algorithms
for time and cost effective failure analysis.
As one can see from comparison of Figure 8 and Figure
9, under relatively low current and temperature stress
there are no devices failures and more than that, there is a
small increase in emission power versus test time, while
under increased temperature and current stress the
threshold current is increasing and emission power is
decreasing with time. Without going into more complex
analysis, one can conclude that power decrease with time
Fig. 5. Picture of the VCSEL chip with Fig. 6. VCSEL chip mounted under high temperature and current stress has a component
electroplated contact pads on a TO header
related to increase of threshold current ( see Figure 10) as

The devices from this group showed stable operation with

no failures during 5000h, as it is shown in Figure 8.
[1].VCSEL mean time to failure (MTTF) value at 25°C and
10 mA bias current was estimated to be in the range of 32
million hours and about 2 million hours at 70 °C [7].

Fig. 9. Plots of changes in power at 10 mA driving current versus time for

a set of 24 devices under current and temperature stress

Fig.7. . (a) -Spectral emission at 20°C (the numbers near curves indicate the
operation current, curves are shifted down for clarity), (b)- Light-Current-
Voltage characteristics up to 100°C

An example of performance versus test time plots, used

103

102
(P/Po)*100, %

101
Fig. 10. Plots of changes in threshold current versus time for a set of 24
devices under current and temperature stress

100

99
0 2000 4000 6000
Time, hours
Fig. 8. Power change for 11 devices from qual group showed stable
operation with no failures during 5000h

in evaluation MTTF values ( as will be presented in [7]) .are

depicted in Figure 9-11. The test conditions used for
acquisition these plots will be described elsewhere [7].
As one can see from these plots there are more or less
steady decreasing of the emission power for all tested
devices, and in a few of them the rate of degradation is Fig.11. Plots of changes in slope efficiency near threshold current versus
quite fast ( devices under numbers 236, 250 252 and 256). time for a set of 24 devices under current and temperature stress
In this paper we will not try to give a rigorous
explanation of the root causes of the device failures, this

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well as related to decrease of slope efficiency ( see Figure devices (e.g., accurate positioning of the observation area is
11). essential) and needs to be advanced also as a technique by
itself.
IV. ANALYSIS OF THE DEVICE STRUCTURE USING
A feasibility study of the fabrication of focused ion beam
STATE OF THE ART NANO RESOLUTION TOOLS
(FIB) cross sections was already successfully performed in
As one can conclude from the results of the tests of the
cooperation with CIME-EPFL. The results of the feasibility
devices under current and temperature tests, there are
study are presented in Figure 12 and Figure 13. A functional
device failures during accelerated life tests. Failure analysis
VCSEL was wax-mounted on a standard aluminum holder
is a very challenging, time consuming and costly
and coated with a very thin gold layer to release the
investigation . One of scientific objectives of the ongoing
electrostatic charges. The milling around the sample was
projects on wafer fused longwavelength VCSELS is to
performed before the tomography was started in order to
establish the relationship between degradation in VCSEL
avoid the deposition of the material from the milled section.
device performance(e.g., reduction in output power, increase
This gave an already important result, showing that some of
in threshold current, reduction in slope efficiency, electrical
the Au-coating was able to penetrate through the Pt barrier,
short circuits, etc.)
as evidenced in Figure 14. Device tomography was
performed by cutting through the sample every 0.5 um in an
automatic mode. In this feasibility study, we were using the
automatic mode, but the manual

Fig.12. FIB milling around the sample to avoid deposition of the material
from milled section

Fig.14. Energy Data Dispersive Scans (EDS) confirming the presence of

gold that escaped the Pt barrier

mode in the vicinity of the tunnel-junction allow for getting

enough resolution to identify the current confinement
aperture , see Figure 16a . In Figure 15 we can notice the
appearance of a gap in the structure.The gap could have
occurred through the penetration of the etching agents during
processing steps. The excess etching time of some layers in
the VCSEL structure during processing may have unwanted
results such as the GaAs under-etching along fused
interfaces. Under-etching of GaAs may cause

Fig. 13. SEM picture of the identified local diffusion of the gold in InP
layer

and devices structure. Understanding this relationship will

lead to the identification of specific failure modes and
corrective actions for avoiding them, demonstrated using
modified fabrication approaches. Achieving this scientific
goal will entail the development and perfection of novel
analytic tools, such as position-defined transmission electron
microscopy (TEM), scanning electron microscopy (SEM)
and cathodoluminescence (CL), which will also be useful in
a broader area of nano-characterization of complex nano-
devices and nano-systems. It should be emphasized that
usually such characterization is implemented on micro-
Fig.15. Detailed views of selected elements of the VCSEL structure
structured and nano-structured materials rather than devices,
let alone devices fabricated in an industrial environment. the partial delamination of the top DBR from the active
The application of such characterization tools is, however, structure. Figure 16b depicts the schematic of the top
much more difficult and the linkage of the observations to view of the structure, where the dashed line represents the
failure modes is extremely complicated for the case of top DBR mesa edge, the irregular shape is constructed from

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the successive SEM/FIB images and the full gray line failure analysis tool is destructive, as well as cross section
represents the image position depicted in Figure 15. If such image acquisition using FIB.
a feature will be discovered to be common for wafer
V. DISCUSSION
fused devices processed in this particular way, this may
As long wavelength VCSELs are emerging as attractive
have a certain impact on VCSEL device reliability.
light-sources for replacing DFB lasers for a number of
applications, and so far their reliability has always been
questioned by the industry as no solid data supporting their
reliability was demonstrated, the documented reliability
and failure analysis data obtained on wafer-fused VCSELs
are of big interest.

a b
Fig. 16a-detailed views of selected elements of the VCSEL structure. b-
Schematic of the top views of the structure, where the dashed line
represents the top DBR mesa edge, the irregular shape is constructed from
the successive SEM/FIB images and the full gray line represents the image
position depicted in Figure 15 b
A time and cost effective way of detecting hidden
features at the fused interface is infrared images taken
in sub threshold operation mode, as it is presented in
Figure 17. A challenging task is to establish correlations
between the contrast observed in infrared near field
pictures like presented in Figure 17.Fig. and features
observed during FIB tomography (Figure 18). Please note
that in this paper the pictures in Figure 15, Figure 17 and Fig.19. CL pictures ( right) at 1220 nm ( top) and 1320 nm ( bottom).
Figure 18are not from the same devices.
Results show that VCSELs fabricated with the wafer-
fusion technique and displaying high performance level,
meet Telcordia generic requirement standards [7], thus
making more actual the development of appropriate
metrology tools for supporting the fabrication technology
and further failure analysis .

Fig.17. Near field picture of the device under sub threshold current pumping

Another power full tool for characterization of the device

structure is cathodoluminescence (CL) [7]. Figure 18. and
Figure 19 are presenting the type of images that one can
acquire during failure analysis work using CL in long
Fig.20. AFM picture at the fabrication step depicted in Figure 4b
wavelength spectral region.
Simulations [4] indicates that a very important operation
parameter of side mode suppression ratio (SMSR) is
sensitive to geometrical dimension of the structured tunnel
junction layer. As one can see on Fig. 4 and Figure 20, the
vertical and lateral configuration of the epitaxial layer in
the vicinity of TJ aperture presents a complex surface with
features at nano metric scale. One can demonstrate ( it
will be presented elsewhere) that a more detailed
information on the 3 dimensional shape can be acquired
using atomic force microscope(Figure 20) and state of the
art optical confocal microscope (Figure 21)
The similar images can be acquired at all processing
Fig.18. SEM picture of the degraded device after DBR removal. Color inset
is the optical microscope picture. There are some residuals after top DBR steps of structuring of the wafer in double fused
removal fabrication process. It is possible even to take pictures of
100 % of the mesas, thus acquiring the necessary
As one can see, the contrast of the image taken on the
information for making statistical correlation between
same sample in spectral rage of 1220 nm is different form
structuring and device performance.
the contrast taken in the range of 1330 nm. Please note the
It is very interesting to develop a confocal microscopy
images in Figure 18 and Figure 19 are taken on a device
tool that will work at wavelengths at which VCSEL
from which top DBR was selectively removed, that is such a
materials is transparent. This will allow to detect in the

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structures the possible voids as depicted in Figure 15. The VI. CONCLUSION
work now is in progress to establish correlation between As the work on failure analysis is on its starting stage,
the contrast seen in near field images as depicted in Figure the continuous open discussion on implementation of
17 and contrast of the CL pictures ( see Figure 19) from advance nano tools for characterization of the device
one hand, and the voids and trenches that was several structure within LPN, BX and international partnership
times detected by FIB in the double fused VCSEL will be crucial for success of this challenging task
structures, as in Figure 15. As FIB investigation is
ACKNOWLEDGMENTS
destructive , lengthy and costly, a relative simple optical
The author acknowledge the extremely productive
non destructive observation have the potential to become a
working environment in EPFL, especially in LPN group
powerful tool for detection nanometric size defects in a
and BeamExpress, that made possible to initiate and
device structure at very early stage of characterization on
maintain research and development of the wafer fused
wafer, thus decreasing the cost of final systems based on
long wavelength VCSELs.
VCSELs.
REFERENCES
[1] Sirbu A, Iakovelv V, Mereuta A, et al. Wafer-fused
heterostructures: application to vertical cavity surface-
emitting lasers emitting in the 1310 nm band.
Semiconductor Science and Technology. 2011;26(1):
[2] Kapon E, Sirbu A. Power-efficient answer. Nature
Photonics,VOL 3 JANUARY 2009;
www.nature.com/naturephotonics. pp.27-29..,
[3] Iakovlev V, Suruceanu G, Caliman a, et al. High-
performance single-mode VCSELs in the 1310-nm
waveband. IEEE Photonics Technology Letters.
2005;17(5):947-949
[4] Backer A, Odermatt S, Santschi R, et al. Transverse
optical mode analysis of long-wavelength VCSELs for
high single-mode power operation. 2008 International
Conference on Numerical Simulation of Optoelectronic
Fig.21. Top view of the surface at the processing step depicted in
Figure 4b, taken using confocal optical microscope Devices (NUSOD)
[5] Kapon E, Sirbu a, Iakovlev V, et al. Recent
Finally, even in the case there will be no structural developments in long wavelength VCSELs based on
defects detected in the VCSEL structure by any state of the localized wafer fusion. 2009 11th International
art nano metrology tools, fabrication of the lamelas ( see Conference on Transparent Optical Networks. 2009:1-4
for TEM CL study presents an ultimate [6] Mereuta A, Suruceanu G, Caliman A, et al. 10-Gb / s
nanocharacterisation tool for revealing the changes in the and 10-km error-free transmission up to VCSELs.
QWs as a result of accelerated life tests. Optics Express. 2009;17(15):12981-12986.
[7] G. Suruceanu, A. Mereuta, J-C. Charlier , A. Sirbu, V.
Iakovlev, A. Caliman, E. Kapon; Reliable Performance
of 1.3µm Waveband VCSELs made by Localized
Wafer Fusion; to be presented at ECOC2011, Geneve
[8] M. Merino, S. Sonderegger, A. Crottini, S. Collin, E.
Pelucchi, P. Renucci, A. Malko, M.H. Baier, E.Kapon,
J.D. Ganiere, B. Deveaud, Time-resolved
cathodoluminescence of InGaAs/AlGaAs tetrahedral
pyramidal quantum structures, Appl. Phys. B 84, 343–
350 (2006),pp. 333-350.

Fig.22. Example of high resolution SEM picture of the TEM lamella

fabricated using FIB. Double arrow lined indicated the position of the
current aperture defined by buried TJ. CL Figure 22 and TEM study of
such a lamella is the subject of ongoing work and it will be presented
elsewhere

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Fundamental Issues in the Manufacturing of

Nanoelectromechanical (NEMS) and Related
Nanosystems
R. SINGH, G.F. ALAPATT, N. GUPTA, K.F. POOLE
Holcombe Department of Electrical & Computer Engineering and Center
for Silicon Nanoelectronics Clemson University, Clemson, SC 29634, USA
[email protected]

Abstract – Nanostructures in dimension below about 10 nm show interesting properties because of the effect
of low-dimension physics. However, to utilize these properties in practice to commercialize NEMS and
related nano-systems require an extremely precise manufacturing process. This paper briefly evaluates the
fundamental issues involved in manufacturing the nano-scale systems.

Index Terms – NEMS, manufacturing nanoelectronics.

trend is shown in Fig. l. For example, the melting point of

I. INTRODUCTION
gold changes by hundreds of degree Celsius as the particle
A Nanoelectromechanical System (NEMS) may include
size goes below 100 nm [10]. Sometimes, but not always,
electronic, optical, magnetic, mechanical, chemical,
these different and new properties can be used for our
biological, energy sources, and sensing components. To
advantages. For instance, a near defect-free material can be
qualify as a nano-scale system, at least one of these
made when its dimension is below a critical dimension [11].
functional components should have a dimension in the range
If these properties can be realized in practical devices, their
of 1 - 100 nm and a property arising due to the extremely
applications will be immense.
small size should be used by the system [1]. However,
significant advantages are seen only at dimensions below
about 10 nm, where quantum confinement effects are
observed [2]. In the last two decades the MEMS technology
has evolved from device manufacturing with right yield and
functionality to system integration of devices such as
oscillators, tunable filters, and auto focusing devices [3].
Extending the MEMS systems to NEMS [4, 5] systems
provide opportunities in new functional capabilities of the
system as well as overall cost reductions. However, there are
key fundamental manufacturing challenges that must be
solved before practical realization of NEMS systems can be
realized [6]. The objective of this paper is to address key
NEMS and related nano-systems manufacturing issues.
Fig.1. Properties of materials as a function of size.
II. ADVANTAGES OF NEMS OVER MEMS
IV. KEY FUNDAMENTAL ISSUES
NEMS is fundamentally a scaled down version of MEMS
To be able to manufacture nanoscale devices two
with many advantages and applications. Due to the nano-
fundamental considerations arise - nanostructure
dimensional feature sizes of NEMS, they have fundamental
homogeneity and process variability [6]. Without
resonant frequencies that exceed 1GHz, better Q factors, and
considering these core issues, a proper manufacturing
the ability to measure even mass with a resolution of about
technique cannot be designed for a nanoscale device.
10-21 grams [4, 7, 8]. NEMS have also been used to detect
viruses captured from liquids [9]. Due to inherent A. Nanostructure Homogeneity
advantages of NEMS, it is possible to develop high- The material used to make the nanostructure must be
resolution sensors, integrated low-power computational homogeneous in all directions, which implies that defects
systems, and mechanical resonators etc. Proof-of-concept must be below an extremely small threshold. In addition,
devices have already been shown to work in research labs. performance, reliability, and yield will be highest when the
However no manufacturing technique exists that can be used degree of homogeneity is high. This also involves reducing
for manufacturing of NEMS and related nanosystems. the variation in global and local thermal and residual stresses
in the material [12,13].
III. FUNDAMENTAL PROPERTIES OF
MATERIALS AT NANOSCALE
Properties of materials are significantly different at nano- B. Process Variability
dimensions in comparison to those in the bulk; a general Process variability is unavoidable during manufacturing

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and it will result in unequal nano-dimensions in the device. A. Top-Down Approach

The important factor here is that the amount of variability Lithography has been the standard technique for
should be kept under control. ITRS data shows that, to transferring patterns during IC manufacturing since its
achieve a 22 nm half pitch, the line width roughness of the beginning. The minimum feature size, quantified as half-
resist material should be less than 1.4 nm and the process pitch has been steadily decreasing since the 1980s. Invention
should be able to align the device with an error less than 5.3 of better light sources and improved methods of exposure
nm, all with a statistical variability of three [14]. This is a have driven this change. As of now, the half-pitch distance is
non-trivial problem when manufacturing nano-dimensions as 32nm and the light source used has a wavelength of 193 nm,
the dimension being manufactured is itself only less than 10 which is about six times the half pitch distance [14]. Further
nanometers and the required tolerances for each processing decrease in the light source wavelength to 13.5 nm using an
step could be less than 1 nm. In Table I we have listed the Extreme Ultra Violet source, has the possibility to decrease
lithography control that either has been achieved for a the half-pitch to the range of a few nanometers [14]. With
particular dimension or is expected in future generation of lithography, patterns of half-pitch distance less than 10 nm
lithography generated critical dimensions. have been created over a decade ago [16].
Thus, the control of dimension size is extremely important Apart from surface patterning abilities, manufacturing the
in manufacturing NEMS based systems. In Fig. 2, NEMS will require profiling abilities along the vertical axis.
Distribution A shows the allowed variation in dimension The Deep Reactive Ion Etching process is currently able to
sizes for exploiting the special properties that can be make vertical profiles with aspect ratios greater than 50.
obtained with NEMS based devices; however, during Thus, the traditional, semiconductor industry, based
manufacturing, due to a lack of absolute control on the manufacturing technology can make nano-dimensional
dimension, the resulting distribution will resemble the structures for research purposes. However, issues relating to
Distribution B shown in Fig. 2. Reduced values of full width non-homogeneity and process control will determine if these
at half maximum (FWHM) will provide better performance, devices can be successfully manufactured on a large scale
reliability and yield of NEMS. without defect related problems. Recently, a defect on one of
Intel's chip was discovered and analysts predict that this
TABLE 1: CRITICAL DIMENSION CONTROL defect is going to cost Intel about $1 Billion [17]. Defects
Critical Lithography Control Self Assembly such as these will determine how successful a product will
Dimension Obtained and Predicted Control be.
(nm) (3 ) (nm) Obtained (nm)
B. Bottom-Up Approach
27 2.8
The bottom up approach involves devices using an atom-
20 2.1 by-atom, approach and is called self assembly [18]. In our
21 3 [15] opinion the meanings of "Self Assembly" have been taken
15 1.6 wrongly. True self assembly process involves programmed
cell death or apoptosis [19]. The so called "self assembly" is
10 1
actually selective chemistry. The atoms or molecules are
7 0.8 forced by chemical, mechanical, or electrical means to
assemble in a particular fashion. Researchers have often
compared this method to the method employed in the
development of an animal or a plant. This technology is
relatively new and there is no commercially available system
capable of performing self-assembly. To demonstrate the
fundamental problems associated with "Self Assembly" we
consider the growth of carbon nanotubes (CNTs). Scanning
tunneling microscope (STM) is used to select CNT of
desired length and diameter [15]. Even with the use of STM,
CNTs of radius 21 ± 3 nm can be obtained. As shown in
Table I, these results are not comparable to the lithography
results. In a previous publication [20] we have investigated
the basic nature of bio-driven systems and found that due to
their fundamental nature of low growth rates as well as their
high defect densities, it is highly unlikely that such systems
Fig. 2. Statistical distribution of dimensions (A = required and B = actually can be used in semiconductor manufacturing.
obtained).
VI. CONCLUSION
V. CURRENT MANUFACTURING PROCESSES In this paper we have addressed the fundamental issues of
To manufacture a NEMS in a commercially viable nanostructure homogeneity and process variability for
fashion, two technologies are currently under consideration. manufacturing NEMS and related nanosystems. The top
The first one is the standard top-down approach and the down approach of lithography will continue to further scale
other is bottom-up approach. Both these prospective down nano-dimension systems. However Bottom-up
technologies are examined in this section. approach has fundamental limitations of high defect
densities and low throughput.

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REFERENCES using nanoelectromechanical devices,‖ Appl.Phys.Lett.,

[1] R. Singh, H. Iwai, R.R. Tummala and S.C. Sun, vol. 85, n.13, pp. 2604-2606, 2004.
‖Dielectrics for Nanosystems: Materials Science, [10] P. Buffat and J. Borel, ‖Size effect on the melting
Processing, Reliability, and Manufacturing: Proceedings temperature of gold particles,‖ Phys.Rev.A, vol. 13, pp.
of the First International Symposium,‖ The 2287, 06/1/. 1976.
Electrochemical Society, 2004. [11] J. Narayan, "Critical size for defects in nanostructured
[2] R. Singh, P. Chandran, M. Grujicic, K.F. Poole, materials,‖ J.Appl.Phys., vol. 100, pp. 034309-5, 08/01/.
U.Vingnani, S.R. Ganapathi, A. Swaminathan, 2006.
P.Jagannathan, H. Iyer, ‖Dominance of silicon CMOS [12] R. Singh, V. Parihar, K. F. Poole and K. Rajkanan,
based semiconductor manufacturing beyond ‖Semiconductor Manufacturing in the 21st Century,‖
international technology roadmap and many more Semiconductor Fabtech, 9th Edition, pp. 223-232, 1999.
decades to come,‖ Semiconductor Fabtech, 30th edition, [13] R. Singh & K. F. Poole, US Patent No.: US 6.569.249
pp. 104-113, 2006. Bl, Date of Issue: May 27, 2003.
[3] K. Lightman, and E. Mounier, ‖MEMS Manufacturing [14] ITRS, ‖Lithography Trends- ITRS 2009 Edition and
Evolution - A MIG and Yole Developpement webcast,‖ 2010 Update,‖ 2010.
February 17, 2011. [15] O. Loh, X. Wei, C. Ke, J. Sullivan, and H.D. Espinosa,
[4] X.M. Henry Huang, C.A. Zorman, M. Mehregany and ‖Robust Carbon-Nanotube-Based Nano-electro-
M.L. Roukes, ‖Nanoelectromechanical systems: mechanical Devices: Understanding and Eliminating
Nanodevice motion at microwave frequencies,‖ Nature, Prevalent Failure Modes Using Alternative Electrode
vol. 421, pp. 496-496, 01/30/print. 2003. Materials. Small,‖ 7: pp.79-86. doi: 10.1002/
[5] K.L. Ekinci and M.L. Roukes, ‖Nanoelectro-mechanical smll.201001166, 2011.
systems,‖ Rev. Sci. Instrum., vol. 76, n.6, 061101, June, [16] S.Y Chou, P.R. Krauss, W. Zhang, L. Guo and L.
2005. Zhuang, ‖Sub-10 nm imprint lithography and
[6] R. Singh, ‖MEMS and NEMS Manufacturing,‖ Proc. applications,‖ pp. 2897-2904, 1997.
MEMS and NEMS: New Technologies and Advanced [17] Market Place, ‖Intel Finds Chip-Design Flaw,‖ Wall
Devices, MIGAS'10-13th Session, pp. 1-117, June 28, Street Journal, February 1, 2011.
2010. [18] B. Amir Parviz, D. Ryan and G.M. Whitesides, ‖Using
[7] A. Husain, J. Hone, H.W.C. Postma, X.M.H. Huang, T. self-assembly for the fabrication of nano-scale
Drake, M. Barbie, A. Scherer and M.L. Roukes, electronic and photonic devices,‖ Advanced Packaging,
‖Nanowire-based very-high- frequency IEEE Transactions on, vol. 26, pp. 233-241, 2003.
electromechanical resonator,‖ Appl. Phys. Lett, vol. 83, [19] M. T. Heemels, R. Dhand and L. Allen, ‖Foreword:
n.6, pp. 1240-1242, 2003. Apoptosis‖, Nature, vol. 407, pp 769-770, 2000.
[8] Y.T. Yang, C. Callegari, XX. Feng, K.L. Ekinci and [20] R. Singh, T. Boland, R. Mulye, G. Gaur, J. Steelman, D.
M.L. Roukes, ‖Zeptogram-Scale Nanomechanical Mass Arya, N. Srinidhi, and P. Deshmukh, ‖Prospects of
Sensing,‖ Nano Letters, vol. 6, n.4, pp. 583-586, 2006. Incorporating Directed Self Assembly into
[9] B. Ilic, Y. Yang and H.G. Craighead, ‖Virus detection Semiconductor Manufacturing‖, Semiconductor
Fabtech, 36th edition, pp. 67-72, 2007.

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Topological Insulator Materials and

Nanostructures for Future Electronics,
Spintronics and Energy Conversion
Valeriu KANTSER,
IIEN, ASM, str. Academiei 3/3, MD 2028, Chisinau, Republica Moldova
[email protected]

Abstract – Two fundamental electrons attributes in materials and nanostructures - charge and spin –
determine their electronic properties. The processing of information in conventional electronic devices is
based only on the charge of the electrons. Spin electronics, or spintronics, uses the spin of electrons, as well as
their charge, to process information. Metals, semiconductors and insulators are the basic materials that
constitute the components of electronic devices, and these have been transforming all aspects of society for
over a century. In contrast, magnetic metals, half-metals, magnetic semiconductors, dilute magnetic
semiconductors and magnetic insulators are the materials that will form the basis for spintronic devices.
Materials with topological band structure attributes and having a zero-energy band gap surface states are a
special class of these materials that exhibit some fascinating and superior electronic properties compared to
conventional materials allowing to combine both charge and spin functionalities. This article reviews a range
of topological insulator materials and nanostructures with tunable surface states, focusing on nanolayered
and nanowire like structures. These materials and nanostructures all have intriguing physical properties and
numerous potential practical applications in spintronics, electronics, optics and sensors.

Index Terms – Topological insulator, nanowire, nanoribbon, bismuth selenide, magnetotransport, metal-
insulator transition, , structure interfaces, thin film.

Actually, Dirac electrons with finit gap in materials have a

I. INTRODUCTION
long history starting from bismuth that has three-
Depending on the electronic band structure and transport
dimensional massive Dirac electrons in its band structure
characteristics uncountable number of materials and
substances can be classified quite simply in terms of their
conductive behavior into one of three types — insulators,
semiconductors and metals. More than three decade ago
there was established that spin-orbit interaction (SOI) has an
important pattern on band structure of solid state matter.
Among different qualitative features induced by SOI the
band inversion of electronic spectrum near the Fermi level
has been discovered. Such type of electronic spectrum was
identified in different type of semimetalic and narrow-gap
semiconductors Bi1-xSbx, Pb1-xSnxTe, Bi2Te3, HgTe, TlBiTe2
etc. In the context of low dimensional structure
investigations the band spectrum inversion was shown to
generate new type of interface gapless states with linear
spectrum at the heterocontact boundaries. Last years Fig.1. Band spectrum inversion – the origin of genesis of the topological
investigations [1,2] have reopened the interest to materials insulator state
with inverted band spectra. Due to new type of the symmetry
break like that characteristic for the integer and fractional The most robust observable consequence of a nontrivial
quantum Hall effects the electronic states was shown to have topological character of these materials is the presence of
topological nature and materials have been named toplogical gapless helical edge states (interface states of inverted
insulators (TI) (Fig.1). Thus in TI a new state of matter heterocontacts), whose gapless states is protected by time-
appear, distinguished from a regular band insulator by a reversal symmetry and is thus robust to perturbations that do
nontrivial time-reversal topological invariant, which not break this symmetry (Fig.2). Like the Hall state the
characterizes its band structure, and non-trivial interplay of ―bulk‖ of the electron gas of TI is an insulator, but along its
charge and spin degree of freedom of band electrons. In suface, the states can be gapless. Within a certain parameter
results new physics and phenomena related to this states range the surface states of TI are well described by a Dirac
have greatly emerged. Several of such new TI properties are cone, allowing for parallels with graphene and relativistic
reviewed in the paper as well as some old observed physics, and prohibiting backscattering.. A prerequisite for
properties of materials with band inversion. Many intriguing such experiments is a highly tunable surface state which is
properties of TI can be ascribed to the existence of two-band decoupled from the residual bulk carriers. Despite
gaplees Dirac electrons in its low-energy band structure. considerable recent evidence of TI surface states in ARPES
and STM , transport experiments are complicateddue to

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significant parallel conduction through bulk states, limited layer thickness and others factors are highlighted for
surface density tunability, and uncertainty quantun well and superlattice structures based on Bi1-xSbx,
Pb1-xSnxTe, Bi2Te3 in the framework of two-band effective
mass method. In the superlattice structures like PbTe/SnTe
with layer thickness a and b respectively the state of the
topological insulator can be realized (Fig.3).

Fig.2 The electronic band structures of topological insulators, a new class of

quantum matter with (a) a robust metallic state at the surface/edge and
insulatingproperties in the bulk/surface, and (b) a conductive state at the
surface or edge withzero gap and the same linear energy dispersion as
graphene.

of the surface to bulk coupling. At the same time the

spectrum and characteristics of topological surface states
(TSS) depending on geometrical configuration can be
manipulates by different factors: electrical and magnetic
fields, strain and deformation ets. For this reason TI are
being explored with a view towards applications, as a
potential platform for tailoring nanostructures and
nanomaterials properties. This topics cover the second part
of the paper. Fig.3. Topological extended states in PbTe/SnTe superlattice structures
The last part of the paper deals with behavior of TSS if TI
nanostructures in the nanowire and nanotube like The dispersion relation E(K), K being the crystal
configuration Some aspects of transport through TSS are momentum, can be found from [4]
discussed: anomalous Aharonov-Bohm conductance cosq(a+b) = cosh(Kb) cos(ka) –
oscillations; magnetic quantum oscillations, edge [(p2 – r2)/2pr] sinh(Kb) sin(ka).
accumulation and currents of moment.Thermoelectric aspect Where k==(E2 – E2gA/4)1/2/hv,
of TSS are discussed in the context of TI materials Bi2Se3 K==(E2gB/4 − E + V)1/2/hv,
and Bi2Te3 knowing as the best thermoelectrics. r =(E – EgA)/2hvk,
p=(EgB/2 − E + V) )/2hvK
The phase diagram of the band and topological insulator
II. TOPOLOGICAL INSULATOR NANOLAYERED states are established in dependence of the semiconductor
STRUCTURES gaps and thickness. The gapless electronic states with Dirac
Along with the extensive researches of materials and like linear spectrum were revealed to occur when E gPbTe * a =
properties of three- dimensional (3D) topological insulators EgSnTe * b. Such superlattice structures can be considered as
(TIs),[1] attention has increasingly been paid on ultrathin a new type of metamaterial of semiconductor layers and
films and nanostructures of such materials for enhanced metallic sheets. The plasmonic and metamaterial
effects and properties associated with the topological states characteristics of such layered structures are discussed. Flat-
of electrons [2,3] In the same line of thoughts, multi-layered lens focusing of electrons on the surface of a topological
structures constituted of TIs and normal band insulators, insulator Bi2Te3 is analysed. The early studied interface
such as superlattices (SLs) or multiple quantum well states in inverted heterocontact with magnetic ordering are
(MQWs) of …Bi2Se3/ZnSe…have been attempted by the reanalyzed in the context of recently discovered
technique of molecular-beam epitaxy (MBE). In this part of antiferromagnetic TI. The occurrence of interface
paper we are using formal analogy of electromagnetic wave ferromagnetism is demonstrated [5].
equation and Schrodinger equationin order to study the
phenomenon of perfect tunneling (tunneling with unitary III. TUNABLE TOPOLOGICAL STATERS IN
transmittance) in multilayered semiconductor NANOWIRES
heterostructure with band inversion and TSS. Using the two- The surface contribution is easier to extract
band model of semiconductor we are showingthat such experimentally in TI nanowires , where the surface-to-
phenomenon can indeed exist, resembling all the interesting volume ratio is more advantageous. In this case, introduction
features of the analogous phenomenon in classical of a magnetic flux piercing the nanowire has allowed to
electromagnetism in which metamaterials (substances with successfully identify the Aharonov-Bohm effect caused by
negative materialparameters) are involved. We believe that the surface state.
these results can open up the way to interesting applications The TSS of cylindrical nanowires and topological
in which the metamaterial ideas are transfered into insulator Bi2Te3 with cylindrical pores are studied. The
semiconductor domain. developed recently low-energy approach for bulk Bi2Te3 is
The evolution of the topological states in dependence of used to highlight TSS on the cylindrical surface. For the bulk

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Bi2Te3 (Bi2Se3) TI near the Γ point of the surface Brilloiun effects, have greatly emerged. In the Hall state the ―bulk‖ of
zone, Hamiltonian has the the electron gas is an insulator, but along its edge, electrons
form circulate in a direction that depends on the orientation of the
H   0 k  0 0  M k  0 z  A1k z z x  A2 x k x x  k y y . magnetic field and these edge states are different from
Model parameters of four bands Hamiltonian (1) have been ordinary states of matter because they persist even in the
defined in the framework of kp theory by comparison with presence of impurities. Recently it was established that the
the ab initio calculations [7]. same ―robust‖ conducting edge states could be found on the
boundary band insulators with large spin-orbit effect, called
topological insulators. In a topological insulator (TI), these
surface states are protected, that is, their existence does not
depend on how the surface is cut or distorted. Such type of
topological states and its related effects (in particular
quantum spin Hall effect) are analized for different type of
semimetalic and narrow-gap semiconductor materials Bi1-
xSbx, Pb1-xSnxTe, Bi2Te3, HgTe and their nanostructures.
Recent photoemission experiments reveal that Bi2Te3 and
other like termoelectrics are a TI with a single Dirac cone on
the surface, consistent with electronic structure predictions.
In this part of the paper we try to analyze how new surface
topological states could lead to improved thermoelectric
performance. The physical system to be studied here is a thin
film and nanowire of Bi2Te3. If the film is thin enough the
surface states on both sides hybridize and open a gap [6].
Fig.4. Electronic structure of TI Bi2Te3 nanowire with a radius of 10 nm.
The TSS forming inside the bulk gap (Fig.4) corresponds
to one dimensional bands indexed by total angular
momentum. For nanowire or nanopore of radius R, the
wavefunction to vanish at the boundary r = R is required,
which is automatically ensured by expanding in the
orthonormal set of radial Bessel functions Jm or Ym with
integer m. In comparison with gapless character os TSS of
flat surface all TSS modes of cylindrical surface have a
finite gap described qualitatively by relations Egs ~v/R
(Fig.5). In results nanowire and nanopore composites of TI
have distinct from layered ones pecularities and several are
discussed in the paper [8]

Fig .6. ZT for the thin film including bulk contributions at 150 and 175
Kelvin. The straight line in each figure corresponds to the best known ZT at
Fig.5 Dependence of the direct band gap at the Γ point of the topological the same temperature. Dashed line indicates the ZT for the surface states
insulator Bie2Te3 (solid line) and Bi2Se3 (dashed line) nanowires on alone and Dashed-Dotted line indicates ZT for bulk Bi2Te3.
radius.
Although the film thickness required to open an
IV. TOPOLOGICAL INSULATOR NANOSTRUCTURES observable gap for TI surface states (1-10 nm) is small, it is
AND ENHANCED THERMOELECTRICAL accessible with current growth techniques and very recently
PERFORMANCE the hybridization gap has been observed by in-situ
Last years investigations of new electronic states of photoemission on thin films of Bi2Se3.Using the electron
materials and structures - topological states - as well as new dispersion the in-plane (longitudinal for nanowire) transport
physics and phenomena related to this states, which are coefficients for the surface states together with bulk ones
generated by new type of the symmetry break like that were obtained and calculated as well as for the figure of
characteristic for the integer and fractional quantum Hall

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merit ZT (Fig 8) [9]. by the half-integer total angular momentum j is formed,

As is evident from Fig. 6, at temperatures below 150 K, where each mode contains a rightand a left-mover. The spin
which are important for several Peltier cooling applications, direction is always tangential to the surface and
the thermoelectric performance of the topological insulator perpendicular to the momentum.
thin film is signifcantly enhanced because of the high ZT of In the simplest singlemodecase, the spin polarization of a
the protected edge topological states. At low temperature the right (left) moverhas a counter-clockwise (clockwise)
bulk contribution is smaller than the surface contribution so orientation around the waist of the cylinder.
that the unknown chemical potential dependence of bulk The cylindrical symmetry leads to a decrease of the band
properties is not too significant. Crucially, the gap in the gap with decreasing of both NW radius and ratio bulk
hybridized surface mode band structure can be controlled by volume/surface area, while the confinement effect leads to
tuning the thickness of the film to get high ZT in a specific an increase of the band gap at a rather small value of the NW
temperature range. The geometry of thin films is also very radius.The observation of the Aharonov-Bohm oscillations in
effective in reduction of phonon thermal conductivity, so Bi2Se3 nanostructures provides important insights into the
there will be even larger enhancement for the topological topological surface states.
insulator like Bi2Te3 thin films. The same approach applies The topological states of Bi2Te3 thin film surfaces
as well to nanowires. hybridize and band gap is opened. In results, increased
thermoelectric performance of film and nanowire can occur
V. CONCLUSIONS at low temperatures. The analyzed results may lead to a new
Materials having signature of topological insulator are a method of improving the thermoelectric figure of merit for
special class of materials that exhibit fascinating and more efficient thermal-to electric energy conversion and
superior electronic, magnetic and optical properties thermal management of devices.
compared to conventional materials. The discovery of REFERENCES
topological insulator state of matter has generated great [1] Y. Xia, D. Qian, D. Hsieh, L. Wray, A. Pal, H. Lin, A.
interest in the search for new classes of such materials, and Bansil, D. Grauer, Y. S. Hor, R. J. Cava, and M. Z.
some classical materials with band inversion spectra have Hasan, Nat Phys 5 (6), 398 (2009)
been revisited. The phase diagram of the band and [2] J. G. Checkelsky, Y. S. Hor,R. J. Cava, and N. P. Ong,
topological insulator states are established in dependence of PRL 106, 196801 (2011)
the semiconductor gaps and thickness in Ti multilayered [3] Kentaro Nomura1 and Naoto Nagaosa, PRL 106,
structures (materials A and B). The gapless electronic states 166802 (2011)
with Dirac like linear spectrum were revealed to occur when [4] Kantser, V. G, Lelyakov, I. A. Malkova, N. M.,
EgA * a = EgB * b. Such superlattice structures can be Semiconductors vol. 26, p. 896-899, (1992)
considered as a new type of metamaterial of semiconductor [5] Kantser V., Malkova N, PhysRevB.56,p.2004, (1997)
layers and metallic sheets. [6] H. D. Li, Z. Y. Wang, X. Guo, T. L. Wong, N. Wang,
Analysis of TI nanowires draw a consistent picture for the and M. H. Xie, Appl Phys Lett 98 (4) (2011)
surface states inside the bulk gap, even for very thin [7] B. A. Bernevig, T. L. Hughes, and S. C. Zhang, Science,
nanowires: a one-dimensional (1D) electron waveguide with vol. 314, pp. 1757, 2006.
modes indexed [8] I.Begenari,V.Kantser NanoLett, in press
[9] P. Ghaemi, Roger S. K. Mong and J. E. Moore, cond-
mat 1002.1341v2, (2010)

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Functionalised AlGaN/GaN Heterostructures for

Electronic Saccharide Sensing
A. SARUA1, T. SCHULLER1, M. KUBALL1, S. FLOWER2, T. D. JAMES2, J. FOSSEY3, Jo DAS4,
S. DEGROOT4, M. GERMAIN4
1
H.H. Wills Physics Laboratory, University of Bristol, Bristol, BS8 1TL, United Kingdom
2
Department of Chemistry, University of Bath, Bath, BA2 7AY, United Kingdom
3
School of Chemistry, University of Birmingham, Birmingham, B15 2TT, United Kingdom
4
Interuniversity Microelectronics Center, Leuven, 3001, Belgium
[email protected]

Abstract – A novel field-effect sensor device based on functionalised AlGaN/GaN heterostructure was
developed for sensing of various saccharides in solutions. Device was functionalized with a boronic acid
chemical receptor, a thiol group and alkane chain linker. Electrical measurements on fabricated devices were
performed to demonstrate their response to buffered saccharide solutions (fructose, galactose and glucose) of
varying concentrations. The obtained results provide basis for the development AlGaN/GaN-based electronic
sensor devices incorporating boron receptor chemistry.

Index Terms – GaN, AlGaN, sensors, HFET, saccharide.

In this paper, we present a novel electronic saccharide

I. INTRODUCTION sensor structure using boronic acid functionalised
In recent years there has been large interest for use of AlGaN/GaN heterostructure and thiol linker for proof-of-
GaN based structures for various electronic and optical concept demonstration of specific chemical sensors based
devices for telecom and solid-state lighting markets. upon field-effect device structures.
However, AlGaN/GaN heterostructures have also shown II. EXPERIMENTAL DETAILS
great potential for field-effect based electronic chemical and AlGaN/GaN heterostructures were grown on Si(111)
biochemical sensors [1,2,3]. In these structures formed two substrates by metal organic chemical vapour deposition.
dimensional electron gas (2DEG) at the interface between Thickness of GaN layer was about 2.5 µm, covered with 20
the AlGaN and GaN layers provides high density carriers nm of Al0.25Ga0.75N layer. Square die of 0.5 x 0.5 cm were
confined near the surface, which has been widely exploited cleaved from the wafer. Standard Ti/Al/Ti/Au ohmic contact
for RF device applications. Together with excellent chemical pads, separated by 2mm, were deposited by e-beam
and thermal stability of these materials this makes them evaporation through a shadow mask and then annealed at
good candidates for variety of chemical sensing applications. 850 °C for 30s under nitrogen ambient. Subsequently, a
To functionalize GaN structures various approaches were NiCr/Au layer was deposited in the space between contacts
explored, typically silane [4] and alkene [5] groups were to allow receptor attachment and act as a Schottky gate. On
involved to create a linker between receptor and surface. each die a pair of identical devices was fabricated, to act as a
However, both these approaches have limitations, requiring reference and a functionalised active sensor device. Devices
additional extensive processing or indirect bonding to were mesa-isolated via scribing.
surface via less stable oxides. On other hand, thiol based Reference device was fully masked as was the most of
attachment is known to provide straight-forward bonding active device structure, apart of rectangular functional area
either directly to semiconductor surfaces or on thin gold between ohmic contacts. Die was then placed in a 5 mM
films [6, 7] and is a possible alternative to existing methods. solution of prepared by chemical synthesis boronic acid thiol
In-situ detection and analysis of saccharides is of great (BAT) product in ethanol for 24 hrs. Mask was then
importance for a variety of domestic and medical removed and contact angle measurements were used to
applications. However, accurate, reliable and cost-effective confirm functionalisation of the prepared surfaces.
electronic saccharide sensors are not readily available. III. RESULTS AND DISCUSSION
Typically, electronic saccharide sensors are fabricated via Figure 1 shows a schematic diagram of a device structure,
the immobilisation of a specific enzyme [8]. However, such receptor and thiol linker (BAT) and functionalisation steps.
devices suffer from high fabrication costs and complexity as In comparison to organosilane functionalisation [4], thiol
well as reduced stability of the finished devices [9]. based method benefit from much simpler chemistry and
Alternatively, boronic acid receptors have been shown to fewer fabrication steps, and can be used to bond receptors to
bind to saccharides effectively via covalent interactions in thin gold layers or directly to the surfaces. While alkene
aqueous media [10,11,12].This lead to development of non- based linkers are also offer a simple pathway for GaN
electronic fluorescence sensor approaches based on fuctionalisation [5], the method relies on use of hydrogen
carbohydrate sensing ―click-fluor‖ [13]. terminated GaN surface, which is very unstable and have

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very limited life time. underwent several hundred cycles of analyte deposition and
subsequent washing and cleaning without any significant
loss in response, which suggest robust GaN surface
functionalisation using thiol based linkers.
Necessary improvements in the low concentration
detection limit (below 0.1 M) for sugars is essential for
future applications of sensor devices and can be achieved via
further optimisation of fabrication process and by
modification in the BAT receptor design.

IV. CONCLUSION
Here we demonstrated a proof-of-concept for saccharide
electronic sensor device based on AlGaN/GaN field effect
structure. A novel approach of receptor design and
functionalisation based on preassembled by chemical
synthesis boronic acid receptor and thiol-alkane linker
(BAT) allowed to achieve specific sensitivity of fabricated
structure to different saccharide concentrations in solutions.
This offers a way for robust and simple functionalising of
GaN based structures not only for saccharide detection, but
Fig. 8. Schematic diagram of a functionalised AlGaN/GaN sensor device. also by replacing boronic acid with other molecular
The BAT receptor molecule bonds to the gold layer between the Ohmic
contacts. receptors to a wider range of detected species.
Figure 2 displays measured sensor current, I, in the active ACKNOWLEDGMENTS
functionalised device before and after exposure to analytes: a The authors would like to thank Mike Redwood for his
solution of 1M fructose in the buffer. Also given is a technical assistance, as well as Great Western Research and
comparison with the reference device, which experiences the EPSRC for funding.
only a negligible change in current in reaction to the analyte. .
REFERENCES
[1] R. Neuberger, G. Müller, O. Ambacher, and M.
Stutzmann, ―High-Electron-Mobility AlGaN/GaN
Transistors (HEMTs) for Fluid Monitoring
Applications‖ phys. stat. solidi (a), 185, pp. 85–89,
2001.
[2] S. C Hung, B. H. Chou, C. Y. Chang, C. F. Lo, K. H.
Chen, Y. L. Wang, S. J. Pearton, Amir Dabiran, P. P.
Chow, G. C. Chi, F. Ren, ―Minipressure sensor using
AlGaN/GaN high electron mobility transistors‖, Appl.
Phys. Lett. 94, p. 043903, 2009.
[3] B. S. Kang, B. S, H. T. Wang, T. P. Lele, Y. Tseng, Y.
F. Ren, S. J. Pearton, J. W. Johnson, P. Rajagopal, J.
C. Roberts, E. L. Piner, K. J. Linthicum, ―Prostate
Fig. 2. Electrical response of reference and active devices exposed to 1M specific antigen detection using AlGaN/GaN high
fructose solution. Time interval between 15 and 25 seconds corresponds electron mobility transistors‖, Appl. Phys. Lett., vol.91,
to deposition of analyte (no electrical data). no.11, pp.112106-112106-3, Sep 2007.
Following confirmation of sensor activity, the device was [4] R. M. Petoral, G. R. Yazdi, A. L. Spetz, R. Yakimova
exposed to buffered saccharide solutions of fructose, and K. Uvdal ―Organosilane-functionalized wide band
galactose and glucose with concentrations between 1M and gap semiconductor surfaces‖, Appl. Phys. Lett. 90 (22),
0.1M. The detected response was greatest for fructose, pp. 223904 - 223904-3, 2007.
followed by galactose and glucose was the weakest, which [5] H. Kim, P. E. Colavita,, K. M. Metz, B. M. Nichols, B.
follows the established stability order for simple boronic Sun, J. Uhlrich, Xiaoyu Wang, T. F. Kuech and R. J.
acids [12,14]. This result confirms that observed sensor Hamers ―Photochemical Functionalization of Gallium
response is due to specific interaction between the boronic Nitride Thin Films with Molecular and Biomolecular
acid and the saccharide molecule rather than some secondary Layers‖ Langmuir 22 (19), pp. 8121-8126, 2006.
interactions with one of the other groups present in BAT. [6] T. Ishida, M. Hara, I. Kojima, S. Tsuneda, N. Nishida,
For all three analyte concentrations above 0.8M saturation H. Sasabe, and W. Knoll ―High Resolution X-ray
behaviour was observed for the sensor device. In the low Photoelectron Spectroscopy Measurements of
concentration region, only fructose can be reliable detected Octadecanethiol Self-Assembled Monolayers on
below 0.2M. Generally, despite non-optimised process Au(111)‖ Langmuir 14 (8), pp. 2092-2096, 1998.
parameters, sensitivity of the fabricated structures was [7] M. D. Porter, T. B. Bright, D. L. Allara, C. E. D.
compatible with non-electronic chemical method described Chidsey ―Spontaneously organized molecular
in Ref. 13. During electrical measurements devices assemblies. 4. Structural characterization of n-alkyl thiol

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monolayers on gold by optical ellipsometry, infrared in Saccharide Recognition‖ RSC Publishing:

spectroscopy, and electrochemistry‖ J. Amer. Chem. Soc. Cambridge, UK, 2006
109 (12), pp. 3559-3568, 1987 [12] D. G. Hall, ―Structure, Properties, and Preparation of
[8] K. Matsumoto, H. Kamikado, H. Matsubara and Y. Boronic Acid Derivatives. Overview of Their Reactions
Osajima, ―Simultaneous determination of glucose, and Applications, in Boronic Acids: Preparation and
fructose and sucrose in mixtures by amperometric flow Applications in Organic Synthesis and Medicine‖, ed.
injection analysis with immobilized enzyme reactors‖ D. G. Hall, Wiley-VCH Verlag GmbH & Co. KGaA,
Anal. Chem. 60, pp. 147–151, 1988. Weinheim, FRG., 2006.
[9] S. Park, H. Boo, T. Dong Chung, ―Electrochemical non- [13] D. K. Scrafton,, J. E. Taylor,, M. F. Mahon,, J. S.
enzymatic glucose sensors‖ Analytica Chimica Acta, Fossey and T. D. James, ―Click-fluors‖: Modular
556, pp. 46-57, Jan 2006 Fluorescent Saccharide Sensors Based on a 1,2,3-
[10] T. D. James, S. Shinkai, ―Artificial receptors as Triazole Ring‖ The Journal of Organic Chemistry 73 (7), pp.
chemosensors for carbohydrates‖ Top. Curr. Chem. 218, 2871-2874, 2008.
pp. 159-200, 2002. [14] J. P. Lorand, J. O. Edwards, ―Polyol Complexes and
[11] T. D. James, M D. Phillips, S. Shinkai, ―Boronic Acids Structure of the Benzeneboronate Ion‖ J. Org. Chem.
24, pp. 769-774, 1959.

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More Efficient Nanostructured Material for

Noncontact Body Temperature Measurement
Anatolie CASIAN, Ion BALMUS, Viorel DUSCIAC, Veaceslav NICIC
Technical University of Moldova
[email protected]

Abstract – Existing methods of human body temperature measurement are briefly analyzed. The
opportunities of different type of medical thermometers are described. The advantages of the latest infrared
skin thermometers and of new thermal imaging systems are evidenced. The thermoelectric power factor
which determines the sensitivity of infrared detectors is modeled in highly conducting nanostructured organic
crystals. The optimal parameters that ensure the highest value of the power factor at room temperature are
evaluated. It is shown that in existing crystals of tetrathiotetracene-iodide after the optimization of carriers’
concentration it is possible to obtain higher values of power factor than in the best known inorganic
materials. It is proposed to use these crystals as more efficient material for sensitive elements of
thermoelectric sensors in infrared skin thermometry.

Index Terms – infrared skin thermometer, nanostructured organic crystals, thermoelectric power factor,
thermoelectric infrared sensor.

Thus, temperature is temperature is related to the motion

of the particles that constitute the sample. But also it means
I. INTRODUCTION
that the sample contains a big number of particles.
From the point of view of daily uses temperature is
The human body temperature is a very important
connected with the quality of thermal energy contained in
parameter which determines into a large measure the state of
different objects and it serves to express quantitatively the
man health. Therefore it is necessary to have good methods
common notions of hot and cold. The simplest way to sense
and adequate devises for quick and reliable measurement of
this is to touch the given object and to decide, if it is warm,
temperature. Since the temperature scale has been
hot or cold. But quantitatively, temperature is measured with
established and the notion of normal body temperature was
thermometers. The notion of temperature is defined for
introduced a variety of methods and devices for temperature
objects that are in thermal equilibrium, or for the parts of
measurement have been applied. During a long time the
them that are in local thermal equilibrium, i.e. in such state
thermometers with mercury into a glass tube were the most
in which no further changes occur. These objects or their
used. Although such thermometers are simple in use, they
parts must contain a big number of constituent atoms or
are dangerous for the environment, because the glass can
molecules. If there is no heat transfer between two objects
break, the mercury can spill, but it is known that the mercury
(for example, the object and the thermometer), both objects
vapors are poisonous. Therefore later the mercury was
have the same temperature. There are different temperature
replaced by other not poisonous liquids. Nevertheless, the
scales. Most of countries use the Celsius scale (°C) for
glass can break and it is not conveniently.
temperature measurements with 0°C for freezing point of
Unfortunately, until now an ideal method and an ideal
distilled water and 100°C for boiling one at the sea level.
thermometer are not yet found, although body temperature
Celsius scale has the same value of 1 degree as the Kelvin
measurement is very important not only for correct
scale (K) used by scientists, but fixes its null point at 0°C =
diagnosis, but also for further investigation and treatment of
273.15K, the freezing point of water. A few countries,
patients. In pediatrics the rectal measurement is still
including the United States, use also the Fahrenheit scale for
considered as the most precise, although it has several
different purposes. It is a historical scale on which water
disadvantages as discomfort, emotional distress, requirement
freezes at 32 °F and boils at 212 °F.
of significant time for measurement, possibility of
In the science, the statistical thermodynamics gives a
complications connected with perforation or introduction of
formal definition of temperature [1, 2]. Temperature is a
infections [3]. As a result of these disadvantages and of
measure of statistically average kinetic energy of the
recommendations of UK National Institute of Health and
particles forming a material object. This definition includes
Clinical Excellence (NICE) general guide [4] some medical
the notion of number of particle degrees of freedom. A
institutions have abandoned rectal measurements.
simple particle (an atom or a molecule as material point) has
Sublingual cavity and axillae measurements are more
three degree of freedom. To average kinetic energy of a
convenient than rectal ones, but are less precise. Relatively
simple particle it corresponds (3/2)k0T (1/2 for each degree
new alternative for body temperature measurements are
of freedom), were T is the temperature, and k0 is the
tympanic and infrared skin thermometers. The first measures
Boltzmann constant
by the help of a special sensor the quantity of infrared heat
_______________________________________________
produced by tympanic membrane. The measurements are
This work was supported by the Project No. 104 b/s of
also not sufficiently precise. The infrared skin thermometer
Academy of Sciences of Moldova.
is the latest developed method of body temperature

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measurement. It measures the quantity of infrared heat material of such quantum wells. However, the technology to
produced by temporal arteries. Only a few studies have been product such structures is complicated and expensive.
carried out on this subject. Harvard Medical School, USA In the last years organic materials attract more and more
has proven that Exergen Corporation‘s Infrared temporal attention as materials with more diverse properties and less
artery thermometer is more accurate than infrared ear expensive. Already it exists a new generation of organic
thermometry and more accurate than even rectal based electronic devices. It was also shown [9, 10] that
thermometers in responding to change in fever. among organic compounds it is possible to find materials
In the last time different thermal imaging systems that which will have considerably increased thermoelectric
provide a thermographic image of human body temperatures power factor. Such materials unite together the advantages
(typically the face) at a distance obtain more and more of low-dimensional quantum systems and of multi
applications. The IR-160R Automated Body Monitoring component materials with more diverse and complicated
System has temperature measurement accuracy of 0.25 interactions.
degrees C. An advantage of this noncontact temperature Our latest investigations [11, 12] have shown that the
measurement is the exclusion of contamination spreading, quasi-one-dimensional nanostructured organic crystals of
that is possible by contact methods. A Japanese electronic tetrathiotetracene-iodide can have very promising
firm NEC/Avios has launched in January 2011 a mirror with thermoelectric properties. In this paper we will model the
a system which measures the temperature distribution on the power factor in dependence of crystal parameters in order to
human face, determines the average temperature and on this find those that ensure the highest value.
base calculates the body temperature. But it is clear that in
III. CRYSTAL MODEL
order to increase the effectiveness of these measurements it
The quasi-one-dimensional organic crystals of
is necessary to have good infrared sensors.
tetrathiotetracene-iodide, TTT2I3 are formed of segregate
The aim of this paper is to propos optimized parameters of
chains or stacks of planar molecules of tetrathiotetracene
a nanostructured organic material as more efficient sensitive
TTT, and iodine. The distance between molecules along
element of thermoelectric detectors of infrared radiation for
chains is two times smaller than between different chains.
sensors of temperature measurements.
Therefore the overlapping of electronic wave functions of
II. THERMOELECTRIC SENSORS OF INFRARED TTT molecules along chains is big, but between chains is
RADIATION negligibly. Only TTT chains are conductive because the
Thermoelectric detectors are largely used for the detection iodine electronic wave functions are strongly localized. The
of infrared radiation in the long wave lengths diapason of conduction mechanism along chins is of band type, but
spectrum where the photoelectric detectors are not sensitive, between chains it is of hoping type. The latter gives small
usually for wave lengths longer than 1.5 μm. In the same contribution and is neglected. The charge carriers are holes.
time, it needs to note that the Earth atmosphere has windows The TTT2I3 crystals can be considered as nanostructured
of transparency only in several intervals of infrared spectrum material, because the distance between conducting chains is
for wave lengths between 2,0 – 2,5 μm, 3,2 – 4,2 μm, 4,5 – of the order of one nanometer.
5,2 μm and 8,0 – 13,5 μm. In order to increase the detector The parameters of TTT2I3 are: the mass of molecule M =
sensitivity it is important to collect the infrared radiation 6.5105me (me is the mass of free electron), the lattice
from the possible larger spectral interval. Also, it is very constants a =18.35 Å, b = 4.96 Å, c = 18.46 Å (the direction
necessary to have more efficient thermoelectric materials. of chains is along b), the sound velocity along the chains vs =
Intensive investigations are made in this direction in many 1.5105 cm/s, the carriers concentration for ordinary
scientific laboratories. stoichiometric crystals n = 1.21021 cm-3. The electrical
The main parameter that determines the opportunity of a conductivity along the chains  at room temperature varies
material to be used in detectors of infrared radiation is the in the crystals grown from solution between 800 and 1800
thermoelectric power factor P = S2, where  is the -1cm-1 [13], whereas for crystals grown from gas phase,
electrical conductivity and S is the thermopower (Seebeck which are purer and more perfect, it varies between 10 3 and
coefficient). New materials are needed with as higher as
104 -1cm-1 [14]. The electrical conductivity is very sensible
possible values of the thermoelectric power factor P. One
to crystal impurities and defects. The thermopower S along
would think that for this it is sufficiently to increase in the
stacks is less sensitive to crystal impurities and defects and
same material the electrical conductivity and the
at room temperature varies between 40 and 45 V/K for
thermopower. But these requirements are contradictory. In
crystals grown from solution [13] and S = (363) V/K for
ordinary materials the increase of  leads to the decrease of
those grown from gas phase.
S and vice versa. In order to overcome this situation it needs
In order to describe the thermoelectric properties of
to search and investigate new materials with more
TTT2I3 crystals we will apply the model presented in [15].
complicated electronic and phonon spectra.
The electronic states are described in the tight binding and
The best bulk thermoelectric material Bi2Te3 has values of
nearest neighbor approximations. So as the conduction band
thermoelectric power factor P ~ 40 W/cm.K2 near room width is not very large, the effective mass approximation is
temperature. Recently, high values of power factor have
not applicable and the variation of electron and phonon
been measured in low-dimensional quantum well quasi-momentums into the whole Brillouin zone is taken into
superlattice structures [5]. For example, in [6] values of account. The dispersion law for holes is taken in the usual
power factor of the order of 62-66 W/cm.K2 were obtained for tight binding approximation cosinusoidal form, but for
in n-PbTe/PbEuTe quantum wells which are almost 1.7 longitudinal acoustic phonons the exact one-dimensional
times higher than that measured in Bi2Te3. Theoretically [7, expression is used.
8] even higher values of the power factor are expected in the

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The model takes into account simultaneously two electron- of Fermi energy or carriers‘ concentration. And sharp
phonon interactions and also the scattering of carriers on dependence of relaxation time on energy ensures
impurities and defects. It is important, because under certain simultaneously increased values of the thermopower.
conditions between both electron-phonon interactions the
interference can take place. The first interaction is similar to
that of deformation potential, and the second is polaron
similar, but the induced polarization is considered. Due to the
interference, both electron-phonon interactions considerably
compensate each other for a narrow strip of states in the
conduction band. As a result, the relaxation time of carriers as
a function of carrier energy takes the form of Lorentzian with
rather pronounced maximum.
Such behavior of relaxation time will ensure simultaneously
high values of electrical conductivity and increased values of
the thermopower. This situation is favorable to expect a
growth of the thermoelectric power factor P.
IV. MODELING OF THE THERMOELECTRIC POWER
FACTOR
The linearized kinetic equation for no equilibrium holes
distribution function has been deduced. Near room
temperature the scattering of carriers on acoustical phonons Fig. 1. Relaxation time as a function of energy in the
can be considered elastic. In this case the kinetic equation is conduction band. The dash-dotted line is for only first
solved exactly and, replacing the phonon distribution interaction, when D = 0,  = 0.
function by its high-T limit, the following expression for the
relaxation time is obtained The expression for the power factor P is presented
Mvs2 w2[ E (  E )]1 / 2 through the transport integrals Rn as follows
 E   , (1)
2a 2k0Tw2 2[( E  E0s, p )2  4w2  2 D] P  R12 /(e 2T 2 R0 ) , (2)
where w is the energy transfer of a carrier from a molecule to where
the nearest one along the chains, E is the carrier energy, 
2e2az
0  E   , Δ is the width of the conduction band, Δ = 4w, Rn    E  E F n E   E 1 / 2 ( E ) f0dE . (3)
 2bc
w is the derivative of the transfer energy w with respect to 0
the intermolecular distance, k0 is the Boltzmann constant, Here z is the number of chains through the transversal
  2e 2 0 /(a 5 w ) is the ratio of amplitudes of above section of the unit cell, EF is the Fermi energy, f 0 ( E ) is the
mentioned electron-phonon interaction mechanisms, e is the derivative of Fermi distribution function with respect to E.
The integration in Eq. (3) is carried out on all energies in the
carrier charge, 0 is the average polarizability of molecule,
conduction band, so as it is not too large.
E0  2w(  1) /  is the resonance energy which The expression (2) has been calculated for TTT2I3 crystals
corresponds to the maximum of  (E ) , when 0  E0   . in dependence of dimensionless Fermi energy  F  E F / 2w
The dimensionless parameter D in Eq. (1) describes the for  = 1.6 and different values of parameter D, mentioned
scattering of carriers on impurities. It is proportional to the above. In ordinary TTT 2I3  F is a little less than 0.4 and z =
linear concentration of impurity and may be made much less 4.
than unity, if the crystal purity is sufficiently high.
In Fig. 2 the calculated dependences of P on  F at room
The parameter  is not known in TTT2I3 crystals, because
the molecule polarizability is not known. We will take  = temperature are presented. It is seen that the power factor P
has also maximums which are rather large. These maximums
1.6, that corresponds to 0 = 42 Å3. For comparison, in
are the result of competition between the increase of
antracene  0 = 25Å3, but TTT molecule is bigger and  0
electrical conductivity and the decrease of thermopower. The
must be greater too. The dependence of relaxation time on lowest maximum is of the same order as in Bi2Te3, the
carrier energy is presented in Fig.1 for γ = 1.6 and different middle one is two times higher, and the last is almost four
degrees of crystal purity (D = 0.2, 0.1 and 0.05). The dash- times higher.
dotted line corresponds to the case, when only the first But the maximums are placed at lower values of Fermi
electron-phonon interaction mechanism is applied. It is seen energy than those that correspond to ordinary crystals. At
that in this case the relaxation time is a very smooth function  F a little less than 0.4 the power factor is very small. In
of energy with a small maximum of the order of 0.510-14s.
When both electron-phonon interactions are included, the order to increase P it needs to diminish  F , or carriers‘
relaxation time obtains a more pronounced maximum which concentration. It is possible because the TTT 2I3 crystals
grows with the decrease of D and becomes even sharp at D = admit non stoichiometric composition. The iodine plays the
0.05 (solid line in Fig.1). This sharp maximum corresponds role of acceptors. In order to diminish the carriers‘
to the purest crystal and is more than 15 times higher than concentration in needs to diminish the iodine concentration
that of dash-dotted line. The maximums of relaxation times and to obtain a compound of the type TTT 2I3-, where  is
determine maximums of electrical conductivity as functions the deviation of stoichiometry.

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For optimal parameters the maximal value of P = 153

W/cm.K2 is predicted. It is expected that in crystals with
higher degree of purity the thermoelectric power factor will
achieve still greater values.

REFERENCES

[1] V.G. Levich, Vvedenie v statisticheskuiu fiziku, Gos.

izdatelistvo tehniko-teoret. literatury, Moscva, 1954.
[2] D. Kondepudi, Introduction to Modern Thermo-
dynamics, Wiley, Chichester, (2008), Section 32.
[3] B.F. Paes et al. Accuracy of tympanic and infrared skin
thermometers, ACD Online First Published on August
24, 2010 as 10.1136/adc 2010. 185801.
[4] National Collaborating Center for Women‘s and
Children‘s Health. NICE Clinical Guideline 47, May
Fig.2. Power factor P as a function of dimensionless Fermi energy F for
2007, http://guidance.nice.org.uk/GC47.
[5] M. S. Dresselhause, J. P. Heremance, Recent
 = 1.6.
developments in low-dimensional thermoelectric
materials In: Thermoelectric Handbook; Macro to
Thus, for  F = 0.2 (n is diminished by 1.6 times from Nano, Ed. by Rowe, CRC press, FL, 2006, Chap. 39.
1.21021 cm-3 to 7.51020 cm-3) and D = 0.05 it follows P = [6] T.C. Harman, P.J. Taylor, M.P. Walsh, and B.E.
LaForge, Quantum dot superlattice thermoelectric
134 W/cm.K2, a very good result.
materials and devices, Science, Vol. 297, 2229 (2002).
For this carriers‘ concentration the electrical conductivity
[7] A. Casian, I. Sur, H. Scherrer, Z. Dashevsky,
 = 9.3103 -1cm-1 and the thermopower S = 120 V/K. As Thermoelectric properties of n-type PbTe/Pb1-x EuxTe
it is seen from Fig.2, the maximum of P corresponds to  F = quantum wells, Phys. Rev. B, 61, 15965 (2000).
0.12, when P = 153 W/cm.K2. Even in less pure crystals for [8] I. Sur, A. Casian, and A. Balandin, Electronic thermal
which D = 0.1, the maximum of P is still high, ~ 80 conductivity and thermoelectric figure of merit of n –
W/cm.K2. type PbTe/Pb1-x Eux Te quantum wells, Phys. Rev. B,
Surely, if the crystal purity will be still more increased, so 69, 035306 (2004).
that the parameter D will be less than 0.05, one can expect [9] A. Casian, V. Dusciac, High values of thermoelectric
power factor expected in quasi-one-dimensional organic
even higher values of the power factor than the highest in
crystals, J. of Thermoelectr., 1, 29-37, 2007.
Fig.2. One may think that this will be possible.
[10] A. Casian, V. Dusciac, V. Nicic, Promising low-
V. CONCLUSIONS dimensional organic material for IR detectors,
The thermoelectric power factor P, which is the main Romanian J. of Phys., 55, 205-212, 2010.
physical parameter that determines the opportunity of a [11] A. Casian, J. Stockholm, V. Dusciac, V. Nicic, Low
material to be used in sensitive elements of infrared radiation dimensional organic crystal Tetrathiotetracene-Iodide as
detectors, has been modeled in nanostructured quasi-one- thermoelectric material, J. of Nanoelectronics and
dimensional organic crystals of tetrathio-tetracene-iodide, Optoelectronics, 4, 95-100, 2009.
TTT2I3, in dependence of crystal parameters. A more [12] A. Casian, Violation of the Wiedemann-Franz law in
complete crystal model is used that take into account two quasi-one-dimensional organic crystals, Phys. Rev. B
electron-phonon interactions and the scattering of carriers on 81, 155415, 2010.
impurities. One interaction is similar to that of deformation [13] I.F. Shchegolev, E.B. Yagubskii. Cation-Radical Salts
potential and the second is of polaron type. of Tetrathiotetracene and Tetraselenotetracene:
It is shown that, due to the interference of these electron- Synthetic Aspects and Physical Properties. In Extended
phonon interactions, the thermoelectric power factor P as a Linear Chain Compounds, N.-Y.: Ed. by I. S. Miller,
function of Fermi energy (or carriers‘ concentration) obtains Plenum Press, 1982, v. 2. pp. 385-435.
maximums which depend on crystal purity. For ordinary [14] B. Hilti and C.W. Mayer Electrical Properties of the
crystals with stoichiometric concentration P is very small. Organic Metallic Compound bis (Tetrathiotetracene)-
But if the carriers‘ concentration is diminished by 1.6 times Triiodide, (TTT)2I3. Helvetica Chimica Acta, 61, Nr 40,
from 1.21021 cm-3 to 7.51020 cm-3, P is increased in the 501, (1978).
crystals with the highest degree of purity up to 134 [15] A. Casian, V. Dusciac, and Iu. Coropceanu. Huge
W/cm.K2, a very good result. carrier mobilities expected in quasi-one-dimensional
organic crystals. Phys. Rev. B 66, 165404 (2002).

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Single-Crystal Microwires Based on Doped Bi

for Anisotropic Thermoelectric Devices
L. KONOPKO1,2, A. NIKOLAEVA1,2, T. HUBER3, A. TSURKAN1
1
Institute of Electronic Engineering and Nanotechnologies “D. Ghitu”, AS of Moldova
2
International Laboratory of High Magnetic Fields and Low Temperatures, Wroclaw 53-421, Poland
3
Department of Chemistry, Howard University, 500 College St. N.W., DC 20059 Washington, U.S.A.
[email protected], [email protected], [email protected], [email protected]

Abstract – We have investigated the possibility to use a microwire of BiSn to design an anisotropic
thermoelectric generator. The glass-coated microwire of pure and Sn-doped bismuth was obtained by the
Ulitovsky method; it was a cylindrical single-crystal with orientation (1011) along the wire axis; the C3 axis
was inclined at an angle of 70º to the microwire axis. It is found that doping of bismuth wires with tin
increases the thermopower anisotropy in comparison with Bi by a factor of 2 – 3 in the temperature range of
200 – 300 K. For a Bi microwire with a core diameter of 10 μm with a glass coating with outer diameter of 35
μm, the transverse thermopower is ~ 150 μV/(K*cm); for BiSn, 300 μV/(K*cm). The design of an anisotropic
thermogenerator based on BiSn microwire is proposed. The miniature thermogenerator will be efficient for
power supply of devices with low useful current. In addition to the considerable thermopower anisotropy of
BiSn wires in a glass coating, they exhibit stable thermoelectric properties, high mechanical strength and
flexibility, which allows designing thermoelectric devices of various configurations on their basis.

Index Terms – anisotropy, bismuth, microwires, thermoelectricity, thermogenerator.

obtaining of high-performance materials with high

I. INTRODUCTION
thermopower anisotropy and reproducible parameters, and
The search for new unconventional sources of electric
the problem of the design, calculation, and preparation of
power is now the research trend of particular concern and
devices based on ATs.
high priority.
Bismuth single crystals exhibit a thermopower anisotropy
As a source of heat for thermoelectric generators, the
of ≈ 50 μV/K in a temperature range of 100 – 400 K, which
thermoelectric method of thermal energy conversion into
makes it possible to design ATs with a sensitivity of ≈ 10 –
electric energy involves unconventional renewable sources
15 mV/W and rapid response time τ = 10-2 s; they find
of thermal energy: from solar energy to the heat of human
practical application, in particular, as heat flow meters in
body. [1,2]
microcalorimetry [5,6].
The appearance of new more efficient materials for
anisotropic thermoelements (ATs) is reviving interest in the The value and temperature dependence behavior of the
transverse thermoelectric effect. The efficiency of ATs is thermopower anisotropy of Bi can be rather easily controlled
governed to a considerable extent by thermopower by doping and introduction of twin interlayers [7]. Bismuth
anisotropy value. The principle of operation and the features turned out to be appropriate in various radiation sensors and
ATs were extensively studied both in scientific and applied microelements. The fundamental difference of ATs from
aspects [3,4]. traditional thermoelements is that the thermopower
A transverse AT, as a voltage source in measuring comprises the geometric factor l/h, where l is the sample
length and h is its thickness. The thermopower of traditional
systems, has some advantages:
thermoelement does not depend on the geometric sizes of
(i) The thermopower, unlike a conventional thermocouple,
these thermocouples, whereas the thermopower of ATs is
is proportional to the temperature gradient (T1 - T2) / h proportional to the length and inversely proportional to the
instead of the temperature difference T1 - T2. Thus, thickness; thus, we can increase the thermopower by
decreasing the width h, it is possible to increase voltage at increasing the AT length.
the same temperature difference.
(ii) Voltage V is proportional to length l; thus, it is II. SAMPLES AND EXPERIMENT
possible to increase voltage by increasing the length of the We have studied the possibility of using a microwire of
plate. bismuth doped with Sn to design an anisotropic
(iii) To obtain voltage, we need no junctions that are thermoelectric generator. Glass-insulated single-crystal
wires of pure and Sn-doped bismuth were prepared by the
required for increasing sensitivity. In the case of ATs, it is
Ulitovsky method; they were cylindrical single crystals with
sufficient to increase the length of the crystal employed in
the (1011) orientation along the wire axis; the C3 axis was
order to enhance sensitivity.
inclined at an angle of 70o to the wire axis. The technique
In this regard, there are some problems in obtaining described in [8,9] allows preparing single-crystal wires with
efficient ATs: the problem of material science, including diameters from 50 μm to nanometers. It is known that the

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size effect significantly changes the thermoelectric

properties and leads to an increase in thermoelectric
efficiency [10].
The developed technology allows obtaining a glass-
insulated single-crystal microwire of Bi and its alloys with
Sn with a length up to a few meters and with a given
diameter from 100 nm to 50 μm. The specific resistivity was
studied as a function of the doping impurity composition,
wire diameter, and crystallographic orientation.
To study the thermopower anisotropy of the wires, we
used samples with C3 oriented along the wire axis, which
were obtained by the methods of zone and laser
recrystallization.
The transverse thermopower αtrans = U/ΔT, where U is the
voltage across the sample, ΔT is the transverse temperature
gradient. To measure the transverse thermopower αtrans in
microwire segments with a length of 10 cm, we made a
special device consisting of two copper plates with different
temperatures. A glass-insulated microwire segment with a
length of 10 cm was placed between these plates in such a
way as to keep good thermal contact between the glass cover
of the microwire and the surface of the plates throughout the
length of the microwire (Fig. 1). To obtain a uniform
temperature gradient, a resistive heater was placed on one of
the plates; it occupied 80% of the entire surface of the plate.
The temperature gradient was measured by a differential
copper-constantan thermocouple, two junctions of which Fig. 2. Angle diagrams of TMR R(Θ) of Bi–0.05Sn (d =0.6 µm) with
were situated in the middle of the plates near the surfaces standard (a) and trigonal (b) orientations, H = 0.5 T, T =4.2 K.
being in contact with the microwire. In wires with C3 oriented along the wire axis, the
anisotropy of the transverse magnetoresistance is governed
only by L-carriers, because, as the magnetic field rotates in
the basal plane, the contribution of T-holes to the
magnetoresistance does not depend on the direction. The
rotation diagram structure corresponds to the sixfold rotation
axis symmetry. The minima in the diagrams correspond to
the sample orientation when one of the binary axes C2 is
parallel to H.
Fig. 3 depicts the dependences of the longitudinal
magnetoresistance (LMR) R(H), H || I for the Bi-0.05 at% Sn
wires with the (1011) and (111) orientation along the wire
axis and ShdH oscillations at H ┴ I for wires with C3
oriented along the wire axis.
Fig. 3 shows that ShdH oscillations of the
magnetoresistance R(H) in Bi wires doped with an acceptor
Fig. 1. Physical form of the device for measuring transverse thermopower in impurity of Sn can be seen in the longitudinal and transverse
samples of a glass-insulated microwire. orientations both in wires with C3 oriented along the wire
axis and in wires with the (1011) orientation along the axis.
Analysis of the SdH oscillations (Fig. 3) shows that the
The method of ShdH oscillations was used for estimating glass-insulated single-crystal Bi-0.05 at% Sn wires under
the Fermi level in doped Bi wires. study really had two orientations: C3 along the axis and C½
III. RESULTS AND DISCUSSION along the wire axis.
Fig. 2 shows the diagram of rotation of the transverse The Fermi energy of holes in T in the Bi-0.05 at% Sn
magnetoresistance of the Bi- 0.05 at% Sn wires with (a) the wires was calculated in terms of the two-band Kane model
(1011) standard orientation and (b) C3 orientation along the using the expression 1.
wire axis. The angular dependence of the transverse 1
magnetoresistance (TMR) R(Θ) in the Bi-0.05at%Sn wires 1  2  1  2
2

with the (1011) orientation along the axis is similar to  FT   par   gT   par    gT   (1)
dependence for bulk samples: the dependences are 2   2  
symmetric about directions Θ = 0o and Θ = 90°. At Θ = 0, H Where εpar is the energy in the parabolic band
|| C3; at Θ = 90°, H is parallel to the binary axis C2. approximation;

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eh  T1 Fig. 4 shows that the maximum thermopower anisotropy

 par  (2) occurs at temperatures of 250-300 K; it is 100-120 μV/K,
2c  mcT which is more than twice as high as the anisotropy α in pure
is the Fermi energy of holes in T calculated downwards Bi in the same temperature range.
T
from the band top in T; mc is the small cyclotron mass of

T-holes;  gT is the gap in the T-point of the Brillouin zone

1
that amounts to 200 meV according to [11,12];  T is the
value of inverse period of the ShdH oscillations from the
smallest section of the hole ellipsoid in the T-point of the
Brillouin zone.

Fig. 4. Temperature dependences of thermopower α(T) (scale on the left)

and resistance R(T) (scale on the right) of Bi–0.05 at% Sn wires (d =0.6
µm) with standard (1,2) and trigonal (1‘,2‘) orientations.

The transverse thermopower of glass-insulated microwire

segments with a length of 10 cm of Bi and Bi-0.05 at% Sn in
the diameter range d = 3 – 20 μm was measured at room
temperature; the diameter D involving the glass insulation
varied within 15 – 40 μm. The highest transverse
thermopower per unit length of the microwire equal to 100
μV/(K*cm) was obtained for a bismuth microwire with d = 8
μm. For the Bi-0.05 at% Sn microwire, the maximum
transverse thermopower per unit length of the microwire is
significantly higher: it is 290 μV/(K*cm) in a microwire
with d = 5.5 μm.
These results allow expecting that, after finding the
optimum design solution of the place of a long microwire in
the plate in the external temperature gradient, it will be
possible to prepare an anisotropic thermoelectric generator
for feeding devices with low useful current.
In addition to the considerable thermopower anisotropy,
glass-insulated BiSn wires exhibit stable thermoelectric
Fig. 3. (a) Field dependencies of LMR R(Н) (H||I) of Bi-0,05 ат% Sn wire properties and high mechanical strength, which allows
designing thermoelectric devices of various configurations
(d = 1 μm) with standard (10 1 1) (1) and trigonal (2) orientations at T = 2.1
K. Insert: dependences of the quantum number n of the ShdH oscillations on on their basis. The fact that the efficiency of an anisotropic
reverse field H-1. (b) Field dependencies of TMR R(Н) ( H  I ) of Bi-
generator comprises the wire length and thickness yields
0,05 ат% Sn wire with trigonal orientation at θ = 0° (1) and θ = 67° (2) broad possibilities of their optimization; the efficiency and
according to figure 2 (b), at T = 2.1 K. Inserts: left – field dependencies of the economic feasibility of the process of preparation of the
derivative of TMR at θ = 0° (1) and θ = 67° (2) at T = 2.1 K; right - wires will enable applying them as anisotropic generators on
dependences of the quantum number n of the ShdH oscillations on reverse an industrial scale.
field H-1 at θ = 0° (1) and θ = 67° (2) at T = 2.1 K.

IV. CONCLUSION
In addition, it was taken into account that at H || I, as in
It is found that doping of bismuth wires with tin increases
wires of pure Bi of the given crystallographic orientation [9],
the thermopower anisotropy in comparison with Bi by a
the ShdH oscillations are registered from the cross-section factor of 2 – 3 in the temperature range of 200 – 300 K.
of the hole T-ellipsoid close to the maximum (the sample According to the results, for a Bi microwire with a diameter
axis is tilted by an angle of 20o from the bisector axis). It of 10 m with a glass coating of 35 m, the transverse
was found that TF in Bi-0.05 at% Sn wires is located in the thermopower is ~ 150 μV/(K*cm); for BiSn, 300
zone of L-holes. μV/(K*cm), that can be used to create ATs for feeding
To study the anisotropy of the thermopower and devices with low current.
resistance, the temperature dependences (T) and resistance
R(T) of Bi–0.05 at% Sn wires with different orientations in a
temperature range of 4.2 – 300 K were investigated (Fig. 4).

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ACKNOWLEDGMENTS [6] W. Lukosz, Z. Natursch, A 19, 1599 (1964).; G.A.

This work was supported by the SCOPES Grant # Ivanov, V.M. Grabov, Fizika i Tehnika
IZ73Z0_1 27968 and ASM Project # 11.836.05.05A. Poluprovodnikov 29, 1040 (1995).
[7] I.M. Pilat, S.V. Chayka, S.I. Pirojenko, N.V. Kruglova,
REFERENCES
Fizika Tverdogo Tela 17, 176 (1975).
[1] D. Chinory, Solar Power Generator. The British
[8] N.B. Brand, D.V. Gitsu, A.A. Nikolaeva, and Ya.G.
petroleum Company Pic, Patent, BBH 17.09.86, MKI
Ponomarev, Zh. Exp. Teor. Fiz. 72, 2332 (1977). [Sov.
24 2/04 H01 35/02, MKH F460.
Phys. JETP 45, 1226 (1977)].
[2] Yu.S. Bortnikov et al., Izv. Akad. Nauk SSSR. Energia i
[9] D. Gitsu, L. Konopko, A. Nikolaeva, and T. Huber,
transport 5, 3 (1961).
Applied Physics Letters 86, 10210 (2005).
[3] P.I. Baranskii, I.S. Buda, I.V. Dakhovskii, A.G.
[10] Y.M. Lin, X.Z. Sun, M.S.Dresselhaus, Phys. Rev. B.:
Samoilovich, Phys. Stat. Sol. (b) 67, 201 (1975).
Condens. Matter Mater.Phys. 62, 4610 (2000).
[4] A.R. Regel‘, G.A. Ivanov, V.M. Grabov, L.I.
[11] N. Brandt, P. Mulier, Ya. Ponomarev, Sov. Phys. JETP
Anatychuk, O.Ia. Luste, Patent No. 245859 (1968).
44, 1196 (1977).
[5] L.I.Anatychuk, Termoelementy i termoelektricheskie
[12] N.A. Red‘ko, N.A. Rodionov, Pis‘ma v JETP 42(6), 246
ustroistva. Reference book. Kiev: Naukova dumka
(1985).
1979, 766 p.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Superconducting Spin Switch Based on

Superconductor-Ferromagnet Nanostructures for
Spintronics
Jan KEHRLEa, Vladimir ZDRAVKOVa,b, Claus MUELLERa, Guenter OBERMEIERa, Matthias
SCHRECKa,
Stefan GSELL , Siegfried HORN , Reinhard TIDECKSa, Roman MORARIb,c, Andrei PREPELITSAb,
a a

Evgenii ANTROPOVb, Alexei SOCROVISCIUCb, Eberhard NOLDc, Lenar TAGIROVa,d, Anatoli

SIDORENKOb,c
University of Augsburg, D-86135 Augsburg, Germany
Institute of Electronic Engineering and Nanotechnologies “D. Ghiţu” ASM
Kishinev, MD2028, Moldova
Institute of Nanotechnology, D-76021 Karlsruhe, Germany
Solid State Physics Department, Kazan State University, Kazan, 420008, Russia;
[email protected]

Abstract – Very rapid developing area, spintronics, needs new devices, based on new physical principles.
One of such devices – a superconducting spin-switch, consists of ferromagnetic and superconducting
layers, and is based on a new phenomenon – reentrant superconductivity. The tuning of the
superconducting and ferromagnetic layers thickness is investigated to optimize superconducting spin-
switch effect for Nb/Cu41Ni59 based nanoscale layered systems.

Index Terms – spin-switch, superconductivity, proximity effect, spintronics, nanotechnology

several nanometers. The S and F layers were deposited by

magnetron sputtering on commercial (111) silicon substrates
I. INTRODUCTION
at room temperature. The base pressure in the ―Leybold
Fulde, Ferrell [1], Larkin and Ovchinnikov [2] predicted
Z400‖ vacuum system was about 2×10-6 mbar. Pure argon
that an unconventional, nonuniform superconducting pairing
(99.999%, ―Messer Griesheim‖) at a pressure of 8×10 -3 mbar
(FFLO) with a non-zero momentum of a pair may occur in a
was used as sputter gas. A silicon buffer layer was deposited
ferromagnetic background, i.e. in the presence of an
using RF magnetron. It produced a clean interface for the
exchange field. In conventional (s-wave) superconductors
subsequently deposited niobium layer. To obtain flat and
such state can only be observed in a very small range of
high-quality Nb layers with thickness in the range of 5-15
parameters and has not been realized up to now
nm, the rotation of the target around the symmetry axis of
experimentally. However, Buzdin et al. [3] predicted FFLO-
the vacuum chamber was realized. A dc-motor drive moved
like pairing in S/F layered structures, where the pair
the full-power operating magnetron along the silicone
amplitude in the F-material establishes due to penetration of
substrate of the 80×7 mm2 size during the deposition. Thus,
the singlet electron pairs from the superconductor through
the surface was homogeneously sprayed with the sputtered
the S/F interface. More advanced analysis was worked out
material. The effective growth rate of the Nb film in this
by Tagirov [4] and Fominov et al. [5]. The most spectacular
case was about 1.3 nm/sec. The deposition rate for a fixed,
prediction of these theories is that not only Tc oscillations but
non-moving target would be about 4-5 nm/sec.
also complete suppression of superconductivity may occur in
a certain range of thicknesses of the F-layer followed by its
unusual re-entrance with increasing of the F-layer thickness.
Superconducting spin-switch based on proximity effect in
Ferromagnet – Superconductor – Ferromagnet (F/S/F)
layered system was investigated then theoretically in [6,7]
using hypothetical materials and their thicknesses. The
thicknesses tuning of the superconducting and ferromagnetic
layers in SF -structures is the goal of the present work, to
Fig.1. Sketch of the layers stack in the deposited S/F-specimen.
investigate and optimize superconducting spin-switch effect
for Nb/Cu41Ni59 based nanoscale layered system.
The next step of the procedure was deposition of a wedge-
shaped ferromagnetic layer utilizing the intrinsic spatial
II. FILMS DEPOSITION AND CHARACTERIZATION
gradient of the deposition rate of the sputtering material. The
We developed a special advanced technological process of
Cu40Ni60 target was RF sputtered with a rate of 3-4 nm/sec,
superconducting layers preparation [8] for reliable
resulting in practically the same composition (Cu41Ni59) of
fabrication of S/F structures with the layer thickness scale of
the alloy in the film. To prevent a destructive influence by

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the atmospheric conditions, the last deposited layers were transition temperature Tc reveals an expressed non-
coated by a silicon cap of about 5-10 nm thickness (see a monotonic behavior with a deep minimum at dCuNi about 7.9
sketch of the prepared samples in Fig. 1). nm. For the series of specimens with dNb ≈ 6.2 nm the
Samples of a width of about 2.5 mm were cut transition temperature Tc decreases sharply for increasing
perpendicular to the wedge to obtain a set of S/F bilayer ferromagnetic Cu41Ni59 layer thickness, until dCuNi ≈ 3.8 nm.
strips with varying Cu41Ni59 layer thickness dF, for Tc(dF) Then, for dCuNi ≈ 3.8-24 nm,
measurements. Aluminum wires of 50 μm in diameter were
bonded to the strips by ultrasonic bonder for four-probe
resistance measurements.
8
S23_12_1001.pro: SEM 1 Profil FZK IMF1
07 Dec 3 10.0 keV 0 FRR 9.7957e+001 max 7 S23, dNb  14.1 nm
Nb1/Full (Binom3)

S23_12_1001.pro 6
100
Si Si O
5

TC (K)
90
Nb
Nb
Si 4 S22, dNb  7.8 nm
80 Cu

70 O
Ni 3
N
Atomic Concentration (%)

60
Ni C 2
1 S21,dNb 6.2 nm
50

40 Cu 0
30
0 5 10 15 20 25 30 35 40
dCuNi (nm)
20
O
10 C
N Fig.3 Non-monotonous Tc (dF) dependence for Nb/Cu41Ni59 bilayers with the
Nb
0
0 20 40 60 80 100 120 140 Nb layer thickness, dNb≈ 6.2 nm, dNb ≈ 7.8 nm, and dNb ≈ 14.1 nm. Solid
Sputter Time (min) Rate 1nm/min Si-ox. lines are fits using the theory [4].

Fig. 2. Scanning Auger electron spectroscopy (AES) of a the superconducting transition temperature vanishes (at
Si(substrate)/Si(buffer)/Nb/Cu1-xNix/Si(cap) sample, dNb =7.5 nm and least Tc <40 mK, which is the lowest temperature measured).
dCuNi=32.9 nm (thickness according to the RBS data).
For dCuNi > 24 nm the transition into a superconducting state
To study the quality of interfaces between the layers we is observed again. Finally, Tc increases to a little bit above
performed Auger electron spectroscopy (AES) 1 K showing an outstanding reentrant superconductivity
measurements of specimens. A defocused Xe-ion beam behavior with evidence for a second disappearance of the
erodes a crater into the film with inclination angles of the superconducting state at dCuNi > 37.4 nm. Altogether, the
scarps of only a few degrees or below. An electron beam Tc(dCuNi) curves given in Fig. 3 represent all types of non-
then scans the shallow crater. The emitted Auger electrons monotonic Tc(dCuNi) behaviors predicted by the theory [4].
reveal the lateral distribution of elements. As a result, one This phenomenon of the reentrant superconductivity in the
reconstructs the elemental concentration as a function of the S/F bilayer has been presented in our recent publications
sample depth profile. The AES data for the Nb/Cu1-xNix [9,10].
specimen are shown in Fig. 2. There are about 59 at.% Ni (in
agreement with the RBS data) and 39.0 at.% Cu in the Cu1- IV. SIMULATION AND DISCUSSION
xNix film. There is a small concentration of O, C and N
impurities at the Nb/Cu1-xNix interface as a result of physical To describe the experimental data we used the calculation
absorption of gases from the residual atmosphere of the procedure described in [9,10]. The results for
vacuum chamber. The Cu1-xNix/Si(cap) interface is free of superconducting critical temperature Tc calculations for
contaminations. parallel and anti-parallel directions of ferromagnetic layers
The samples for the Tc(dS) measurements were prepared magnetizations for a core-structure Cu41Ni59 /Nb/ Cu41Ni59
with the same procedure, but with a Cu41Ni59 film of with superconducting layer thicknesses dNb = 12.5nm, 14 nm
constant thickness on the top of a wedge-shaped Nb layer. In are presented in Fig. 4.
addition, single flat Nb films and single CuNi-wedge shaped One can see that a maximal spin-switch effect value ∆Tc
layers were prepared in a similar way for materials of the order of 1-2 K is achievable only in a very strict
characterization. region of superconductor and ferromagnetic layer
thicknesses. Otherwise one can expect only negligible value
III. SUPERCONDUCTING PROPERTIES OF of ∆Tc.
NB/CU41NI59 BILAYERS
Fig. 3 demonstrates the dependence of the V. CONCLUSION
superconducting transition temperature for SF samples on
It was found from the calculations, based on our
the thickness of the Cu41Ni59 layer. For specimens with
experimental parameters that maximal spin-switch effect
dNb ≈ 14.1 nm the transition temperature Tc reveals a non-
value with the order of magnitude 1-2 K is achievable only
monotonic behavior with a very shallow minimum at about
for the strict range of superconductor and ferromagnetic
dCuNi ≈ 6.8 nm, it is just the qualitative behavior. The
layers thicknesses. This range of controlled thicknesses is

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accessible using advanced vacuum technology [8-10] in Superconductor/Ferromagnet Nanolayered Structures―

developed by us for preparation of the F/S/F-core structure (GZ: HO 955/6-1, UA participants), and the project of the
for a superconducting spin-switch construction. Moldavian State Program ―Investigarea supracondubilităţii
neomogene în nanostructucturi stratificate supraconductor-
feromagnet şi elaborarea valvei de spin în baza lor‖ (R.M.,
A.P., E.A., A.S. and An.S.).

REFERENCES
[1] P. Fulde and R. Ferrell, Phys. Rev. 135, A550 (1964).
[2] A.I. Larkin and Yu.N. Ovchinnikov, Zh. Eksp. Teor.
Fiz. 47, 1136 (1964) [Sov. Phys. JETP 20, 762 (1965)].
[3] A.I. Buzdin and M.Yu. Kupriyanov, Pis'ma v ZhETF
52, 1089 (1990) [JETP Lett. 52, 487 (1990)].
[4] L.R. Tagirov, Physica C 307, 145 (1998).
[5] Ya.V. Fominov, N.M. Chtchelkatchev, and
A.A. Golubov, Phys. Rev. B 66, 014507 (2002).
[6] L.R. Tagirov. Phys. Rev. Lett. 83, 2058 (1999).
[7] A.I. Buzdin, A.V. Vedyayev, and N.V. Ryzhanova,
Europhys. Lett. 48, 686 (1999).
[8] A.S. Sidorenko, V.I. Zdravkov. R. Morari Device for
Fig.4. Tc(dF) curves of a superconducting F/S/F spin-valve core structure preparation of superconducting layers, Patent of RM
with dS = dNb= 12.5 nm (a), dS = dNb= 14 nm (b) calculated using the 175 (134) Y din 2010, Cl.Int. H01 L 21/00.
following set of parameters for (a) and (b) respectively: Tc0,Nb(dCuNi = 0 nm) [9] V.I. Zdravkov, J. Kehrle, G. Obermeier, S. Gsell,
= 7.7, 8.1 K; in all cases ξS = 6.6 nm; NFvF/NSvS = 0.22; TF = 0.6; M. Schreck, C. Müller, H.-A. Krug von Nidda,
lF/ξF0 = 1.1; ξF0 = 10.5 nm.
J. Lindner, J. Moosburger-Will, E. Nold, R. Moari,
ACKNOWLEDGEMENTS V.V. Ryazanov, A.S. Sidorenko, S. Horn, R. Tidecks,
and L.R. Tagirov, Phys. Rev. B 82, 054517 (2010).
The authors are thankful to A.F. Andreev, A. Buzdin,
[10] A. S. Sidorenko, V. I. Zdravkov, J. Kehrle, R. Morari,
R. Gross, H. Hahn, A. Zaikin, M. Kupriyanov and V.
E. Antropov, G. Obermeier, S. Gsell, M. Schreck,
Ryazanov for stimulating and fruitful discussions. The work
C. Müller, V. V. Ryazanov, S. Horn, R. Tidecks, and
was partially supported by A.v. Humboldt grant -
L. R. Tagirov. in: Nanoscale Phenomena -
Institutspartnerschaften ―Nonuniform superconductivity in
Fundamentals and Applications. H. Hahn, A. Sidorenko,
layered SF-nanostructures Superconductor/Ferromagnet‖
and I. Tiginyanu, Eds. Springer-Verlag, Berlin-
(R.M. and An.S.), by DFG under the grant „Study of the
Heidelberg, 2009, p.3-11.
Superconducting Proximity Effect Spin-Valve Phenomenon

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

High Resolution Position Inductive Transducers

for Harsh Environmental Conditions
1
Nicolae JULA, 2Tudor URSU, 3Cristina Nicoleta DIACONESCU, 2Radu OBREJA
1
Military Technical Academy – Bucharest, ROMANIA
2
S.C. Sistem Euroteh – Buzau, ROMANIA
3
Technical University Gheorghe Asachi – Iasi, ROMANIA
1
[email protected] [email protected]
,
[email protected],[email protected]

Abstract – In this paper the authors present certain theoretical, conceptual and technological aspects on main
types of high resolution inductive transducers for harsh environmental conditions. Inductive resolvers, as
well as inductive RVDT, have a priority in these applications, even other types of position transducers, as
optical, capacitive or magnetic encoders are in competition.
In the world there are many researchers that continue activity of conceptual and technological development
to increase the resolution level of the inductive resolvers and inductive RVDT, as well as to obtain smaller
and smaller dimensions, just it is requested in such kind of applications. On the other hand, the inductive
transducers are more adapted at harsh mechanical and climatic conditions that are usual for special
applications.
The paper is referring, especially, to inductive transformers type resolver.

Key words – inductive transducers, high resolution, harsh conditions

demonstrated that the level of accuracy and global physical

I. GENERAL ASPECTS
resistance of item are kept in these special harsh conditions.
Writers‘ opinion is to consider in the position inductive
Position inductive transducers are used as main
transducers class: rotary inductive transformers, to
components in the applications where it is required very high
measure the angular position, components that are generally
accuracy. For example, a modern measurement and control
named rotary inductive potentiometers and include resolvers,
system including a synchro-resolver transmitter type and a
microsyns and RVDT; linear inductive transformers, to
synchro-resolver receiver type represents a most frequent
measure the linear position, components that are generally
solution to acquire the position information in very accurate
named linear inductive potentiometers, including specially
manner for large range of applications.
the transducer LVDT type.
In fact, position inductive transducer is used to translate
We have to remark that, especially in the last time, the
into electric magnitude an angular or linear dimension and
users have replaced in certain applications the inductive
consists of an asynchronous electric machine, especially
transducers with encoders (based on optical, capacitive or
developed to produce one system of alternative outputs
magnetic phenomena) and it was expressed by some
having variable amplitude.
producers a concept according with that the inductive
It may be considered that this electric machine is a kind of
transducers shall be replaced totally and forever with the
retort at the general electric transformer that has all elements
encoders. But, the reality has demonstrated that this concept
fix, so has only a certain magnitude of output.
is completely wrong because it is not based on the whole
However, the real purpose was not to be a retort, but to
spectrum of criteria. Some users and producers have
solve some important needs that the progress of systems and
considered only the price, but when high accuracy is
applications has required at a certain moment. We have to
requested the price of inductive transducers seems to be not
remark that there is an important difference to the situation
decisive.
of a classic asynchronous electric machine: position
Moreover, some characteristics as: robustness, high
inductive transformer generates output signals as a
resistance at harsh environment conditions, a perfect
transformation component and this one depends
capacity to operate in an atmosphere with smog, fog, vapour
insignificantly from rotation speed. Generally, the
or suspension assure to use the inductive transducers very
component depending of rotation speed is taken into
long time in the future.
consideration inside of global error factory.
Through the evolution of machine development, builders
Over time, the authors had conceived, developed, built
and system integrators alike, agree that the inductive
and tested many types of position inductive transducers,
transducer is unsurpassed in its ability to reliably supply
paying special attention to analyse back e.m.f. accuracy
rotary position data in the harshest environment conditions.
relative to different types of winding schema, as well as to
So, any segregation is not useful: the inductive transducers,
do a right interpretation regarding the results obtained on
as well as the encoders, are used and will be used by
vectorial measurements methods. Also, were made many
different users just according with their needs, interests and
tests in special environment conditions, similar to harsh
affinity.
conditions for special applications. These tests have

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II. INDUCTIVE TRANSDUCERS TYPE RESOLVER voltages on the secondaries are given by the following
equations:
2.1. Construction. Primary Input: V(R1–R2) = VR = E1max sin ωt
Representative equations and diagrams Sine Secondary: V(S2–S4) = VS = VR TR sin(θ) Cosine
As we have mentioned above, resolver is the position Secondary: V(S1–S3) = VC = VR TR cos(θ) ,
sensor or transducer which measures the instantaneous where θ is the mechanical angle of the rotor as shown in the
angular position of the rotating shaft to which it is attached. resolver schematic (fig. 2 and fig. 3).
Resolvers and their close cousins, synchros, have been in use
since before World War II. Resolvers are typically built like
small motors with a rotor (attached to the shaft whose
position is to be measured), and a stator (stationary part)
which produces the output signals.

a.

a.

b.

Fig. 2 BL (brushless) transmitter and receiver resolver a. Schematic on

b. construction of BL transmitter resolverb. Schematic on construction of BL
Fig. 1 a. Showing resolver construction with housing, sinus and cosinus receiver resolver
windings, bearings and rotary transformer b. Typical control of
electromechanical servo-system

The word resolver is a generic term for such devices

derived from the fact that at their most basic level they
operate by resolving the mechanical angle of their rotor into
its orthogonal or Cartesian (X and Y) components. From a
geometric perspective, the relationship between the rotor
angle (θ) and its X and Y components is that of a right
triangle.
Fundamentally, then, all resolvers produce signals
proportional to the sine and cosine of their rotor angle,
relative to fix position of the stator. Since every angle has a
unique combination of sine and cosine values, a resolver
provides absolute position information within one electric
revolution (360°) of its rotor (only it has 2 poles). This a.
absolute (as opposed to incremental) position capability is
one of the resolver‘s main advantages over incremental
encoders. However, we have to remark that the absolute
character is related only one electric revolution, so to have
an absolute reference for whole physical rotation
(mechanical 360°) it must to build the resolver only with two
poles. Like all transformers, the resolver requires an AC
carrier or reference signal (sometimes also called the
excitation) to be applied to its primary. The amplitude of this
reference signal is then modulated by the sine and cosine of
the rotor angle to produce the output signals on the two
secondaries. In any transformer, there is a value which
relates the output voltage produced by the secondary to that b.
fed into the primary. For resolvers, this quantity is called the
Fig.3 a. Resolver produces a set of analogical outputs sine – cosine b.
transformation ratio or TR and is specified at the point of Absolute character of the resolver
maximum coupling between primary and secondary. If we
define the reference voltage V(R1–R2) as VR, then the If we excite the resolver primary (VR) with the

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recommended sinusoidal reference signal, the secondary forcing a counter to track the position of the resolver. This
voltages are also sinusoidal at the same frequency and implicit arc tangent calculation is based on the trigonometric
nominally in phase with the reference. Their amplitude is identity:
proportional to the amplitude of the reference, the sin(θ - δ) = sinθ cosδ - cosθ sinδ
transformation ratio of the resolver and the sine or cosine of This equation says that the sine of the difference between
the mechanical angle of the rotor. Using a typical value of two angles can be calculated by cross multiplying the sine
TR as 0.5, we can look at the secondary voltages for and cosine of the two angles and subtracting the results.
different rotor angles as they would appear on an Further, as long as the difference between the two angles is
oscilloscope (fig. 4). relatively small (δ = θ ± 30° ), the approximation sin(θ - δ )
≈ θ - δ may also be used, further simplifying the equation.
Thus, if the two angles are within 30° of each other, the
difference between the angles can be calculated using the
cross multiplication shown above.
In the R/D converter, this equation is implemented using
multiplying D/A converters to multiply the resolver signals
(proportional to sin θ and cos θ ) by the cosine and sine of
the digital angle, δ , which is the output of the converter, as
a. b. shown below. The results are subtracted, demodulated by
multiplying by the reference signal, and filtered to give a DC
signal proportional to the difference or error between the
resolver angle, θ, and the digital angle, δ. The digital angle,
δ, stored in the counter, is then incremented or decremented
using a voltage controlled oscillator until this error is zero, at
which point δ = θ (the digital angle output of the converter is
equal to the resolver angle). This incrementing and
decrementing of the digital angle, δ, causes it to track the
c. d. resolver angle, θ, hence the name of this type of converter.

e. f.
Fig. 4 Explanation on resolver operating principle

While it is helpful to know how the resolver signals

appear as functions of time since that is what one sees when
one looks at them with an oscilloscope, it is often more Fig.
convenient to work with the envelope (amplitude at the 5 Schematic on operating principle of analogue – digital converter (resolver
to digital converter)
reference frequency) of the signals with respect to rotor
position. Shown in fig. 4e is the envelope of the sine Above were presented some general aspects on bipolar
secondary signal with respect to rotor position. The process resolver. But, to increase the accuracy, the resolver is built in
of removing the carrier signal—leaving just the envelope— a version with more poles (2p) – 4, 8, 16, or 32 pairs (p) of
is called demodulation and is performed by the Resolver-to- poles. On this way, the resolver is loosing the absolute
Digital (R/D) converter. The demodulated sine and cosine character and it is necessary to add a supplementary set of
resolver signals are shown in fig. 4f. windings in a bipolar configuration. In this situation, the
The resolver-to-digital converter performs two basic operating main and simplified equations are:
functions: demodulation of the resolver format signals to Primary Input: V(R1–R2) = VR = E1max sin ωt
remove the carrier and angle determination to provide a Sine Secondary: V(S2–S4) = VS = VR TR sin(pθ) Cosine
digital representation of the rotor angle. The most popular Secondary: V(S1–S3) = VC = VR TR cos(pθ)
method of performing these functions is called ratiometric pθ = arctan(sin(pθ) / cos(pθ)) = arctan(Vs/Vc)
tracking conversion. Since the resolver secondary signals
represent the sine and cosine of the rotor angle, the ratio of 2.2. Typical windings for resolver
the signal amplitudes is the tangent of the rotor angle. Thus
the rotor angle, θ, is the arc tangent of the sine signal divided The topology of windings used in resolvers has a
by the cosine signal: θ = arctan(sin(θ) / cos(θ)) = sinusoidal character that means a non homogenous
arctan(Vs/Vc) distribution of wiring in different slots – the distribution is
The ratiometric tracking converter performs an implicit according with a sinusoidal rule to obtain as final effect an
arc tangent calculation on the ratio of the resolver signals by output signal very closed with a sine form. However, using

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only a sinusoidal type of winding do not solve completely


K
Nj=W/2∙sin(jπ/2K)/[ sin( jπ/2K)], j=1,2…K
the problem because there are other many factories that i 1
influence the accuracy level of resolver, as; quality of The diagram of this field is shown in fig. 6b.
magnetic material, using slot solution, mechanical building
asymmetries, the influence of the temperature on the 2.3. Some consideration regarding
material properties and winding characteristics etc. Some vectorial measurement methods
from these factories are controllable, but some of them are
random. It is very important to take into consideration the Testing resolvers at very small angular increments or at
controllable factories even from design stage, to reduce at better than 1 arcsecond (.00028 degrees) accuracy requires a
minimum their influence. high precision instrument. A high precision ratio transformer
In a bipolar resolver (absolute character), a frequent can provide the accuracy and resolution needed for testing
solution used to obtain a good accuracy is a lamination resolvers at small angular increments. To check the angular
having many slots, to be possible to do better sinusoidal accuracy of a resolver the AC reference, resolver, ratio
distribution. transformer and a phase angle voltmeter (PAV) are
If we discuss about multipolar resolvers, the number of connected as shown in Fig.7.
slots per pol, from phisical point of view, is limited, Since S4 is the cosine output of the resolver, the output of
frequently between 1 and two. In this situation, a special the ratio transformer should equal the sine output:
winding schema is used, but the final accuracy is a basis [ tan(θ) = sin(θ) /cos (θ), or sin(θ) = tan(θ) cos (θ) ]
accuracy (two poles) divided at number of pole pairs (p). S1 is the sine output of the resolver; the output of the ratio
Below it is shown an example of sinusoidal winding, in a transformer should be equal with S1 output of the resolver.
concentric configuration, used for bipolar resolver (when it If the two outputs are equal, the PAV will indicate a null
is possible to have more slots per pole). Let us to consider a condition. If the PAV does not indicate a null condition, the
winding having 4k slots, as it is shown in fig. 5. The setting of the ratio transformer is adjusted until a null
concentric windings have different dimensions (paths), from condition is indicated. The arctangent of the ratio
1÷2 to 1÷k+1. The windings from the slots j, (j, 2k-j) and transformer setting is the angle that the resolver output is
(2k-j, 2k+j), have the same numbers of turns Nj /2, and are indicating. On the other hand, for different positions of
equally distanced from the two poles. resolver rotor relative to resolver stator, the measurement
If we consider to have W turns per pole, so: system measures and computes:
 [tan(φ)]sin= (Usin)f / (Usin)q si (U)sin =sqrt( (Usin)f2+/ (Usin)q2)),
K
J 1
Nj  W / 2 , respectively
Also, let us to consider that at a moment of time - to – [tan(φ)]cos= (Ucos)f /(Ucos)q si (U)cos =sqrt( (Ucos)f2+/ (Ucos))q2,
the electric current trough winding is I√2sinωto . where:
Usin)f = the part of sine output having the same
phase with input
Usin)q = the part of sine output having 900 phase
shift with input
Ucos)f = the part of cosine output having the same
phase with input
Ucos)q = the part of cosine output having 900
phase shift with input
For example, if a resolver shaft were set to angle of 20°,
the ratio transformer would be set to the tangent of 20°
which is 0.3639702. The null meter does not indicate a null
and the ratio transformer are adjusted until it does. The final
setting of the ratio transformer is 0.3639200; the arctangent
a.
of that value is 19.9975°.
The resolver error is therefore 0.0025°, that means -
9arcseconds.

b.
Fig. 6 Relative to sinusoidal winding, in bipolar concentric configuration,
for construction with 4k slots
Fig. 7 Schematic on the stand to do vectorial measurement of resolvers
Using the fundamental relations from
electromagnetism and superposition method, we can find 2.4. Aspects on resolver accuracy
the solution for winding number in the slot marked with j:
The accuracy of the resolver has to be analysed in

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

connectied with the configuration of resolver and transducers because of its ruggedness and ability to provide
application. a very high degree of angular accuracy under severe
If a single phase resolver is used, we can consider only the conditions.
error relative to the fidelity of the signal according with ideal There are not optical parts to keep clear of smoke or oil that
sinus form. Let us consider that the induced voltage, when often disrupt the operation of optical encoders. Because the
the load of resolver is null, can be expressed: Ebo = VR TR resolver has two outputs that are subjected to tangent
sin(θ). On the other hand, the induced voltage in load function, the input signal anomalies have a low influence.
conditions can be expressed: Eb = VR TR sin(θ) – j X I The resolver saves size and weight, being substantially
cos2(θ). The last relation can be expressed and as: Eb = Ebomax smaller than other transducers approaches and easily
sin(θ) / (1+b cos2(θ)). On this way, we can define a relative integrated into any system.
error as:
Δ Eb = (Ebo - Ebr) / Ebomax = (b cos2(θ) sin(θ) / ((1+b cos2(θ)).
In the most part of applications, are used both windings, so we have to
consider the differences between the amplitude of the two signals, as well
as the error of quadrature.
The main factories that are influencing the accuracy
are: the status of general machining (technologies,
mechanical accuracy, heat treatment etc.), than the quality of
the materials; the total impedance of the measurement Fig.8 Resolvers produced at S.C. Sistem Euroteh
system; excursion of amplitude of input voltage, as well as
REFERENCES
the value of the input frequency; excursion of the
[1] MAGUREANU, R. Masini electrice speciale pentru
temperature during operation; rotation speed of the resolver
sisteme automate - Editura Tehnica, Bucuresti, 1981
etc.
[2] JULA , N . Senzori şi traductoare Editura Academiei
III. RESULTS AND CONCLUSIONS Tehnice Militare, Bucureşti, 1999
[3] SYDNEY, A. D., LEDGERWOOD, B.
Most part from authors are working from long time as K.Electromechanical components for
researchers, designers and producers of special electric servomechanismsMcGraw-Hill, Book Company, Inc.,
machines. In these conditions, the resolver was one of main 1961
components to develop, to design and to produce. Different [4] VERNITRON Motion Control Division Pancake
configurations, different sizes and different parameters are Resolvers
subjected with the author‘s activity. Bipolar resolvers 05, 08, [5] MAFTEI, G., URSU, T. Optimizarea distribuţiei
11, 15 or bigger sizes were developed for different înfăşurărilor sinusoidale EEA – Electrotehnica-
applications, in many fields. Electronica- Automatica 1978
20 seconds of arc or 1 minute of arc accuracy were [6] admotec Advanced Motion Technology Understanding
obtained on resolvers 19 or 29 sizes, having 32 poles. The Resolvers and Resolver-to-Digital Conversion - USA
methods of design used the most modern concepts, including 2000
numerical analysis of electromagnetic field. The methods of [7] TEGAM Testing Resolvers Using a Precision Ratio
testing are based on vectorial measurement systems. Transformer USA 2000
As conclusion, we can remark that the resolver component [8] What Is A Resolver? USA 2001
is superior to many other kind of absolute or relative position [9] Product Catalog S.C. Sistem
Eurotehwww.sistemeuroteh.ro

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Electrostatic Ion Shutter with Ejecting Electrode

as a Part of a Ion Mobility Spectrometer
Anatoly V. GOLOVIN
National Research Nuclear University MEPhI, Moscow, Russia
[email protected]

Abstract – In portable hand-held devices for trace explosive and narcotic detection the most perspective is use
of a principle of ion mobility spectrometry [[1],[2]] owing to the best combination of cost, compactness,
parameters of detection and a wide range of found out substances. Classical designs of a ion mobility
spectrometer are represented by a set of the metal electrodes forming area with homogeneous longitudinal
electric field, in a combination to an electric shutter and area of ionization to a source of ionization on the
basis of a radioactive isotope. The extremely perspective problem is development of a compact not radioactive
source of the ionization, allowing to generate ions both positive, and negative polarity and having low power
consumption. The use pulse corona discharge as a source of ionization for a ion mobility spectrometer is
represented to the most perspective. Application in a design of a pulse corona discharge ionization source
allows, unlike systems with isotope 63Ni ionization, to do without application of an electrostatic ion shutter
which separates ionization and drift chambers. However application of an ion shutter allows to achieve the
best parameters of resolution and sensitivity. In the given work the scheme of operation and results of
application of an electrostatic ion shutter as a part of a ion mobility spectrometer with a pulse corona
discharge ionization source will be considered.

sources of ionization most often applied in serial devices,

and thus to provide good parameters on detection of
I. INTRODUCTION
substances.
One of basic elements of a design of a ion mobility II. ION MOBILITY SPECTROMETER WITH
spectrometer is the spectrometry cell consisting of two ELECTROSTATIC ION SHUTTER
adjacent areas of ionization and drift, separated by an
electrostatic ion shutter [[3]]. In a described ion mobility Figure 1 represents the electrostatic ion shutter of
spectrometer the pulse (10 Hz) corona discharge ionization Tundal type [[4]], consisting of two transparent grids from
source has been applied. Application corona discharge thin stainless steel, located on distance about 1 mm from
allows to solve problems, characteristic for the radioactive each other, added with a ejecting electrode.

Figure 1. Eelectrostatic ion shutter with ejecting electrode.

Electric potentials on a ejecting electrode and on that provides regulation of duration of a cumulate of ions in
ion gate grid 1 change on commands of operating electronics the ionization chamber and in ion gate chamber. The formed

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

ions get from ionization chamber to ion gate chamber with a expense of fuller transfer of a charge from reactant-ions
certain delay. It leads to possibility to regulate duration of to molecules of investigated substance.
ion-molecular interaction in the ionization chamber. Work of  Phase 4 – moving bunch of ions to ion gate chamber.
electrostatic ion shutter with ejecting electrode during one  Phase 5 – under the influence of field Е1 in the field
cycle of measurement is divided into 7 consecutive phases of ionization and Е2 in the field of ion gate ions are
(Figure 2): injected in drift area. Thus by means of an
 Phase 1 – switch on of field Е1 in the ionization chamber electrostatic shutter begins possible to inject a thin
that corresponds to preparation for the beginning of a bunch of ions that essentially increases the resolution
cycle of measurement. The end of this phase corresponds of a ion mobility spectrometer.
to the beginning of the corona discharge impulse.  Phase 6 – the direction of field Е2 changes on
 Phase 2 – under the influence of field Е1 there is a opposite, thus the electrostatic ion gate is closed.
movement of ions, formed by corona discharge, from a Remained in the ionization chamber ions under the
ejecting electrode to ion gate grid 1. influence of field Е1 move to ion gate grid 1 and will
 Phase 3 – the field in the ionization chamber Е1 becomes be neutralized on it.
equal to zero, ions stop. In the stopped bunch there are  Phase 7 – the initial condition of electric potentials
ion-molecular reactions between molecules of on ejecting electrode and ion gate grid 1 is restored.
investigated substance and formed by corona discharge The system is prepared for a following cycle of
reactant-ions. Sensitivity of a spectrometer can be raised measurement.
by means of increase in duration of this phase at the

Figure 2. Distribution of fields in the ionization chamber Е1 and ion gate chamber Е2 during functioning of electrostatic shutters

In case of negative ions an increase in duration of the Also research of influence of time of injection of ions
Phase 2 leads to a reduction of a total charge of ions. Thus from ionization chamber in drift chamber (the Phase 5) has
the spectrum structure remains invariable. The total charge been conducted (Figure 4). During the given experiment the
on a collector for negative ions is maximum at the minimum dynamic range of change of duration of injection of ions and
duration of the Phase 2. In case of positive ions at increase in influence of the given parameter on spectrograms in cases of
duration of the Phase 2 leads to a reduction of amplitude of positive and negative ions was investigated.
peaks of fast ions and increase in amplitude of peaks of slow At work with negative ions the smooth increase in
ions. Thus, by means of an increase in duration of the Phase amplitude of peaks and the general charge of system is
2 it is possible to cut fast positive ions and to focus attention characteristic at increase in duration of injection of ions from
on slow ions that can be useful at detecting of ions of ion gate chamber in drift chamber. Thus, the choice of
substances with low mobility. For positive ions the increase duration of injection of ions in area of drift doesn't get
in size of the general charge is characteristic at increase in essential influence on possibility of detecting of separate
duration of the Phase 2 from 0 to 0,3 ms that is shown on categories of the substances forming at ionization slow or
Figure 3. Mobility of positive ions essentially below fast ions, and is in a greater degree defined by resolution
mobility negative, therefore doesn't occur falling of a charge requirements. For this case value of saturation for fast ions
because of neutralization of ions on the ion gate grid 1 at of the Phase 5 equals 1,50 ms. At the further increase in the
duration of the Phase 2 less than 0,3 ms. The increase in the given parameter the increase in amplitude of peaks of fast
common charge at this interval arises because of increase in ions doesn't occur, however the amplitude of peaks of slow
cumulative time of injection of ions in drift chamber. ions considerably increases.

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Figure 3. Dependence of a total charge on a ion collector at positive polarity depending on duration of the Phase 2 electrostatic ion shutter.

Figure 4. Comparative spectrograms of positive ions of laboratory air at change of the Phase 5 electrostatic ion shutter.

Thus, at detecting of some substances in positive polarity ACKNOWLEDGMENTS

with the characteristic slow ions formed during ionization, The author wish to thank Dr. V.S. Pershenkov and Ph.D
the increase in duration of injection of ions from ion gate V.V. Belyakov for numerous discussions and collective of
chamber in drift chamber (Phase 5) is necessary. scientific group of micro- and a nanoelectronics department
for the help in design, assembling and carrying out of
III. CONCLUSION
scientific researches.
During work performance the scheme of an electrostatic
ion shutter as a part of a ion mobility spectrometer with
REFERENCES
pulse corona discharge ionization source has been
developed. In classical structure of an electrostatic ion
[1] Borsdorf H., Eiceman G.A., Ion Mobility Spectrometry:
shutter of Tundal type the ejecting electrode which is
Principles and Applications // Taylor & Francis. – 2006.
structurally a part of corona discharge ionization source has
[2] Belyakov V.V., Ion mobility spectrometer // Utility
been added. Thus, possibility of regulation of duration of a
patent № 035034. – Russian Federation, 2006.
finding of ions in ionization chamber has been entered
[3] Karpas Z., Eiceman G.A., Ewing R.G., Algom A.,
during course of ionic-exchange reactions and time of
Avida R., Friedman M., Matmor A., Shahal O., Ion
passage of ions directly through an ionic shutter with
distribution profiles in the drift region of an ion mobility
possibility of allocation of a narrow clot of the ions getting
spectrometer // Int. J. Mass Spectrom. Ion Proc. – 1993.
in drift chamber. At an estimation of influence of the given
– Volume 127. - P.95–104.
structure of an electrostatic ionic shutter on detecting of ions
[4] Tyndall A.M., The Mobility of Powsitive Ions in Gases
it is shown that at detecting of positive ions it is required to
// Cambridge University Press. – 1938. – Cambridge. -
establish more time of injection of ions from ion shutter area
U.K.
in drift area, than at detecting of negative ions.

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The Simulation of Pulsed Heater for a Sampling

System for the Ion Mobility Spectrometer
Evgeniy MALKIN
National Research Nuclear University MEPhI, Moscow, Russia
[email protected]
Abstract – The development of the sampling device with pulsed heating of the intermediate carrier for ion
mobility spectrometer is described in this article. Numerical simulation of a pulse heater structure of is
presented. The design of the sampling device using a pulsed heating of the intermediate carrier is developed.
Experimental results of approval of the sampling device are presented.

mobility spectrometers, such as the Vapor Tracer, Ionscan,

I. INTRODUCTION
Sabre, Quantum Sniffer, as well as a spectrometer,
Safety in public transport, places of a mass density of
developed at the Department of Micro-and Nanoelectronics
people, at the site of potential danger or high priority
MEPhI [1], have a heating unit of the intermediate carrier,
remains extremely important. For these purposes points of
which is constantly at high temperature. This leads to
the control established at the airports, railway stations, port
significant power consumption and time required to get the
and customs terminals, should be equipped by the high-
device to normal operating conditions.
sensitivity equipment, that is sensitive to ultra low
The obvious solution to reduce energy consumption is the
concentrations of explosives. The ion mobility spectrometry
use of pulsed heating of the intermediate carrier. In this case,
has been most demanded and widespread technology in
the intermediate carrier is placed in a heating device at low
these areas for the detection of trace of explosives over the
temperature, which prevents evaporation of samples during
past few years. Among the main advantages of devices based
the positioning and the dependence of the results of further
on this principle, it is possible to note simplicity of a design,
analysis of operator actions. In our case the analysis is
compactness, low cost and possibility of operation in the
started with moment of heating beginning. However, this
field in real time.
approach is accompanied by a number of technological and
Ion mobility spectrometers can detect the substance by
structural problems associated with the requirements on the
sampling air from the environment and the research of
dynamics of heating and cooling, as well as issues of
composition of particles at different solid surfaces
cleaning the device after a sample analysis. A similar
(documents, clothes, tickets, case handles, etc.). The most
approach is used in the design, use of pulsed heating of the
effective is the selection of trace of particles from the surface
gas-discharge lamp [2-3].
of objects with intermediate carrier, followed by heating and
The purpose of this work is to simulate the pulsed
evaporation of the sample. The need for heating the
heating of the intermediate carrier sampling device for ion
intermediate carrier with the sample determined by a small
mobility spectrometer.
amount of substance in the sample and low vapor pressure
for a number of explosives. All existing portable ion

Figure 1. The structure of the segment and the equivalent circuit of the pulsed heater.
pulsed heater with dimensions of 25x25 mm for the heating
II. H EAT TRANSFER MODELING
section of the intermediate carrier at 200° C for 10 seconds,
The major task of development was the creation of a

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

and then cools it to the initial temperature for the same grid to support intermediate carrier.
period of time. Typical segment of the strip heater is shown in Figure 1.
The heater consists of 12 same elements spaced 1 mm Its dimensions are 2x1 mm. The figure also shows elements
apart. The heater element represent a strip of stainless steel of the thermal equivalent circuit model parts of the segment.
in the thickness of 0,125 mm with the sizes 25x1 mm. For To calculate the dynamics of heating and cooling were
support, positioning and removal of heat, each element has a performed numerical simulations of the structure using the
number of legs that are soldered to the printed circuit board. circuit simulation package SPICE. The model take account
For heating the intermediate carrier with the sample is used of the thermal resistance and heat capacity the section of
the heat transfer from the heater operating in pulsed mode, pulsed heater and air gap, supporting grid and section the
through an air gap. On top of 1 mm from the heater install heated intermediate carrier with the particles of the sample

Figure 2. Dependence of temperature of a heater (1) and the intermediate carrier (2) from time.

Figure 3. Changes of temperature of heaters in time.

Numerical calculation of the intermediate carrier heating ten-second interval it is possible to realize about 4 steps of
dynamics for step change of temperature has been carried heating of system. To improve the dynamics of heat
out. To accelerate the transition to the next level of the necessary to reduce the air gap between the heater and the
temperature of the intermediate carrier force increase in intermediate carrier to reduce its thermal resistance, and to
power pulsed heater and then get to the steady-state level is ensure removal of the heat from the heater surface to the
used. Model dependence of heating temperature on the time environment. Rapid cooling of the heater pulse is provided
shown in Figure 2. From these results it is visible that for a at a low temperature of the substrate through the attachment

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

and support leg time of measurement. Further work will be directed to study
the dynamics of evaporation of the sample in the analysis of
III. EXPERIMENTAL RESULTS trace amounts of explosives.
Figure 3 shows the experimental dependences of the
resistance heater at pulse heating. Curve shows the single- REFERENCES
stage heating and cooling the heater pulse. [1] V. Belyakov, A. Golovin, D. Kushneruk, V.
IV. CONCLUSION Pershenkov, M. Tihanov. Portable device for detection
The device sampling with pulsed heating of the of trace amounts of explosives, Chip News, № 4, p. 40-
intermediate carrier is developed. 41, 2007.
The numerical simulation of a heater has allowed [2] V. Belyakov, A. Golovin, V. Vasiliev, D. Kushneruk, V.
optimizing the dynamic characteristics of the device for Pershenkov, M. Tihanov. A device for detecting trace
power consumption and the dynamics of heating and cooling amounts of explosive materials on the fingers of human
is carry out. and documents // Sensors and Systems 2009. № 7. P.44-
Tests of the device showed the possibility of rapid heating 49.
and cooling of the intermediate carrier for the typical cycle [3] Flash Vapor Sampling for a Trace Chemical Detector
Patent No. US 7.098.672 B2, Date of Patent: Aug.29,
2006.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Periodic Signals From a Nanopore Coulter

Counter
Y. RUDZEVICH1,Y. LIN1, G. EVANS1, A. ORDONEZ1, O. LUPAN1,2 and L. CHOW1
1
University of Central Florida, PO Box 162385 Orlando, FL 32816-2385, U.S.A.
2
Technical University of Moldova, Republic of Moldova
[email protected]

Abstract – In this work, we report the observation of periodic signals from a Coulter counter that employed glass
pipettes. These periodic signals occurred even when no nanoparticles were presented in the counter. Observed
phenomenon may be related to the translocation events through glass pipette. Further studies are needed to better
understand these results.

Index Terms – Coulter counter, nanopipette, nanopore, translocation.

200B amplifier in voltage clamp mode with a low-pass

I. INTRODUCTION Bessel filter at 2 or 5 kHz bandwidth. The signal was
Traditionally, determination of the size and concentration digitized by Axon Instruments Digidata 1440A Series with
of nanoparticles has been performed through sampling rate 250 kHz, and recorded with AxoScope 10.2
chromatography, gel electrophoresis, or dynamic light (Axon Instruments).
scattering. However the Coulter Counter technique [1] also
provides a promising and reliable method for particle
counting and sensing in a simpler manner. This method can
be briefly described as two chambers, filled with particle-
laden solution, separated by a membrane with a single tiny
pore. The ionic current through the pore, created by electric
potential applied between the chambers, depends on the
diameter of the pore, and changes when pore is partially
blocked. In most cases the blocking of the pore is caused by
translocation of small particles. By monitoring these signals
we can count the number of particles translocated through
the pore from one chamber to another, and the particle size
can be determined, if the pore size is known. This technique
is a useful tool for nanotechnology and biomedical
applications.
Here we report the observation of periodic signals from
Fig. 1 SEM Image of the nanopipette tip (coated with Pt for SEM)
certain experiments when nanoparticles were not presented
in the chamber. These results are very surprising and
counter-intuitive. Here we present main results of our
findings and some discussions.
II. EXPERIMENTAL
Nanopipets were fabricated from borosilicate capillaries
with inner diameter 0.8 mm and outer diameter 1.5 mm.
These capillaries are pulled using a glass pipettes puller
(P2000, Sutter, Novato, CA), to achieve an orifice size of a
few hundred nanometers. Multiple parameters can be used to
control the size of the capillary tip, such as filament current,
heating duration, and pulling force.
SEM image of the capillary tips are taken to determine the
size (Figures 1 and 2). The nanopipette was filled with 0.1
mol/L potassium chloride (KCl) solution (Fisher Scientific)
with pH = 5.5 and submerged in the bath with the same
solution. A Ag/AgCl 0.2 mm thick electrode was embedded
into the capillary until it reaches the conical part. The Fig. 2. SEM image of the tips, demonstrating a cone-shaped tip
reference Ag/AgCl electrode was immersed directly into the
bath, as shown in Figure 3. Average distance between III. RESULTS AND DISCUSSIONS
electrodes was 5-7 mm. For testing purpose, we check I-V The experimental set up is commonly used in Coulter
dependence, and as expected, the I-V curve behaves counting of nanoparticles. At usual cases, we observed the
ohmically. For ionic current recording we used the Axopatch

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typical baseline current and translocation signals, as shown current is observed when applying negative voltage.
in Figure 4 below. However, we encountered some interesting phenomena
when using a syringe to inject the KCl solution into the
micropipette. We test it simply applying positive and
negative voltage. Without any introduction of nanoparticles,
instead of a typical baseline of current that represents the
ionic conduction through micropipette, we observed a clear
periodic signal shown in Figure 5. This result exhibits a base
line current of about 2.51 ± 0.03 nA, which represents the
ionic current passing through the micropipette when there is
no nanoparticles in the solution. The amount of this current
can be estimated by the following equation [2]:

I 0  n(t )  e  A( x, t )  v( x)ion (1)

where n(t)=n++n- is a sum of positive and negative ion

Fig. 3. The schematic set up of our translocation experiment. densities, e is elementary charge, A(x,t) is the cross section,
a) v(x) is average ion velocity which is derived from v(x)
=E, where  is mobility of K+ and Cl- and E is electric field
at the orifice.
The multiple dips shown in Figure 5 stand for the sudden
drop of current every time the ionic path in capillary is
blocked. This change of current is related to the variation of
resistance. Figure 6 shows the event current as a function of
time using a different micropipette and with an applied
voltage of 500mV.
We have conducted further investigation to study this
interesting signal which appears in our measurements at
room-temperature. We repeated our experiments several
times without introducing any nanoparticles; the periodic
signals persisted. The periodic signals, which stand for the
event current, are uniformly distributed, compare to the
randomly pikes in normal nanoparticle translocation picture
(Figure 4).

b)

Fig. 4. Particles translocation experiment with pipette of 800 nm pore size, Fig. 5. Event current as a function of time with an applied voltage of
a) shows clear blockade signals with positive +0.4V potential applied, and 300mV.
b) no translocations observed after switching voltage to negative sign.

These signals related to the translocation of nanoparticles, As we increase the applied voltage, we notice the
which are blocking the ionic conduction during frequency of the periodic signals also increases. We found a
translocation. As we can see from above, the nanoparticle linear dependence of this frequency on the applied voltage
translocation signal, distributed randomly, are obtained only which is not shown here. Interestingly, unlike the
when positive voltage is applied. While only a baseline translocation signals in Figure 4, these periodic signals

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reverse their polarity when voltage polarity is switched. The

data in Figures 7 and 8 show that when the applied voltage
changes to negative voltage the event currents also reverses
it direction as expected. However both the frequency of the
periodic signals and the magnitude of the event current
remain unchanged.

Fig. 8. Signals recorded after switching polarity

IV. CONCLUSION
It has been observed that periodic signals from a Coulter
counter that employed micropipette. These signals appeared
Fig. 6. Event current as a function of time with an applied voltage of when a syringe is used to inject KCl solution into the
500mV. micropipette. The frequency of the periodic signals is linear
proportional to the applied voltage. These periodic current
signals are reversible under polarity change of the applied
The interesting results we observed are hard to explain,
voltage.
since no particles are involved. Extra care and multiple
repeated experiments should minimize any possible ACKNOWLEDGMENTS
contamination of nanoparticles in the solution or pipette. In L. Chow would like to thank National Science Foundation
addition, the major challenging fact is the perfect regularity (NSF-ECCS-0901361) for financial support.
of these periodic signals, which are linearly proportional to
the applied voltage. At this moment, we do not have any
plausible explanations for our observations. We point that REFERENCES
nanobubble in aqueous solution may relate to our [1] Coulter, W.H., 1953. U.S. Patent No. 2,656,508.
observations [3-6]. [2] Stober, G., Steinbock, L.J., and Keyser, U.F. Journal of
Applied Physics 105, 084702, 2009.
[3] M. A. Hampton and A. V. Nguyen, Nanobubbles and
the nanobubble bridging capillary force, Adv. Coll.
Interface Sci. 333 800-806, 2009.
[4] Saleh, O.A., and Sohn, L.L. Review of Scientific
Instruments 72(12), 4449 - 4451, 2001.
[5] R. A. Pushkarova, R. G. Horn, Surface forces measured
between an air bubble and a solid surface in water,
Colloids Surf., A 261 147-152, 2005.
[6] N. Mishchuk, J. Ralston and D. Fornasiero, Influence of
dissolved gas on van der Waals forces between bubbles
and particles, J. Phys. Chem. A 106 689-696, 2006.

Fig. 7. Signals recorded before switching polarity

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APPENDIX A
APPENDIX C

Fig. A. Data recorded in experiment with 200 nm pore size, with different
voltages, 100-400 mV.

APPENDIX B

Fig. B. A single peak of data recorded for 200 nm pore size with potential
+100 mV

Fig.C. Current histogram of data recorded in a experiment with different

voltages. Time of recording is 10 seconds for each voltage. The highest
peak indicates a baseline current, when a plateau on the side illustrates the
event current. It is also clear from this histogram that frequency of event
current is increasing with voltage.

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About the Using of Polarization Methods in

Investigating the Polarization Sensitive
Nanosystems
C.Yu. ZENKOVA, I.V. SOLTYS
Chernivtsy National University, Chernivtsy, Ukraine
[email protected]
Abstract –The paper shows the possibilities of defining the degree of correlation of mutually orthogonal
superposing circularly-polarized and linearly-polarized plane waves. The proposed results widen possibilities of
metrological use the methods of spatial polarization modulation for investigating the properties of polarization
sensitive systems and nanoobjects.

Index Terms – spatial modulation of polarization, visibility, degree of coherence.

• multiple light scattering of coherent radiation in

I. INTRODUCTION
turbid media, as well as transmission of optical
radiation through optical waveguides;
One of the manifestations of the coherence of superposing
• heterodyning (nonlinear mixing) of optical waves
fields, one of the diagnostic indicators of coherence is the
of different states of polarization, as well as at near zone of
spatial periodical polarization modulation of the resulting
a field scattered by random phase objects.
spatial distribution. The depth, the level of such a
At the same time the information contained in the
modulation is connected with the degree of coherence,
polarization distribution of interacting circular waves of a
correlation of superposing fields. The interconnection of the
similar polarization, essentially enriches the ideas on the
degree (or level) of the polarization modulation of the
properties of optical fields. The paper offers for investigation
resulting field and the characteristics of coherence in the
the results of computer simulation, which allow to define
approximation of plane waves is rather thoroughly studied
both coherent peculiarities of vector optical fields and the
within the framework of the stokes-polarimetric approach [1,
ways of forming periodically modulated polarization
2].
distribution in the registration plane.
The manifestation of the superposing wave coherence in
the case when it is necessary to take into consideration the
longitudinal z-component of the field, and the modulation II. THE BASE OF THEORETICAL APPROACH AND
polarization of the resulting field realized in the plane of COMPUTER SIMULATION
incidence is studied in a number of papers offered by the
authors [3]. The possibility of measuring the field coherence The time-averaged intensity distribution [4,5] of a random
function through estimating the degree (level) of field electromagnetic field formed at instant t by the sources
   
polarization modulation is shown and justified in the Q1 , Q2 , Q3 and observed at point r at the observation
framework of such an approach [4, 5]. Thus, these papers
plane can be put down as,

suggest a method for defining the degree of coherence of    
linearly-polarized fields, where the polarization distribution I (r )   ii(1) (r )   ii(2) (r )   ii(3) (r ) 
takes place in one of the planes – the plane of observation. ij
The offered paper widens the proposed method and    
demonstrates the possibility of using it for circularly- 2 tr[W (Q1 , Q,0)]tr[W (Q2 , Q2 ,0)] ij(1,2) cos[1 ] 
polarized fields at the formation of two polarized    
 2 tr[W (Q1 , Q1 ,0)]tr[W (Q3 , Q3 ,0)]ij(1,3) cos[ 2 ] 
distributions in two mutually orthogonal planes. Thus this
   
 2 tr[W (Q2 , Q2 ,0)]tr[W (Q3 , Q3 ,0)]ij( 2,3) cos[ 3 ]
paper proposes to widen the possibilities of metrological use
 , i, j = x,
of the method of spatial polarization modulation of the field 
for estimating the coherence of superposing waves by y, z. (1)
considering the case of superposition not only of linearly ( m)  ( m)  *(m) 
polarized in the incidence plane waves, but, in the general Here ii (r )  Ei (r , t ) Ei (r , t )  i, j = x, y, z, (m
case, of circularly polarized interacting waves as well. =1, 2, 3) describes the time-averaged intensities of
Practical importance of this problem increases owing to the corresponding sources, the angle brackets denote the time
development of the techniques of confocal microscopy of averaging and the superscript * stands for complex
isolated molecules, including long molecules oriented along conjugation. The coherence properties of vector optical
the direction of beam propagation and systems of 3D fields are described using the mutual coherency matrix
 
imaging of such molecules, when accounting z-component W (Qm , Qn , t ) [6] characterizing correlation of the fields at
of a field is absolutely necessary. Generally, such situations  
occur in solving of many problems: two different spatio-temporal points Qm and Qn , being
   
• transmission of radiation through optically determined as W (Qm , Qn , t )  Ei (Qm , t ) E *j (Qn , t )  .
anisotropic crystals;

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Within the framework of such approach itself in the spatial intensity modulation. We employ a
 
Wij (Qm , Qn , t ) holographic recording system in an immersion liquid (Fig.
 ij( m,n)      , (m, n = 1, 2, 3, 1). Such a system fulfills the strict angular requirements for
tr[W (Qm , Qn ,0)]tr[W (Qn , Qn ,0)] the waves in the recording region. We set the reference wave
i, j = x, y, z) and determines the degree of correlation of the intensity equal to the net intensity of the plane waves in the
field components. 1  k ( R1  R2 ) ,  2  k ( R1  R3 ) , recording region, thus ensuring a larger percentage
modulation and therefore a higher recording efficiency of the
 3  k ( R2  R3 ) are the phase differences
of the interference fringes that visualize the polarization
 
corresponding fields at the registration plane, R1  r  Q1 , modulation of the field. The same scheme was used for the
readout of a hologram. The prism positioned in an
    
R2  r  Q2 , R3  r  Q3 are distances of point r from immersion liquid was used for coupling out radiation
diffracted by the holographic grating.
the sources centers.
Changing a phase of the reference wave within the
interval 0..2 results in periodical changing of visibility of
the registered interference pattern following the harmonic
law [4,5].
The visibility modulation depth (VMD) is determined as

M  max[V ]  min[V ]
   

tr[W (Qm , Qm ,0]tr[W (Q3 , Q3 ,0)] ( m,3)
4   ij
m ij  ij( m) (r )   ij(3) (r )
m = 1, 2; i, j = x,y z. (2)

Choosing a reference wave to be completely correlated

with one of the initial waves, to say  (1,3)  1 , one can see
that the VMD of an interference pattern, M, characterizes, up
to the constant depending on the intensity values, the degree
of mutual coherence of the reference wave and the second of
the initial waves, i.e. M   ( 2,3) . Accounting  (1,3)  1 ,

one concludes that  ( 2,3)   (1,2) . Thus, by proper choice

of intensities of the interfering waves  (1, 2) will be Fig.1. Optical arrangement for holographic experiment: Bs1 and Bs2, beam
splitters; M1, M2, and M3, mirrors; P1, P2, and P3, polarizers; PR, prism;
determined by the VMD of an interference
IL, immersion liquid; H, hologram.
pattern: M   (1, 2) .
It can be ascertained that the maximal intensity of the
Superposition of plane waves of equal intensities linearly reconstructed signal corresponds to the case in which the
polarized at the incidence plane whose degree of mutual electrical vector of the reference wave lies in the incidence
coherence equals zero at the same registration scheme results plane, and the minimal intensity corresponds to the case in
in homogeneous intensity distribution at the registration which the polarization of the reference wave is orthogonal to
plane. The use of the plane reference wave coherent with the incidence plane. Changing the polarization azimuth of
one of the initial waves enables to visualize the intensity the reference wave leads to a decrease in contrast of the
distribution with the certain visibility. In the case of two interference pattern.
uncoherent waves, the VMD is equal to zero. It means that The experimental results are shown in the form of
the VMD is in quite correspondence with the degree of interferograms obtained in various polarization situations. It
mutual coherence of the initial superimposing waves. The is seen from the photos shown in Fig. 2(a) that the
experiments [4,5] carried out for the cases when interference of two plane object waves which are linearly
0   (1,2)  1 completely proved the conclusion that the polarized in the plane of the figure results in the interference
pattern with the period corresponding to the angle of
VMD of a pattern corresponds to the magnitude  (1, 2) of convergence of the two beams, and the visibility is
the superimposing waves. determined by the ratio of the x − and z − components of the
It is possible to perform a correct experiment if some decomposition. The use of the third linearly polarized beam
factors are taken into account. To avoid distortions with the direction of oscillation of the electrical vector
introduced by the optical system, we must take into account perpendicular to the figure plane does not result in any
the fact that the propagation of radiation through a changes in the structure (period) of an interference pattern.
microscope is accompanied by the change of a cone angle of Only the visibility of the pattern is changed due to changing
the beams, so that this angle differs from the right one. This the level of background, see Fig. 2(b). If the state of
leads to the violation of the strict orthogonality of the polarization of the reference beam is linear and the electrical
electrical vectors of the interfering beams and manifests vector lies in the figure plane, then the structure (period) of

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

the registered interference pattern is changed, as a rule, it is homogeneous distribution of intensity

doubled, Fig. 2(c). The doubling of the period of the
interference pattern is the most pronounced in the situation
in which the intensity of the reference beam exceeds the
intensity of the object beams. Such doubling of a period is of
pure polarization nature and has been quite comprehensively
described in the previous experiment and illustrated in Fig.
1. If intensity of the reference beam is spatially nonuniform,
one can observe the mechanism of the period doubling of the
interference distribution – see the picked out fragment in
Fig. 2(d). Thus, similarly to the previous experiment, the
contribution of the polarization component to the correlation
of optical fields has been shown.
The given experiment shows the contribution of the
polarization component into the correlation of optical fields.
The parameter, which was introduced by us directs the way
to the quantitative estimation of this correlation.
The results of computer simulation for the same
arrangement and the same states of polarization of the
superposing initial and reference waves but for different
magnitudes of the degree of mutual coherence of the initial
waves show that the VMD of an interference pattern strictly
corresponds to the degree of mutual coherence of these
waves.
Similar results of defining the degree of coherence of
superposing waves are observed at interacting of two
circularly-polarized waves when the angle of their
convergence is equal to 900 [7]. In this case all three
components (x, y, z) of the interacting fields determine the
formation of the resulting distribution of intensity and
polarization.
Let us consider the result of circularly polarized waves
interference in the general case with the angle 2 between
the initial W1 and W2 waves and the third reference wave
RW, spreading perpendicular to the registration plane (Fig.3,
  
a). Here E (1) , E (2) , E (3) are the electrical vectors of the
waves W1, W2 and RW correspondingly.
The formation of the resulting intensity and polarization
distribution at interacting of two circularly-polarized waves Fig. 2 a-d
(W1, W2) of a similar handedness is determined by the
Images of two resulting interferograms:
relationship among the amplitudes and phases Оx, Оy, Оz
(a) for two object waves with the plane of polarization in the
field components. We shall deal with the special case of the figure plane;
convergence angle 2  90 0 . (b) for two object waves with the plane of polarization in the
The circularly polarized wave can be obtained by figure plane and the reference wave with the plane of
polarization perpendicular to the figure plane;
superposition of two linearly polarized waves, which differ
(c) for two object waves and the reference wave with the
in phase by 900, and spread in two mutually orthogonal plane of polarization in the figure plane;
planes xОz and yОz. The axis z is directed perpendicular to (d) the result of doubling the period of an interference
the observation plane xОy. The result of the superposition of pattern for interference of three beams with polarization
circularly polarized fields will be the intensity distribution, in the figure plane.
which is formed as a result of interference of x-components
(curve 1), y-components (curve 2), z-components (curve 3) . The superposition of the y- field components will cause
of the fields. Figure 1, b demonstrates the result of such the resulting distribution of intensity.
interaction at point O. In this case the x-distribution of We can state with assurance that the spatial distribution of
intensity diverges in localization by a quarter of period with polarization is set by the phase difference between the x and
respect to the y-distribution. z components of the interacting optical fields at different
The amplitude distribution only for the z and y points of the observation plane. (Fig. 1, c). The correlation of
components can be obtained by analyzing plane yОz. Since the interacting field components, i.e. the degree of
the two analyzed waves of a similar handedness are incident agreement the diagonal and the nondiagonal components of
upon a registered plane at the angle of 45 0, the value of the the mutual coherence matrix are additively taken into
y-projection of these waves will be maximum. The x and z consideration when estimating the resulting intensity
wave projections are determined by similar amplitude distribution. To visualize the polarization modulation the
distributions, which when combined, cause the reference wave RW is used, which spreads perpendicular to

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the registration plane. We can distinguish two distributions of polarization

modulation in two mutually perpendicular planes: in the
incidence plane and in the plane perpendicular to it, which
are connected with the change of the phase difference
a) between x and z, y and z field components at different points
of the observation area.
The choice of the reference wave as a circularly-polarized
one and at its interference with the initial waves provides
both the zero-phase difference at the formation of the
linearly polarized state and the zero value of intensity at
certain points of the registration plane.
In this case we achieve the VMD which is equal to 1. This
b)
corresponds to the degree of coherence of the initial waves.
The polarization modulation, which is determined by the
alignment of the phases of field components, becomes more
c) complex and the depth of the polarization changes, which
corresponds to the depth of the intensity modulation, exactly
corresponds to the correlation properties of the initial
Fig.3. The scheme a) demonstrates the interaction of three waves, superposing waves.
W1, W2, RW – are circularly polarized waves in the general case; b)
III. CONCLUSIONS
the field distribution at the registration plane: curve 1 is formed by
the superposition of x-components, curve 2 – by y-components,
The achieved results allow to extend the notion about the
curve 3 – by z-components; c) the modulation polarization scheme. theory of coherence (the metrological use) and is sure to be
useful in investigating polarization sensitive systems of
When projecting the amplitude vector of the electric field biological objects.
onto the axis Оx, Оy, Оz the values of the projections on the
plane xОy will be maximum and the value of the projection REFERENCES
on the axis Оz will be practically equal to 0. Thus, the results [1] T. Setala, J. Tervo, A.T. Friberg, ―Stokes parameters
of the interference of three waves change the distribution of and polarization contrasts in Young‘s interference
the resulting components of the field. The contribution of the experiment‖, Opt. Lett., vol. 31, no. 14, 2006, pp. 2208-
resulting z component to the formation of the terminal 2210.
intensity distribution decreases. The influence of the x- and [2] T. Setala, J. Tervo, A.T. Friberg, ―Contrasts of Stokes
y- components on the formation of the interference picture parameters in Young‘s interference experiment and
changes as well. By changing the amplitude and the phase of electromagnetic degree of coherence‖, Opt. Lett., vol.
the reference wave it is possible to note the zero value of 31, no.18, 2006, pp. 2669-2671.
intensity at certain points of the plane, which allows to [3] O.V. Angelsky, S.B. Yermolenko, C.Yu. Zenkova, A.O.
realize the maximum visibility. It may be concluded, that by Angelskaya, ―On polarization manifestations of
the help of the reference wave it is possible to obtain correlation (intrinsic coherence) of optical fields‖, Appl.
information on the distribution of polarization in the Opt., vol. 47, no. 29, 2008, pp. 5492-5499.
observation plane, which is set by the initial fields. The [4] O.V. Angelsky, C.Yu. Zenkova, M.P. Gorsky, N.V.
decrease of the phone takes place and the visibility of the Gorodyns‘ka, ―On the feasibility for estimating the
picture increases. The reference wave is used for diagnosing degree of coherence of waves at near field‖, Appl. Opt.,
the change of the polarization state at the expense of vol. 48, no.15, 2009, pp. 2784–278.
converting it into the distribution of intensity. [5] O.V. Angelsky, S.G. Hanson, C.Yu. Zenkova, M.P.
The change of the reference wave phase leads to the Gorsky, N.V. Gorodyns‘ka, ―On polarization metrology
spatial modulation of visibility. The influence of one of the (estimation) of the degree of coherence of optical
components (e.g., x-component) on the formation of the waves‖ Optics Express, vol. 17, no. 18, 2009, pp.
resulting intensity distribution increases. It allows to set the 15623-15634.
VMD and to estimate the degree of coherence of [6] J. Tervo, T. Setala, and A. T. Friberg, ―Degree of
corresponding fields. coherence for electromagnetic fields‖, Opt. Express 11,
By the trial-and-error method of determining the value of 2003, pp. 1137–1143.
amplitudes of the field components we obtain the maximum [7] C.Yu. Zenkova, M.P. Gorsky, and N.V. Gorodynska,
(minimum) values of the VMD at certain points of the ―Metrology of degree of coherence of circularly
observation area, which enables to estimate the degree of polarized optical waves‖, Opto-Electronics Rev. vol. 19,
coherence of the initial superposing waves, according to no. 3, 2011, pp. 14-19.

M   (1, 2) .

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Interferometric Method Application for Sub-

micrometers Thickness Measurements of Spin-
coated PEPC and PETPC Polymer Films
A.MESHALKIN1, A.ANDRIES1, E.ACHIMOVA1, L.BETS2, I.ANDRIES3, S.DRAHNEA3
1
Institute of Applied Physics of Academy of Sciences of Moldova
5 Academiei str., 2028, Chisinau, Moldova
2
Institute of Chemistry of Academy of Sciences of Moldova
5 Academiei str., 2028, Chisinau, Moldova
3
Moldova State University
60 Alexei Mateevici str., 2009, Chisinau, Moldova
[email protected]

Abstract - This paper deals with the interferometric thickness measurements of spin-coated thin polymer
films. Spin coating is currently the predominant technique employed to produce uniform thin films of
polymers in sub-micrometer range. But the thickness measurement of such thin films requires the application
of high precision methods. In the paper we design and develop the system based on the common
interferometer MII-4 and digital camera for measurement of the thin PEPC and PETPC polymer films.
Different concentration of polymer solution and spin speed were used in order to obtain thin films with
variable thickness (from 100 nm to 1000 nm) by spin coating technique.

Index Terms – thin polymer layers, spin-coating, interferometric thickness measurements.

[12]. Ellipsometry measures reflectance from a thin film at

two different polarizations. Its precision is very high in the
I. INTRODUCTION sub-micrometer range, but its measurement range is limited
Nowadays polymers play a critical role in the to several micrometers. The operations and calculations of
advancement of the microelectronics and optoelectronic ellipsometry are very complex. For the spectral
industry. They serve as photoresists in microlithography and reflectance/transmittance method, the incident light should
as insulating dielectric materials in chips, displays, cover a range of wavelengths and be adjusted normal to the
interconnects, and photonic devices [1, 2]. A large number sample surface. The spectral reflectance/transmittance
of different deposition techniques are used for the production method is simpler and less expensive than ellipsometry, but
of thin films for optical applications. The most important it can be used for films with thickness comparable with used
categories are thermal vaporization, sputtering, and chemical study wavelength. Determination of film thickness by optical
deposition. It is obvious, that suitable coating materials are interferometry technique is widely used. Measurements are
required for each deposition technique. Properties of thin nondestructive and relatively inexpensive. Interferometry
films including optical, mechanical, electrical and thermal relies on the interference of two or more beams of
properties are influenced by deposition parameters. light. The optical path difference of these beams is related
Polymeric films can be fabricated by use of various to film thickness.
techniques [3]. The self-assembly [4], the co-extrusion [5] In this paper, we report the results of the fabrication of
and the spin coating [6, 7] have ever been used for polymeric films based on polyepoxypropylcarbazole and
fabrication of the layer structures based on polymers. polyepitiopropylcarbazole and application of interferometric
However, obtaining of thin polymer films with required PC based measurement system for high precision analysis of
thickness and accurate control of the layer thickness remains film thickness.
one of the important problem in thin film researches. Spin II. EXPERIMENTAL
coating is one of the technological and accessible method of Synthesis of polymer. Polyepoxypropylcarbazole (PEPC)
obtaining polymeric thin films. M. Kimura et al. [8] first and polyepitiopropylcarbazole (PETPC) were selected since
fabricated multi-layered structures using polystyrene and they are known to have excellent film forming properties
polyvinylalcohol. Recently, A.L. Alvarez et al. [9] also and photoinduced properties. A set of PEPC and PETPC
demonstrated polymeric multi-layered structures obtained used in this investigation were synthesized by
by spin coating of polyvinylcarbazole and polyvinylalcohol. polymerization of epoxypropylcarbazole and
In both cases, accurate control of the optical thickness up to epithiopropylcarbazole at the presence of 1-3% potassium
a quarter wavelength was not achieved. So, the measurement methylate on the anionic mechanism at temperature 80-
of the thickness of transparent films become one of the 120˚C within 2-6 hours. For the full drying they were stored
important problem in optics research and in industry. The in a vacuum drying chamber at 50˚С up to constant mass.
most common thickness measurement types available From the characterization by polymer viscosity using
commercially are ellipsometry [10], the spectral calibrated standards results a molecular weight Mw 2000-
reflectance/transmittance method [11] and interferometry 3000. In Fig. 1 the chemical structure of polymers PEPC and

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PETPC are presented. cm2 of liquid dispensed on the disk at rest, subsequently
accelerated in about 10 s to 3000 rpm and spun for 20 s. The
broad range of thicknesses can be covered by using polymer
solution with increasing solids content or for a given
solution by changing the final spin speed.
The used coating cycle is presented in Fig. 2.
3000

Spinning
2500
20 secs
3000 RPM
2000

1500

1000

Rate
500
Deposition Ramp 1 Ramp 2
10 secs 10 s 10 s
0
0 10 20 30 40 50 60
Dwell
Fig. 2. Rate/time schedule of spin-coating for polymer films.

Determination of film thickness.

For the determination of film thickness in this work the
modified interferometric PC based measurement based on
Fig. 1. Сhemical structure of polymers PEPC and PETPC.
MII-4 interference microscope was applied.
Formation of polymer films from solution. A thickness characterization of the samples was achieved
The thin polymer films were prepared from homogeneous by a MII-4 interference microscope (Fig.3). with CCD-
polymer solution by spin coating procedure using camera recorded the micrographs. The interference pattern
programmable spin-coater ―SGS Spincoat G3P-8‖. The of light reflected from a flat reference surface and the
thickness of the polymer film was varied by changing the investigated sample was recorded in PC. A magnification of
concentration of polymer solution and the rotation speed of 490 times was used. The area from which a data analysis is
spin coating. In sample series A, PEPC concentration of the performed was 0.3 mm diameter circle. This enables a height
solution was kept fixed (10 wt% solutions of the PEPC resolution better than 100 nm [12].
polymer in chloroform) and spin speed was varied which
results in different film thicknesses. In sample series B, the
PEPC concentration was varied (from 2.5 to 12.5 wt%
solutions in chloroform CHCl3) at fixed spin speed. The
physical and chemical properties of used solvent chloroform
is shown in Table 1.
TABLE 1. PHYSICAL AND CHEMICAL PROPERTIES OF
CHLOROFORM.
Chemical name Trichlormethane
Chemical formula CHCl3
Chemical structure

Molecular weight 119.38

Color Colorless
Melting point -63.5 ˚C
Boiling point 62 ˚C
Density, at 20˚C 1.483 g/cm3
Refractive index, 1.4459
n D20 Fig.3. Optical scheme of MII-4 interference microscope. 1 – reference
beam, 2 – object beam, O – objectives, D – diaphragms, M – mirrors, P -
Organic solvents Miscible with principal beam-splitting plate, C – compensating plate, S – sample.
organic solvents. Miscible with
alcohol, benzene, ether, The interference fringe shift in interferogram introduced
petroleum ether, carbon by different height of layer is shown in Fig. 4.
tetrachloride,carbon disulfide, III. RESULTS AND DISCUSSION
oils. Good surface quality and uniformity of the films was
Operation conditions for polymer solution deposited on 5 confirmed by the smooth interference fringes in the
cm diameter optical glass substrate (BK7) was as follows: 2

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interferogram obtained by MII-4. Several samples were

prepared out of the same solution. To check the 1,0
reproducibility of observed structures, several samples were

Thikness, m
0,9
prepared and examined. In this experiment a very accurate
0,8
surface cleaning was achieved and it was confirmed by many
repetitions of the preparation that manifest the same 0,7

morphology. Though each individual sample shows a 0,6

different surface features the statistical features of the film 0,5
morphology remain the same.
0,4

0,3

0,2

0,1

0,0
0,0 2,5 5,0 7,5 10,0 12,5
Concentration, %
Fig. 6. Thickness as a function of PEPC solution. The thickness was
analyzed from the shift of the fringes. One fringe shift corresponds to λ/2.

IV. CONCLUSION
The fabrication of a polymeric films based on PEPC and
Fig.4. The interference fringe shift D in interferogram introduced by PETPC by spin-coating method was demonstrated. The
different height of layer. Photo of interferogram obtained by thickness of layers was analyzed by interferometric
computerized MII-4. measurements. It was shown, that the thickness of thin
The interferograms of the polymer films spin-coated from polymer films could be analyzed with high resolution by the
solutions with different polymer concentrations taken by a proposed method. The described methods allow fabricating
CCD camera are shown in Fig. 5. thin layers by controlling the concentration of polymer in
solution and/or spin coating speed and provide accurate
thickness measurement by interferometric method.
ACKNOWLEDGMENTS
The research described in this publication was supported by
the project no. 11.836.05.04A in the framework of the
National Programme ―Nanotehnologies and nanomaterials‖.
The authors thank Enaki Mihail and National Center for
Materials Study and Testing for the AFM researches.
REFERENCES
1 2 [1] Polymers for Electronic and Photonic Applications;
Wong, C. P., Ed.; Academic Press: San Diego, CA,
1993.
[2] Garrou, P. In Thin Film Technology Handbook;
Elshabini-Riad, A., Barlow, F., Eds.; McGraw-Hill:
New York, 1997; Chapter 9.
[3] M.V. Jacob, C.D. Easton, G.S. Woods, C.C. Berndt.
Fabrication of a novel organic polymer thin film. Thin
3 4 5 Solid Films, 516(12), 2008, p.3884-3887.
Fig. 5. Interference fringe shift in interferograms introduced by
different thickness of layer obtained from following concentrations of [4] Mohan Srinivasarao, David Collings, Alan Philips,
PEPC solution: 1 – 2.5 wt%; 2 – 5.0wt%; 3 – 7.5 wt%; 4 – 10.0 wt%; 5 Sanjay Patel, "Three-dimensionally ordered array of air
– 12.5 wt%. bubbles in a polymer film," Science, 292, 2001, 79.
The thickness of spin-coated films determined from the [5] Michael Ponting, Tiffani M. Burt, LaShanda T. J.
fringe pattern in the interferogram was found to be increased Korley, James Andrews, Anne Hiltner, Eric Baer.
with the increase of polymer concentration in solution. It was ―Gradient multilayer films by forced assembly
shown that by raising the polymer concentration from 2.5 to coextrusion‖, Industrial & Engineering Chemistry
15.0 wt%, the final film thickness increase from 160 to 960 Research, 49 (23), 2010, pp 12111–12118.
nm at a spin speed of 3000 rpm. Applied methods of [6] David B. Hall, Patrick Underhill, John M. Torkelson,
thickness measurements have shown a quasi-linear thickness ―Spin coating of thin and ultrathin polymer films‖,
dependence on polymer concentration. (Fig.6.). Therefore, a Polymer Engineering & Science, 38(12), 1998, p. 2039–
smooth polymer films can be fabricated just by controlling 2045.
the polymer concentration in solution. Applied method for [7] T. Komikado, A. Inoue, K. Masuda, T. Ando, S.
determination of thickness of films in dependence on polymer Umegaki, Multi-layered mirrors fabricated by spin-
concentration in solution can be successfully extended to coating organic polymers, Thin Solid Films, 515(7-8),
other polymer films in order to obtain required thickness 2007, p. 3887-3892.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

[8] M. Kimura, K. Okahara, T. Miyamoto. Tunable S.H., Choi D.H. Ellipsometric study of polymer thin
multilayer-film distributed Bragg reflector filter, J. films: Nonlinear optical guest-host system, J. Appl.
Appl. Phys. 50, 1979, p. 1222-1225. Phys., 97(8), 2005, p. 083543.
[9] A.L. Alvarez, J. Tito, M.B. Vaello, P. Velasquez, R. [11] A.M. Nasr, H.I. Abd El-Kader, M. Farhat.
Mallavia, M.M. Sanchez-Lopez, S. Fernandez de Avila, Characterization of photoactive polymer thin
Polymeric multilayers for integration into photonic films using transmission spectrum. Thin Solid Films,
devices, Thin Solid Films, 433, 2003, p. 277-280. 515(4), 2006, p. 1758-1762.
[10] Lee K.J., Kang T.D., Lee H.S., Lee H., Cho M.J., Lee [12] Poroshin, V.; Bogomolov, D. Kostyuk, A. PC based
measurement system for interferometric analysis of
etalon roughness. Advanced Engineering, 4(1), 2010, p.
65-68.

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Design of the Holographic Fiber-optic

Electronic Speckle Pattern Interferometer for
Optical Constants of Glasses Measurements.
O. IASENIUC, A. ANDRIESH, E. ACHIMOVA, V. ABASHKIN.
Center of Optoelectronics, Institute of Applied Physics,
Academy of Sciences of Moldova,
5 Academic str., MD-2028, Chisinau, Moldova
e-mail: [email protected]
Abstract – An elaboration the holographic fiber-optic electronic speckle pattern interferometer (ESPI) which
can will be apply for measurement of the optical constants is described. This interferometer with CCD Smart
Camera can be programming based on National Instruments’ graphical programming LabVIEW software.
Using the LabVIEW we can apply flexible program for different software steps for processing of recorded
interferograms (extracting amplitude, phase map and frequency domain, subtraction), obtained by CCD
Smart Camera for feather calculation the optical properties the refractive index and thickness of studying
samples.

Index Terms – digital holographic speckle pattern interferometer, ESPI, optical fibers, LabVIEW.

vibration).
I. INTRODUCTION
The optical properties, especially the refractive index, of II. THE DIGITAL HOLOGRAPHIC FIBER-OPTIC
chalcogenide glasses are currently a subject of systematic SPECKLE PATTERN INTERFEROMETER
research due to they manifest strong photo- and thermally- Breadboard with tapped holes as a stable platform for
induced properties that offer the possibility of using mount interferometer and optical experiments for various
amorphous chalcogenide for high-density information test configurations was used. Fiber-optical design of ESPI
storage, fabrication of diffractive optics such as Bragg was chose to sustain vibration immunity (Fig. 1, 2). There
gratings elements, inorganic photo-resists, and different are 10 mW He-Ne laser (1), wedge prism as beamsplitters
holographic patterns. (2), multimode optical fiber as object arm (3), sample (bulk
But one of the main problems is the precise definition of or thin films of the chalcogenide glasses) (4), object arm (5),
the refractive index and thickness of the samples. Different camera objective (6), optical lever composed from negative
x
methods have been developed to measure the refractive lens and positive lens (7) as microobjective (8) (60 and
index. Many of spectrofotomertic, ellipsometric, NAobjective =1.25) and monomode optical fiber as reference
interferometric methods for determining the refractive index arm (9), rectangular diaphragm (10), CCD Smart Camera
of materials have also been developed. But all they have (11), PC (12).
errors and less precision.
1 2
The holographyc fiber-optic ESPI as a method of small
He-Ne
displacement was formed in 80-th years [1], but to measure
the optical parameters have learned recently. This is high
precision, noncontact, full-field, optical method for 12 3
measuring the optical properties changes.
Data from speckle interference patterns for further 7 8
determining properties of the studying samples is processing
by holographic and programming methods.
9 4
The main aim of this work is to design holographic fiber-
optic ESPI and in future to study a new materials - 10
11
determining of the refractive index, it variations and
thicknesses (thin films and bulk materials) by method of CCD
holographic fiber-optic ESPI. Especially this method can be 6 5
very useful for full-field measurements the index of
refraction after recording process on chalcogenide glasses. Fig. 1. Optical set-up of holographic fiber-optic ESPI.
It should be noted that during the planned research is
expected to establish that the application of digital speckle
There are 3 conditions for effective coupling laser beam
correlation interferometry technique can be extend the
energy and mono mode fiber:
number of experimental data and expand the range of
 Coincidence of the aperture of the objective and
tasks due to flexibility of LabVIEW program, portable set-
up, immunity to the environment influences (temperature, fiber core respect to condition NAobjective≥NAfiber;

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 Diameters coincidence of microobjective focal spot The NI Smart Camera provides control of the image
and monomode fiber core; sensor exposure time through software.
 Adjustment of the modes and wavelength If a squared difference is performed between two
transmission of the laser and monomode fiber. digitized speckle patterns and recorded at different states of
This advantageous interferometric arrangement allows the object, the result will be:
obtaining the speckle pattern fast enough (due to recording
rate of CCD Smart Camera) and with high precision (less I(x,y)=8I0(x,y)Ir(x,y)sin2[υ(x,y)+Δυ(x,y)/2]{1-cos[Δυ(x,y]},
then λ/4). (1)
A digital holographic speckle pattern interferometer relies
on the correlation between two speckle patterns. Each one where Io(x,y) and Ir(x,y) are the object and reference beam
created by the interference between a reference beam and the intensities, and υ(x,y) is the speckles random phase. The
image of an object illuminated by laser [2-4]. Typically the Δυ(x,y) term containes the phase variation between the two
two images are of an object before and after some changes subtracted patterns. This equation represents a ESPI
(in-plane or out-of-plane displacements). Acquired by CCD interferogram description obtained by subtraction technique.
camera's image is converted into a corresponding video 11 10 6. 4.
signal. This video signal is electronically processed by PC . . 3.
through Gigabit Ethernet, so that texture variations of the
speckle pattern are converted into brightness variations. A
speckle interferogram is generated arithmetically by
subtracting two digitized speckle patterns. The similar
operation of subtraction of two stored on PC interferogram 9.
can be made using our program in LabVIEW. In
this case, the distribution intensity of the resulting speckle 1.
pattern will depend on the relative phase shift superimposed
7.
fields. Deformation of the object leads to a change in the
phase of the object speckle field and, consequently, to 2.
changes in intensity of the speckle pattern. Obtained the
digital speckle patterns interference are also subjected to 2. 7.
computer processing in order to increase the contrast fringe 8. 9.
and smoothing of optical noise - the speckle modulation. In
practice, the intensity distribution in the camera detector 1.
plane is stored with the object in its reference state. The
object is then deformed and a second frame is stored. The
two frames are then subtracted and correlation live fringes
are displayed on a monitor (Fig. 3). Images subtraction 11
makes the interferogram easy to form, view, and recording .
no in time. (Recording rate of Smart Camera is about 3. 6. 10
60 fps.). NI 1722 Smart Camera simplify machine vision by .
4.
analyzing images directly on the camera with a powerful,
embedded processor capable of running NI Smart Camera
digital I/O lines are optoisolated for direct connectivity with Fig. 2. Two side photos of the holographic fiber-optic ESPI set-up with
elements numbered respective to Fig. 1.
industrial devices such as triggers and actuators. All smart
camera models incorporate an image sensor, processor, and Interference pattern
digital I/O in a compact, rugged housing. The Smart Camera sample CCD Processing
also includes LEDs for communicating system status, four signal
DIP switches to specify startup options, isolated inputs, and
isolated outputs for connecting to external devices.
Developing applications with the NI Smart Camera requires
one of the following software options:
 Vision Builder for Automated Inspection: (Vision Builder
Speckle-pattern
AI) is configurable machine vision software can use to
Fig. 3. Schematic of ESPI measurement processing.
configure the NI Smart Camera and prototype,
benchmark, and deploy machine vision applications.
Creating applications in Vision Builder AI does not III. LABVIEW
require programming. It allows you to easily configure Most researches today are done with the aid of computers.
and benchmark a sequence of visual inspection steps, as The computers are used to control the experiment,
well as deploy the visual inspection system for acquisition, and processing of data. LabVIEW is a graphical
automated inspection. programming language elaborated by National Instruments
 LabVIEW 2010: LabVIEW Real-Time Module, NI Company [5]. LabVIEW programs are called virtual
Vision Development Module, NI Vision instruments (VIs), because their operation imitates works of
Acquisition Software-IMAQ. LabVIEW is a physical instruments made by user. Specifically, LabVIEW
graphical programming environment for developing is used to interface the computer with programmable
flexible and scalable applications.

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measuring instruments. LabVIEW contains a comprehensive to comprehend, common programming tasks, like
set of tools for acquiring, processing, analyzing, displaying, debugging, become more intuitive as well. LabVIEW
and storing data. Because LabVIEW graphical code is easy
providing unique debugging tools that can use to watch as Image acquisition window (on the right) used for image
data interactively moves through the wires of LabVIEW processing respect options presented on Fig. 5-7:
program and see the data values as they pass from on  Simple squared difference -Fig. 5;
function to another along the wires between VI or sub VI.  Phase map -Fig. 6;
Each VI consists of a front panel and a block diagram. The  Rectangular determination for following unwrapped
front panel specifies the inputs and outputs which make up phase map extraction - Fig. 7.
the user interface. The block diagram consists of icons which The operator starts the primary task, the data acquisition
represent subroutines and program control structures [6]. program, namely the first step is reading a reference image
LabVIEW is a program development application, much file and a recording image file. Program recognizes image
like various commercial C or BASIC development systems, file configurations such as BMP, TIFF, PNG and JPEG. This
or National Instruments LabWindows. However, LabVIEW type definition edits automatically. The reference image in
is different from those applications in one important respect. our case is unloaded object image. The recording image
Other programming systems use text-based languages to represents loaded object. Object loading process can be
create lines of code, while LabVIEW uses a graphical made by suitable way for object under investigation, for
programming language, to create programs in block diagram example heating, vibration, etc. The LabVIEW execution
form. Moreover anybody can use LabVIEW with less engine then distributes data the three our tasks in
programming experience. LabVIEW programs are called dependence of the problem needed and chosen by operator
virtual instruments (VIs) because their appearance and on front panel. These tasks are a pointed above.
operation imitate actual instruments. However, they are The simple difference task VI‘s serve for squired image
analogous to functions from conventional language to increase S/N ratio. This block diagram also produces a
programs. VIs has both an interactive user interface and a histogram equalization of the squired image.
source code equivalent, and accepts parameters from higher- Block diagram for rectangular determinations serves for
level VIs. elimination from complex image low frequencies which are
LabVIEW has extensive libraries of functions and haven‘t useful information about the object. After that step
subroutines for most programming tasks. LabVIEW contains VI Mask recopies image source into new image for
application specific libraries for data acquisition and processing.
instrument control. LabVIEW also contains application- Inside phase map block diagram VI computes optical
specific VI libraries and serial instrument control, data FFT of both images and creates complex images in which
analysis, data presentation, and data storage. high frequencies are grouped in the center while low
The primary step of our program in LabVIEW is images frequencies are located at the edges. Inverse FFT of
acquisition and storage. Acquired images are stored in complex image after VI Mask calculation must be doing for
memory of CCD Smart Camera or in PC ready for final step as phase map calculation. So this block diagram
processing. first produces wrapped phase map and then unwrapped
The front panel of our program is shown on Fig. 4 phase map. After final processing surface changes in-plane
In left side of screenshot one inserts names of two images. or out-of-plane will be presented.

Fig. 4. The screenshot of a LabVIEW user front panel

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Fig. 5. The screenshot of a LabVIEW user block diagram of VI‘s for a simple squared difference processing.

Fig. 6. The screenshot of a LabVIEW user block diagram of VI‘s for a phase map mode.

III. CONCLUSIONS AND PERSPECTIVE can extract phase map, and finally calculate the required
Our work consist of two main objectives: the optical parameters by elaborated method. Important feature
optical set-up design of fiber-optic ESPI and elaboration of this method are the full-field measuring of object
LabVIEW program. The process of measuring by our properties which is important for investigations of optically
installation is reduced to receiving two speckle snapshots of recorded diffraction elements with very small location of
unloading and loading object. They will be recorded by refraction index changes.
using the CCD image sensor. Farther with image processing In our work the methods was used:
of speckle patterns and data processing with LabVIEW we • Speckle-interferometric method of speckle-interferogram

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with Fourier optical processing in objective plane; type of FFT, histogram, phase extraction, S/N of image
• Holographic method of recording images on Smart Camera enhances.
CCD image sensor; In perspective we plan to apply set-up and method for
• Method of forward and inverse Fourier-transformations; measuring the refractive index of As-S-Se-Sn chalcogenide
Methods of processing by using LabVIEW are optical glasses [7-11].

Fig. 7. The screenshot of a LabVIEW user block diagram of VI‘s for a rectangular determination.

REFERENCES
IV. CONCLUSIONS AND PERSPECTIVE
[1] Ch.Vest , Holographic inierferometry, 1982, pp.504.
Our work consist of two main objectives: the optical set-
[2] Yu. Ostrovsky, V. Shchepinov, V. Yakovlev,
up design of fiber-optic ESPI and elaboration LabVIEW
Holographi interference methods for studying the
program. The process of measuring by our installation is
deformation, 1988, pp. 248.
reduced to receiving two speckle snapshots of unloading
[3] S. Yurischeva, A. Osintsev, V. Shchepinov,
and loading object. They will be recorded by using the
Application of the method of digital
CCD image sensor. Farther with image processing of
speckle interferometry to study contact interactions,
speckle patterns and data processing with LabVIEW we can
vol. 8, 2006, pp.120-121.
extract phase map, and finally calculate the required optical
[4] R. Jones, C. Wykes, Holographic and Speckle
parameters by elaborated method. Important feature of this
Interferometry, 1986, pp.327.
method are the full-field measuring of object properties
[5] http://www.ni.com/
which is important for investigations of optically recorded
[6] L. Clark, LabVIEW. Digital signal pricessing and
diffraction elements with very small location of refraction
digital communications, McGraw-Hill Companies,
index changes.
Inc., 2005, pp. 202.
In our work the methods was used:
[7] O. Iaseniuc, A. Andriesh, A. Abashkin, Optical
• Speckle-interferometric method of speckle-interferogram
properties of amorphous (As2S1,5Se1,5)0,99:Sn0,01.
with Fourier optical processing in objective plane;
Moldavian Journal of the Physical Sciences, vol. 4,
• Holographic method of recording images on Smart
2010, pp. 349-355.
Camera CCD image sensor;
[8] M. Iovu, S. Shutov, M. Popescu, J. of Non-Cryst.
• Method of forward and inverse Fourier-transformations;
Solids, vol. 924, 2002, pp.299-302.
• Methods of processing by using LabVIEW are optical
[9] P.Boolchand, D. Georgiev, M. Iovu, Chalcogenide
type of FFT, histogram, phase extraction, S/N of image
Letters, vol. 2, 2005, p.27.
enhances.
[10] A.Andriesh, M. Iovu, J. of Optoelectronics and
In perspective we plan to apply set-up and method for
Advanced Materials, vol. 8, No.6, 2006, pp. 2080 –
measuring the refractive index of As-S-Se-Sn chalcogenide
2085.
glasses [7-11].
[11] D. Harea, M. Iovu, O. Iaseniuc, E. Colomeico, A.
ACKNOWLEDGEMENT Meshalkin, Modification of the optical constants in
The authors of this work wish to express their gratitude amorphous Sb2Se3:Sn thin films under the
to researcher Prisacar A. for elaboration of software for illumination and heat treatment, J. of Optoelectronics
patterns subtraction based on FFT algorithm and general and Advanced Materials, (IF - 0.577), vol. 12, No.11,
assistance and discussion during work. 2009, pp. 2039-2043.

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Improvement of SiO2(Ge)SiO2/Si
Nanostructures by Low Dose γ-radiation
S.T. SHISHIYANU1 , T.S. SHISHIYANU1, E. YILMAZ2, R. TURAN3, N.A.P. MOGADDAM3
1
Department of Microelectronics, Technical University of Moldova, 2004 Chisinau, Moldova
2
Department of Physics, Abant Izzet Baysal University, 14280 Bolu, Turkey
3
Department of Physics, Meddle East Technical University, 06531Ankara, Turkey
[email protected]

Abstract – Effect of γ – radiation on SiO2(Ge)SiO2/Si nanostructures structural defects was investigated by C-V
measurements characterization. The obtained results demonstrated that by low dose γ-radiation (0.1Gy150Gy)
have been essentially reduced the negative charge defects in the nanocomposite structures SiO 2(Ge)SiO2/Si. At
higher doses (350Gy4000Gy) the concentration of positive charge defects slowly increased and C-V characteristics
moved to the position of the C-V characteristics of pure SiO2 (without nc-Ge) having the same curves
configuration. At the average doses (200Gy350Gy) the concentration of negative charge defects and positive
charge defects were approximately equal and the radiation stability of samples was the highest.

Index Terms – Ge nanocrystal, SiO2/Si, structural defects,  –radiation.

From these data we can conclude that in the samples of

I. INTRODUCTION
Ge/SiO2, in dependence of growth methods and thermal
The investigation of radiation effects on nanocrystals Ge
annealing in different ambient (N2, H2), can be formed not
and Si embedded in SiO2 has the major importance, first of
only nanocrystals of Ge, but and different defects as GeO x,
all, to know the specific of radiation stability and
GeO2, GeSi, which have direct impact to properties of
degradation of nanocrystals in comparison with
SiO2Ge/SiO2/Si –nanostructures.
monocrystalline materials (semiconductors – Ge, Si);
By another hand radiation methods can bee efficiently
secondly, for elaboration of the new methods of radiation-
used for defect monitoring of structural defects for
nanotechnology for the nanoelectronic device fabrication,
improvement of fundamental properties of nanostructured
and third, for the implementation of these new
and nanocomposite materials [12-15]. It is shown in [12] that
nanostructured and nanocomposite materials for radiation
by the ion irradiation is possible to change of the number,
sensor fabrications.
size and distribution of the silicon nanocrystallites and
Nanocrystals of Si and Ge embedded in SiO2 - matrices have
improve the photoluminescence intensity. This results are in
attracted much attention due to their possible applications in
accordance with publication [13] where is indicated that
integrated opto-nano-electronics as nanolasers, nano-flash
after irradiation with 400kev electrons or 30-130kev He+
memory and multifunction nanodevices [1-3]. Many authors
ions and the post-irradiation annealing at 1000C, the
have been elaborated different methods of Ge- nanocrystal
photoluminescence intensity of Si-nanocrystals became
obtaining: molecular beam epitaxy on the thin SiO2 layer on
several times stronger than that from the initial samples
Si(001) [1], implantation of Ge+ ions into SiO2 films with
subsequent annealing [2], chemical vapor deposition prepared at 1150C. These results are assumed to be a sum
(PECVD)[3,4], magnetron sputtering [5,6]. In [7] are of the intensities from the initial nanocrystals and from the
presented the comparative study on photoluminescence from new ones that appeared due to irradiation [13]. In [14] it was
Ge/PS, (PS - porous silicon) and Ge/SiO2 thin films; the shown that the low-dose of γ- irradiation (5104  105rad.)
photoluminescence peaks of Ge/PS were located at 517nm leads to remarkable (up to 40%) increase of
and peaks of Ge/SiO2 at 580nm. In [8] the samples of photoluminescence band (1.33eV) intensity. Infrared spectra
Ge/SiO2,obtained by sol/gel method , after annealing at demonstrated that composition and structure of the
700C under H2 reduction, by UV light excitation was nanocomposite matrix were not changed by radiation. The
observed tree peaks of photoluminescence at room effect was explained by radiation induced structural ordering
temperature 392nm(3.12 eV), 600nm(2.05eV) and nanocrystal-matrix interface [14]: low-dose irradiation
770nm(1.6eV). The peak of 1.6eV is attributed to Ge partially eliminated defects (recombination centers) at nc-Si-
monocrystals, peak of 2.05 eV – to defect GeOx and peak of SiO2 interfaces that resulted in enhancement of nanocrystal
3.12eV – to GeO2. The unreduced sample shows only on luminescence. The impact of low-dose γ- radiation on nc-Ge
peak of 3.12eV attributed to GeO2. These results are in SiO2 has been studded in [15].
different of other authors: 570nm(2.16eV) in Ge/SiO 2, The main objective of this paper is investigation of the
obtained by rf-magnetron co sputtering method [9]; 510- effect of ionizing γ- radiation on C-V characteristics and
radiation defect monitoring in SiO2(Ge)SiO2/Si.
680nm (2.42  1.81 eV) at 77K temperature in Ge/SiO2,
prepared by sol-gel method: 680nm (1.8eV) at room
temperature [10]; 689nm (1.8eV) at room temperature [11].

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II. EXPERIMENTAL nanostructured samples, SiO2(Ge)SiO2/nSi, are situated at

The samples used in this work were 100nm Ge rich SiO 2 positive voltages (V>0) to opposite to conventional MOS
layer sandwiched between two SiO2 films deposited on n- structure (SiO2/nSi curve, without nc-Ge) which is situated
type Si<100> substrate by RF magnetron co-sputtering from at negative voltages (V<0); (3) - the accumulation regime
two independent target materials with powers of PSiO2= corresponds to positive high voltage of +(45)V and
300W, PGe= 20W [15]. The bottom SiO2 layer with the depletion- inversion regime corresponds to small positive-
thickness of about 100 nm was deposited on Si to restrain Ge negative voltage of ± 2V; (4)-after cumulative irradiation
atoms from growing epitaxially on the Si substrate in the from 0.1Gy to 4000Gy the C-V characteristics moved from
post-annealing process. The top SiO2 layer with the positive threshold voltage (+3V) to negative threshold
thickness of about 40 nm was deposited to impede the voltage (-1V) corresponding to the decreasing of negative
diffusion of Ge atoms out of the surface. charge defects or increasing the positive charge defects in
In our experiments have been investigated the C-V these structures (Q= VxC). After high dose γ- irradiation
characteristics of the nanocomposite structures, SiO2(nc- (2800Gy4000Gy) the C-V characteristic tend to
Ge)SiO2/nSi, prepared by different post-grown thermal conventional C-V characteristics (SiSiO2 curve), but there
treatment: Set-1 - as grown, Set-2 – after 1 hour annealing at incline is higher due to high concentration of charge defects.
900C in N2, Set-3 – after 1 hour annealing at 1000C in N2 These experimental results indicate that all C-V
and Set 4 – after 1 hour annealing at 1000C in a N2, RTA characteristics in fig.1 can be deviated in two groups: (i) -
15 min H2+N2. In general, the formation mechanism for Ge low-dose (0.1Gy150Gy) characteristics and (ii) – high dose
nanocrystals embedded in SiO2 matrix goes through the (200Gy4000Gy) characteristics.
familiar sequence of nucleation and growth, followed by The low-dose (0.1Gy150Gy) characteristics, in
coarsening of nanocrystals due to Ostwald ripening [16]. accumulation regime at Vfb= +(56)V, have a smaller
The C-V characteristics gave information about state and capacitance and accumulated electrons than that of middle
dynamic charged defects of investigated MOS structures and high radiation dose.
under influence of ionization γ- radiation. All C-V curves The high dose irradiation in interval of 350Gy4000Gy
have been measured before and after radiation at dose from moved the C-V characteristics to negative voltage: flat band
0.1Gry to 4000Gry at frequencies - 1MHz. voltage (Vfb) decreases from Vfb = +4V to Vfb = +1.7V and
middle gap voltage removed from Vmg = +2.2V to Vmg = -
0.45V.
The middle dose radiation (200Gy350Gy) removed very
slowly C-V characteristics: flat band voltage from Vfb= +4V
to Vfb= +3.9V and middle gap voltage from Vmg = +2.2V to
Vmg =+2V; the C-V characteristics have not specific
properties, but they look more radiation stable
(characteristics after 250Gy and 350Gy coincide).
Using the values of ∆Vmg =Vmg(0) - Vmg(U) and ∆Vfb = Vfb
(0)- Vfb(U) we estimated the net oxide trap/charge densities
(∆Not) and the net interface trap-charge density (∆Nit) by
relations [17]:
CoxVmg
N ot   ; (1)
qA

Cox V fb  Vmg 

Fig. 1 The C-V characteristics 1MHz before and after γ- irradiation at
different doses (0.1 Gy  4000Gy), Set 4.
N it  , (2)
qA
III. RESULTS AND DISCUSSION
The C-V characteristics have been measured of the where Cox is the oxide capacitance measured in
samples from different Sets - 1, 2, 3, 4 before and after γ- accumulation, -q =(1.60210-19C) electron charge and A is
radiation at dose from 0.1Gy to 4000Gy. For illustration in the area of capacitor.
Fig. 1 are presented the C-V characteristics for Set- 4. The C-V characteristics of other samples (Set 1,2,3), as
The samples of Set 4 after growth have been 1 hour annealed well as Set 4, have specific differences at low dose
at 1000C in N2 + RTA for 15 min in forming gas H2+N2. irradiation (0.1Gy - 64Gy) and many similarities at high
This regime was used for Ge nanocrystals formation in SiO 2 dose irradiation (350Gy - 4000Gy). Therefore we will
[15]. analyze in details the effects of low-dose irradiation.
In Fig.1 are presented dynamics of C-V characteristics of The charged defect concentration in volume (∆Not) and
nanostructured samples of SiO2(Ge)SiO2/nSi (Set 4) under γ- the interface charge stats (∆Nit) calculated from the
irradiation of dose from 0.1Gy to 4000Gy (a); (b) –C-V experimental results of flat band voltage (Vfb, ∆Vfb) and
characteristics of conventional SiO2/nSi –structure (without middle gap voltage (Vmg, ∆Vmg) and are presented in Fig. 2.
nc-Ge). In Fig.2(a,b) are presented the dependences of the volume
As shown in Fig. 1, there are some specific properties of charged defect concentration (∆Not) and interface charge
these C-V characteristics: (1) all curves have typically form stats concentration (∆Nit) vs dose of γ-radiation for samples
as MOS structures; (2) the C-V characteristics of Sets 2,3,4.

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1.11012cm-3) and interface charge stats – in interval of

(∆Nit= 1.21010cm-3 1.9x1011cm-3). Respectively, the
concentration of negative charged defect (Q-) have been
reduced at low-dose radiation and concentration of positive
charge defects (Q+) slowly increased at high dose to ∆Not
=1.21012cm-3 and ∆Nit=6.51011cm-3 at 4000Gy, Fig. 2.
For all samples of Set-3 the C-V characteristics were
situated at negative voltage at 0.2V1.0V in accumulation
regime and at -1.0V3.2V in depletion regime. After
radiation at low-dose (0.1Gy150Gy) the flat band voltage
(Vfb) changed from +0.2.1V to -1.0V, the middle gap voltage
(Vmg) - from -1.0V to -3.0V; the concentration of volume
charged defect (∆Not) – from 2.61010cm-3 to 5.81011cm-3
and the interface charge stats (∆Nit) – from 1.11011cm-3 to
2.31011cm-3. Respectively, the concentration of negative
charged defect (Q-) have been reduced at low-dose radiation
and concentration of positive charge defects slowly
increased at high dose to ∆Not=7.21011cm-3 at 4000Gy,
Fig.2.
The C-V characteristics of Set 1 (without post-growth
thermal annealing) were situated in region of positive
threshold voltage corresponding to very high concentration
of negative charge defects (Q-), having a complicate shape
and were non stable during the measurements.
We explain the obtained results on the base of model of
negative-positive charge defects correlation at low- and high
dose of radiation. In accordance with this model, it is
supposed that in investigated samples Set 1,2,3,4, before
irradiation existed at least three types of charge defects:
negative charge volume defects (Qa-) like acceptor centers
Fig. 2 (a,b). The volume charged defect concentration (∆Not) and interface (GeOx)-, slow negative interface stats (Qs-) like structural
charge stats concentration (∆Nit) vs dose of γ-radiation, Sets 2, 3, 4. defects (GeSi)- and conventional positive charge defects
(Ob+) like (SiOx)+ in pure SiO2.
In this case the charge neutrality of material can be
We can see in Fig.2 that flat band voltage(Vfb) and middle
expressed by relation:
gap voltage (Vmg), as well as concentrations (∆Not) and
(∆Nit), changed more rapidly after low-dose (0.1Gy2.0Gy)
and slowly changed after dose of 16Gy 150Gy.  
Qb  Qa  Qs  0 (3)
As it is shown in Fig. 2, for the samples of Set 4, as result
of γ-irradiation at low-dose (0.1150Gy) the flat band Before irradiation, samples of Set 1, 2, 3, 4, have the C-V
voltage (Vfb) changed from +5.1V to 4.2V, the middle gap characteristics situated in region of positive voltage (+Vfb,
voltage (Vmg) - from +3V to +2.4V; the concentration of +Vmg) due to majority of negative charge defects:
volume charged defect (∆Not) – from 8.01010 cm-3 to
2.41011cm-3 and the interface charge stats (∆Nit) – from Qa  Qs  Qb (4)
4.01010cm-3 to 1.61011cm-3. Respectively, the
concentration of volume negative charged defects (Q-) have
Under the influence of low-dose γ-radiation (0.1Gy
been reduced at low-dose radiation and concentration of
200Gy) have been decreased of the negative charge defect
positive charge defects (Q+)slowly increased at high dose to
concentration to level of charge neutrality (Qa- + Qs- = Qb+).
∆Not =1.71012cm-3 and ∆Nit=1.61011cm-3 at 4000Gy. In this case the instability and the abrupt change of charge
The specific properties of the C-V characteristics of defect concentration at very low dose (0.1Gy) is due to the
samples Set 2 are: 1) for non radiation, C-V characteristic rapid concentration decrease of slow negative charge states -
are situated in the region of positive voltage (+2V-0.8V); 2) structural defects (GeSi)-. At higher γ-radiation (350Gy
at low-dose radiation (0.116Gy) the CV characteristics 4000Gy) have been increased slowly the concentration of
where instable with some deviation voltage (±0.2V); but at positive charge defects and have been improved the linearity
dose up to 64Gy the C-V characteristics become stable at of C-V characteristics, which become comparable with the
region of negative voltage that corresponds to minimum C-V characteristics of pure SiO2/nSi structures with the same
negative charge defect concentration; 3) at higher dose of configuration.
2004000Gy the C-V characteristics moved slowly to These results of improvement of C-V characteristics of
negative voltage in correspondence with slow increase of the nanocomposite structures ncGe/SiO2 are in accordance with
positive charge defect concentration. Calculation data of photoluminescence improvement of silicon
demonstrated that concentration of volume negative charge nanocrystals ncSi/SiO2 after low dose ion radiation [12],
defects changed in interval of (∆Not=3.11010cm-3  electron radiation [13] and gamma radiation [14].

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IV. CONCLUSIONS 24.com/paper/15584.

[7] X.J. Sun, S.Y. Ma, J.J. Wei, X.L. Xu, ―Comparative
The obtained results demonstrated that by low dose γ- study on photoluminescence from Ge/PS and Ge/SiO 2
radiation (0.1Gy150Gy) have been essentially reduced the thin films,‖
structural negative charged defects in the nanocomposite http://www.ncbi.nlm.nih.gov/pubmed/19093555.
structures SiO2(Ge)SiO2/Si investigated by the C-V [8] Yu Ying, at al., ―New Photoluminescence of Ge/SiO2
characteristics. At higher doses (350Gy4000Gy) the Glass Synthesized by Sol/gel Method,‖ Chinese
concentration of positive charge defects slowly increased Chemical Letters vol.15, n.12, pp.1505-1508, 2004.
and C-V characteristics shown the properties of the pure [9] Y.Maeda, N.Tsukamoto, Y.Yazawa, Appl.Phys.Lett.
SiO2 (without nc-Ge) with the same configuration. At vol.59, n.24, p.3168, 1991.
average doses (200Gy350Gy) the concentration of negative [10] M. Nagami, Y. Abe, Appl. Phys. Lett., vol.65, n.20,
charge defects and positive charge defects were p.2545, 1994.
approximately the same and the radiation stability of the [11] K.S. Min, K.V.Shcheglov, C.M. Yang and H.A.
samples was the highest. Atwater, Appl.Phys.Lett., vol.68, n.18, p.2511, 1996.
[12] I. Antonova, V. Scuratov, M. Gulyaev, D. Marin, J.
Jedrzejewski, I. Balberg, ―Improvement of the
REFERENCES nanocrystals embedded in dielectrics and
[1] N.L. Rowell, D.J. Lockwood, A. Karmous, P.D. nanostructures,‖ IBMM2008.org 16 th International
Szkutnik, I.Berhezier, Supperlattices and Conference on Ion Beam Modification of Materials,
Microstrucrures, 44, p.305, 2008. Dresden, Germany, 31 September, 2008.
[2] A. Singha, P. Dhar, A. Roy, ―A nondestructive tool for [13] G.A. Kaciurin, et al., ―The influence of Irradiation on
nanomaterials: Raman and photoluminescence Subsequent Annealing on Si Nanocrystals Formed in
spectroscopy,‖ Am. J. Phys. vol.73, n.3, pp. 224-230, SiO2 Layers,‖ Semiconductors, vol.34, n.8, pp.965-970,
2005. 2000.
[3] A. Dana, S. Agan, S. Tokay, A. Aydinli, T.J. Finstad, [14] I. P. Lisovskyy, I.Z. Indutnyy, M.V. Muravska, V.V.
―Raman and TEM studies of Ge nanocrystal formation Voitovych, E. G. Gule, P.E. Shepelyavyi. Fizika i
in SiOx:Ge/SiOx multilayers,‖ Phys. Stat. Sol., (C), vol. Tekhnika Poluprovodnikov, vol.42, n.5, pp.591-594,
4, n.2, pp.288-291, 2007. 2008.
[4] S. Agan, A. Dana and A. Aydinli, ―TEM studies of Ge [15] S.T. Shishiyanu, N.A.P. Mogaddam, E. Yilmaz, R.
nanocrystals formation in PECVD grown SiO2:Ge/SiO2 Turan, ―Effect of Gamma Radiation on Raman Spectra
multilayers,‖ J. Phys: Condens. Matter, vol.18, pp. of Ge Nanocrystals embedded in SiO2,‖ Proc. of 5th
5037-5045, 2006. Nanoscience and Nanotechnology Conference
[5] K. Salamon, O. Milat, M. Buljan, U.V. Desnica, NanoTR5, Eskişehir, Turkey, pp.67-69, 2009.
N.Radic, P.Dubcek, S.Bernstorff, ―X-ray study of Ge [16] J.H. Yao, K.R. Elder, H. Guo, M. Grant, ―Theory and
nanoparticle formation in Ge:SiO2/SiO2 multilayers,‖ simulation of Ostwald ripening,‖ Phys. Review B, vol.
On-line Journal of E-MRS Fall Meeting, 2007. 47, n. 21, pp.14 110-14 125, 1993.
[6] U.V.Desnica, M.Buljan, K.Salamon, N.Radic et al., [17] F.B. Ergin, R.Turan, S.T. Shishiyanu, E.Yilmaz. ‖Effect
―Formation of germanium nanocrystals in SiO 2 of γ-radiation on HfO2 based MOS capacitor,‖ Nuclear
using RF magnetron sputtering,‖ http://www.science Instruments and Methods in Physics Research Section
B; vol.268, n.9, 2010, pp.1482-1485.

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Nanoperforated Indium Phosphide for Terahertz

Imaging Bio-applications
D. ESINENCO1, L. SIRBU2, I. VODA3, L. GHIMPU2, R. MULLER4, R. VOICU4, M. DANILA4, A.
LECA5, T. DASCALU5, I.M. TIGINYANU1,2 and V. URSAKI1,6
1
Technical University of Moldova, 168, Stefan cel Mare str., MD-2004 Chisinau, Moldova
2
Institute of Electronic Engineering and Nanotechnologies "D. Ghitu ", 3/3, Academiei str., MD-2028
Chisinau, Moldova
3
Institute of Chemistry of the Academy of Sciences of Moldova, Academiei str., MD-2028 Chisinau,
Moldova
4
National Institute for R&D in Microtechnologies- IMT Bucharest, Erou Iancu Nicolae 126 A str.,
Bucharest, Romania
5
National Institute for Laser, Plasma and Radiation Physics Laboratory of Solid-State Quantum
5
Electronics, PO Box MG-36, Magurele, 077125, Romania
6
Institute of Applied Physics, Academy of Science of Moldova, 5, Academiei str., MD-2028 Chisinau,
Moldova

Abstract – We demonstrate the fabrication of thin InP membranes with porous compact packed structure
that have been cut during electrochemical etching in the same anodic process. Besides, we show the possibility
of pore filling with metal-organic composites. Chemical compounds have been identified by XRD method.
The THz emitting characteristics of InP porous films were drastically changed after filling with sensitized
metal-organic composites. We show that InP porous membranes filled with metal-organic composites are
perfect materials for bio-applications. The experimental study and emulations based on Finite Element Model
(FEM) show also that the obtained nanocomposite materials are promising for nonlinear optical applications,
in particular for the development of THz emitters, THz imaging systems, MEMS, MOEMS, etc.

Index Terms – nanostructurated membrane, Terahertz (THz) spectroscopy, Indium Phosphide (InP), metal-
organic composites, bio-materials.

importance for condensed matter physics and in particular

I. INTRODUCTION
for semiconductors and semiconductor structures because
For many decades the terahertz frequencies that range
the characteristic energies of many elementary excitations lie
between the infrared and millimeter wavelengths was one of
in this spectral range [1]. Among them are plasma
the least explored regions of the electromagnetic spectrum.
oscillations, ionization energies of typical shallow donors
and acceptors, cyclotron resonance and spin-flip energies,
the characteristic size-quantization energies of low
dimensional electron systems, and optical phonon energies.
Furthermore, the relaxation rates of free and bound excited
While experimental techniques developed for both carriers and scattering rates of free carriers coincide with the
neighboring spectral ranges cannot be directly applied at terahertz regime. The photon energies in this part of the
terahertz frequencies many of the methods and theories have electromagnetic spectrum range from about 1 to 35 meV
been adapted to the terahertz range. For instance, single- being much smaller than the energy gap of usual
mode waveguides, widely used in the millimeter range, semiconductors.
cannot be applied at terahertz frequencies because of strong At the same time the terahertz technology has entered
damping, but oversized multimode waveguides are into an unprecedented revolutionary era with ever-growing
commonly used. On the other hand, glass is the standard applications in biology and medicine [2], monitoring and
material for optical components in the visible and near- spectroscopy in pharmaceutical industry and science [3, 4],
infrared but in the terahertz range it cannot be used due to medical imaging [2], material spectroscopy and sensing,
strong absorption. Instead, various crystalline and plastic security, and high-data-rate communications.
materials are used for windows, filters, lenses, etc., in quasi- Over the past few years, unprecedented progress has been
optical arrangements taking over all the advantages of made in the area of THz source technologies, which have
visible optics. This mixture of optical and microwave played an important role in opening up the possibility of
techniques is a characteristic feature of terahertz technology. using THz waves in many real-world applications.
At the same time terahertz specific devices evolved which Miniaturized electron beam sources have been demonstrated
have no counterpart in other spectral range, like impurity and the performances of the solid-state sources and
semiconductor lasers, μ-photoconductivity detectors, metal frequency multipliers have been steadily improved by
mesh filters, grid polarizers, and others. increasing their upper frequency limits and their power
The spectroscopy at terahertz frequencies is of great efficiencies. Terahertz quantum cascade lasers have

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experienced a rapid progress over the last few years. Their a dark room. The monomers were incorporated into the
output power level and operation temperatures have porous layer from Zn(C3N2(C6H5)2NO2)2(CH3OH)2 : C3H6O
remarkably increased whereas their lowest operation and Ni(C3N2(C6H5)2NO2)2(CH3OH)2 : C3H6O solutions.
frequencies have been continuously decreasing. Terahertz Afterwards, the samples were dried for several days at room
optoelectronic sources, including THz photomixers and THz temperature. The morphology of the monomer nanowires in
parametric sources have seen a great improvement in their an InP template is illustrated in Fig. 3, lower part.
performances in terms of optical-to-electrical efficiencies
and maximum output powers at frequencies above 1 THz.
New material systems have been developed for photomixer
sources allowing them to operate at optical
telecommunication wavelengths. Taking the advantage of
low-cost diode lasers and high-power fiber amplifiers and
other telecommunication optical components, it is now
possible to dramatically reduce the cost of the THz system.
II. EXPERIMENTAL SETUP
Crystalline (100)-oriented substrates of S-doped n-InP
with 500 μm thickness (prior to anodic etching) and free
electron concentration of 1.3 × 1018 cm−3 were used. The
anodization was carried out in an electrochemical double cell
as described elsewhere [5]. A four-electrode configuration
was used: a Pt reference electrode in the electrolyte, a Pt
reference electrode on the sample, a Pt counter electrode,
and a Pt working electrode. The temperature was kept
constant with a thermostat. The electrolyte was pumped
continuously through both parts of the double cell with the
help of a peristaltic pump. All equipment involved in the
experiments was computer-controlled. The area of the
sample exposed to the electrolyte was 0.5 cm2. The anodic
etching was carried out in 5 % HCl aqueous solution at room
temperature in potentiostatic regime with the following
range of values for obtaining gradient of diameter of pores:
the applied voltage linearly and exponentially decreases Fig. 1. Schematic representation of cutting membranes from the sample in
from 8.0 to 1.0 V that leads to changing degree of porosity the same anodic process.
with depth. To have a thin porous film, we applied a shock
pulse of bias from the potentiostat. The first pulse was used
to remove the disordered layer of the porous structure (see
Fig 1) and the next pulses were applied to fabricate
membranes with ordered pores which were afterwards used
in our experiments (see Fig 2). Further details of the anodic
etching process can be found in [5]. A TESCAN scanning
electron microscope equipped with an Oxford Instruments
INCA energy dispersive x-ray (EDX) system was used to
analyze the morphology and chemical composition of the
porous samples. As previously shown [5], two types of pores
can be introduced in III–V semiconductor compounds:
crystallographically oriented or ‗crysto‘ pores, and current-
line-oriented or ‗curro‘ pores. Crysto pores are usually
generated at low anodization current densities or applied
Fig. 2. SEM image of porous InP film.
voltages, the mechanism of their formation being related to
direct dissolution of the material. Curro pores are formed at The EDX analysis of coordination compounds
relatively high anodic current densities or applied voltages, demonstrates that they have fully filled the nanostructured
their growth being mediated by oxide formation and its template of n-InP along the entire depth of pores.
dissolution at the pore tip [5]. The setup used for characterization includes a THz time-
Coordination compounds with structural formula domain spectrometer, and a laser amplifier-based optical-
[Zn(C3N2(C6H5)2NO2)2(CH3OH)2] and pump THz probe spectrometer [6]. The transmission through
[Ni(C3N2(C6H5)2NO2)2(CH3OH)2] have been synthesized the sample in the time domain was recorded for each set of
and characterized by X-ray crystallography (Fig. 3, upper samples. Each sample was mounted on a piece of table
part). These complexes have pseudopolimeric structures having a hole with a diameter of 4 mm through which the
being connected to each other by hydrogen bonding (Fig. 3, transmission was measured. The terahertz electric field was
middle part). This behavior made possible the introduction linearly polarized for all measurements, and the terahertz
of these complexes in porous n-InP membranes. The beam was normally incident on the sample surface. All
complex deposition in the porous structure was carried out in measurements were performed at room temperature (Fig. 4).

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Fig. 5. THz signal from a pair of porous InP and composites samples.

Fig. 6. THz spectrum measured in air. Several strong absorption lines due to
water vapor are seen.

Fig. 3. XRD analyses of the complexes (upper part); hydrogen bonding

inside [Ni(C3N2(C6H5)2NO2)2(CH3OH)2] structure (middle part); SEM Fig. 7. Remodeled absorption spectrum. Several strong absorption lines due
image of an InP template filled with coordination compounds. The inset to water vapor are evident.
shows a top of view of the pores (lower part).

Porous InP has been taken as reference material in

studying the THz emission and it has been compared with
the same structure filled with polymer (Fig. 5) [10-12]. One
can see from the THz spectrum that polymers increase the
absorption of THz radiation (Figs. 6, 7). We suppose that the
main impact on absorption is due to the presence of metallic
atoms in this systemized metal-organic structure. Another
contribution to the absorption comes from atmospheric water
vapors, since the experiments were performed without using
a nitrogen gas chamber.
Fig. 4. Experimental setup for the investigation of THz emission from III. SIMULATION MODEL FOR BIO APPLICATIONS
porous InP and composites samples. The samples are placed perpendicular
to incident beam at room temperature. We investigated the terahertz characteristics of porous
The porous InP is one of the most promising material for films with pores filled in with polymers. Two kinds of
the fabrication of THz devices [7, 8]. Recently we have samples have been investigated: (i) clean poly- and
reported a new technology [9] for the fabrication of monomers, and (ii) the ones containing metallic particles
membranes on InP (111) surfaces that can emit ultrafast inside. We used FEM methods implying Mie theory and
coherent terahertz pulses under near-infrared optical Drude model for the description of metallic nanoparticles
excitation. The membranes irradiated by heavy noble gas Kr dispersion. The model, defined in a cylindrical coordinate
or Xe ions demonstrated enhanced terahertz emission. system, comprises a PML layer as thick as twice the
wavelength used for excitation. The simulations were made
for a single pore of 100 nm in diameter made in an A 3B5 like

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semiconductor. The pore was considered to be filled in with Medicine‖ 2438 IEEE Transactions on Microwave
a highly contrast dielectric (our polymer) in terms of electric Theory and Techniques, Vol. 52, NO. 10, Oct. 2004.
permittivity, with nanoparticles with various diameters in the [3] Xin Wu, De Li, Wei-Hua Sun, Feng Gao, Zhi-Jian
range of 10 to 50 nm dispersed in it. We defined an Zhang, and Ru-Wen Peng. „Coupling of THz Surface
excitation pulse of picoseconds replicating the LASER Plasmon Polaritons in Corrugated Stacks of Dielectric
excitation for the real samples [12]. and Semiconductor‖ PIERS ONLINE, Vol. 5, no 2, 101,
Fig. 8 represents a model for bio-applications, where the 2009.
THz radiation is reflected from the surface of porous InP. In [4] Yasser A. Hussein and James E. Spencer „Hybrid
the specular direction we have absorption from the used bio FDTD Analysis for Periodic On-Chip Terahertz (THz)
sample (in our case a chemically synthesized metal-organic Structures‖ SLAC-PUB-10908 Contributed to 2005
structure) that is going to be scanned. IEEE/ACES International Conference on Wireless
Communications and Applied Computational
Electromagnetics, April 3-7, 2005, Honolulu, HI, USA
2005.
[5] S. Langa, I. M. Tiginyanu, J. Carstensen, M.
Christophersen and H. Foell „Self-organized growth of
single crystals of nanopores‖ Appl. Phys. Lett. 82 278,
2003.
[6] A. Charles Schmuttenmaer ―Using Terahertz
Spectroscopy to Study Nanomaterials‖ Terahertz
Science and Technology, ISSN 1941-7411 Vol.1, No.1,
March 2008.
[7] M. Reid, I. I.V. Cravetchi, R. Fedosejevs, I.M.
Tiginyanu and L. Sirbu. „Enhanced terahertz emission
from porous InP(111) membranes‖ Appl. Phys. Lett.,
Vol. 86, 021904, 2005.
[8] M. Reid, I. I.V. Cravetchi, R. Fedosejevs, I.M.
Fig 8. Model of bio-samples detector Tiginyanu, L. Sirbu & Robert W. Boyd. „Enhanced
nonlinear optical response of InP(100) membranes‖
Physical Review B, Vol. 71, 081306, 2005.
IV. CONCLUSION [9] K. Radhanpura, S. Hargreaves, R. A. Lewis, L. Sirbu,
We carried out an experimental study of THz emission from and I. M. Tiginyanu „Heavy noble gas (Kr, Xe)
new synthesized polymers as well as their THz absorption irradiated (111) InP nanoporous honeycomb membranes
characteristics. We have developed a technique to obtain with enhanced ultrafast all-optical terahertz emission‖
porous InP membranes with thicknesses in the range of 30- Appl. Phys. Lett. 97, 181921, 2010.
100 μm filled in with polymers. This technique is expected [10] Alexander M. Sinyukov and L. Michael Hayden
to be useful for medical applications, for instance in „Efficient Electrooptic Polymers for THz Applications‖
detecting and processing images like a huge lattice with J. Phys. Chem. B 108, 8515, 2004.
thousands, millions, or even billions of detectors working [11] Vittorio M. N. Passaro Francesco Dell‘Olio, Biagio
simultaneously. Casamassima 1 and Francesco De Leonardis „Guided-
Wave Optical Biosensors‖ Sensors, 7, 508, 2007.
[12] V. Sergentu, D. Esinenco, L. Sirbu, I. Vodă, I. M.
REFERENCES Tiginyanu, V. Ursaki. „Rayleigh scattering of a metal
[1] S.D. Ganichev. ―Intense Terahertz Excitation of nanoparticle on a flat dielectric surface‖ Tereahertz &
Semiconductors‖ Terahertz Science and Technology, Mid IR Radiation: Basic Research & Practical
ISSN 1941-7411 Vol. 1, No 3, Sept. 2008. Applications The NATO Science for Peace and Security
[2] Peter H. Siegel. „Terahertz Technology in Biology and Programme, Photonics Society, Turunç-Marmaris,
Turkey 3-6 Nov. 2009.

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Nanolamellar Structures of Oxide-AIIIBVI:Cd

Semiconductors Type for use as Detectors of
Radiation in the UV Spectral Region
L.DMITROGLO1, D. UNTILA1, P.CHETRUSH1, I. EVTODIEV1, Iu. CARAMAN2,
G. LAZAR2, V. NEDEFF2
1
Moldova State University, 60 A. Mateevici Str., Chisinau, MD-2009, Republic of Moldova
2
University of Bacau, 157 Calea Marasesti, RO-600115 Bacau, Romania
[email protected]
Abstract – In the paper, optical and photoelectrical properties of GaSe and InSe single crystal films of 10-5÷10-
7
m submicron thickness and of semiconductor-native oxide structures obtained by annealing at (450÷700)°C
in a normal atmosphere, are studied.
The absorption spectrum of InSe lamella as well as of GaSe lamella in the energetic range from the red
threshold up to 4,5 eV contains three bands with a rapid increase of the absorption coefficient which varies in
the limits of (100÷106) cm-1. At the absorption coefficients of (10 0÷102)cm-1 the indirect optic transitions are
present.
At the energies higher than 1,25 eV and 2,01 eV for InSe and GaSe respectively the light absorption are
determined by the direct optical transitions in the centre of the Brillouin zone and at the energies higher than
3,0 eV also by the direct optical transitions in the points of the bands high symmetry.
The resistive photosensitivity bands cover the spectral range Eg≤ hν ≤ 4,5 eV for lamellar photoresistors in
which electric field EC6. The resistive photosensitivity band width could be controlled by the lamella
thickness for d ≥1μm. The open circuit voltage spectral distribution is analysed from which results that at the
oxidation temperature of 700°C in GaSe layer at the heterojunction interface the defects are formed on
which the charge carriers, collected in the junction, are dissipated. The noneequilibrium charge carrier free
path is of 0,8 μm.

Index Terms – GaSe, InSe, semiconductor heterojunction, oxide films, nanolamellar structures.

These along with low surface states concentration determine

I. INTRODUCTION
one of the priority
The actual tendencies of the photonics and
optoelectronic devices development are determined by the
directions of these compounds using as a photosensitive
wide scale implementation of semiconductor materials.
element in the radiation receivers in the visible-UV region of
Among the perspective materials for nanoparticles
spectrum.
fabrication and particullary of nanolamella are compounds
of lamellar class semiconductors of AIIIBVI type, a typical II. THE STUDIED SAPLES AND EXPERIMENT
representatives of which GaSe, GaS, InSe and GaTe are [1- METHODICS
4]. ɛ-GaSe and -InSe single crystals were grown by
These compounds single crystals are formed from Bridgman method. p-InSe crystals were obtained by doping
lamellar packing of Hal-Me-Me-Hal with strong chemical with 0,2  of Cd during chemical compound process of
binding of atoms inside of packing and weak binding (of synthesis. Single crystals were cuted in cylindrical blocks
Van-Der-Waals type) between packing [5]. The chemical with the thickness of 10-12 mm and then cleaved in the
binding anisotropy of the atomic plans in GaSe and InSe lamella with the thickness of hundreds of nm up to 0,3-0,5
compounds allow by cleaving to obtain plan parallel lamella mm. For to simplify the cleavage procedure of the
with smooth surface at atomic level, of low surface states nanometric thickness lamella, the cylindrical blocks were
density [6]. At a normal atmosphere the gas molecules irradiated with ultrasound during 15-20 min. The sound
absorption from the atmosphere occurs and at the same times waves of 0,22 MHz frequency were obtained by an optical
an oxides layer is formed [7]. The oxides variety from GaSe modulator made from single crystal SiO2. The obtained
and InSe compounds surface could be limited to In2O3 and InSe:Cd samples were oxidated in normal atmosphere at
Ga2O3 stable oxides by high temperature annealing of the
temperatures 520°C and 580°C respectively. The heat
sample [8-9]. The oxide layer from the lamella surface of p-
treatment duration was chosen on the base of testing and
GaSe and p-InSe:Cd is electrically positive, the fact which
heterojunctions with the stable in time photoelectrical
leads to the electron afinity decrease relative to the freshly
parameters under the intense illumination with the radiations
cleaved surface by 0,35 eV in GaSe [5]. The high native
from the visible region of spectrum were chosen.
defects concentration in lamellar crystals, determined by the
The electrical contacts for Hall measurements were
atomic plans arrangement in lamellar packing and of
formed by evaporation of In thin layers on (001) surface of
elemntary packing to one another leads to a stability of
single crystal GaSe and InSe lamella. The characteristics of
electrical and optical properties to the ionizing radiation.
p-GaSe:Cd and p-InSe single crystals determined from Hall
measurements are given in the Table 1.

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Spectral dependence of the photocurrent in the direction optical transitions occur at the energies hν≥1,2 eV in
perpendicular to C6 axis and of photovoltage in lamellar InSe:Cd and hν>2,0 eV in GaSe:Cd.
InSe-In2O3 and GaSe-Ga2O3 heterojunctions was measured The more pronounced increase of the absorption
coefficient at the photons energy hν >3,2 eV which is
TABLE1. ELECTRICAL PROPERTIES OF CD DOPED WITH GASE,
observed (fig.1) both in initial lamella as well as after their
INSE
oxidation is related to the opening of new channels of
Simple Conductivi

concentrati

Activation
absorption in the points of high symmetry of Brillouin zone

on (cm-3)

Mobility
(cm2 V-
energy
ty tipe
(points X, L,Σ).

(eV)
Hall

S)
1 1
Spectral dependencies of photocurrent density in
InSe:Cd and GaSe:Cd lamella with low thickness are given
InSe:Cd p 8,5·1014 0,4 28 in Fig.2. The electric field is applyed along the direction
perpendicular to the symmetry axis C6. As one can see from
GaSe undoped p p-2·1014 0,56 3845
the comparison of Fig.1 and Fig.2 the photocurrent density
GaSe-0,01Cd p p-2·1015 0,24 2035 in InSe:Cd photoresistors in the photons energy interval
GaSe-0,1Cd p p- 0,24 - from the fundamental band edge up to 4,0’4,1 eV is
4,2·1015 increasing along with the absorption cofficient  increase.
GaSe-0,2Cd p p- 0,24 - The photocurrent density is deacreasing by an order of
5,7·1015 spectral magnitude 1,2’2,4 eV at the lamella thickness
GaSe-0,5Cd p p- 0,22 1220 decrease from 7,3 μm to 0,8 μm. If to take into account that
8,3·1015 the absorption coefficient in this spectral region does not
on a unit on the base of MDR-2 monochromator. The depend on the sample thickness (the InSe lamella surface
photocurrent through the sample in the regime of perfection excludes the possibility of structural layers
photoresistor as well as through semiconductor –oxide defected at surface formation), then one can observe that in
heterojunction was calculated by potential difference on the the sample 10 of the incident light is absorbed. The
load resistance Rs. The optical and photoelectrical tendency of photocurrent density decrease at the photons
characteristics of the samples in the regime of energy hν>4,2 eV could be explained by the fact that in this
photoconductivity are connected by relation [10]: spectral region the light is absorbed in a thin layer at the
I ph sample surface where the none-equilibrium electric charge
G (1)
eWlI 0 1  R 1  exp  d  carriers recombination rate is higher than in the sample
were the amplification coefficient, τ- is the minority charge volume. The thore rapid decrease of a photocurrent density
carriers life time, tr-the electric charge "e " (electron) time of in this spectral region indicates that the depth of the light
transportation through the sample, W, l- width and lenght of penetration in the sample d < Ln (Ln-electron free path in p-
the sample, I0-the incident light beam intensity, R,  - InSe) and more evident appears the recombination through
reflection and absorption coefficients, d –the sample the states on the both surfaces of the sample.
tickness. The photocurrent spectral dependencies in p-GaSe:Cd
The open circuit voltage of a heterojunction lamella with the thickness of 14,2 μm and 0,9 μm (Fig.3) are
illuminated by a light bean of the intensity I0 is given by identical by their form for the same of p-InSe:Cd. The
relation [10]: monotons photocurrent increase in the photons energy of
1,5’1,9 eV is a results of none-equilibrium charge carrier
1  R I 0 1  exp  d 
   
  generation at a indirect optical transitions.
kT   L n   The photocurrent spectral dependencies in InSe and GaSe
V ln1   (2) lamella are in good correlation with the formula 1, the fact
 eV D  
 
e  D p n p0
 N a v p  S p exp    which indicates that at the electric field in the sample
 Ln  kT  
 10’100 V/cm the amplification coefficient of charge carriers
Were k-is Boltsman's constant, T-temperature, Sp-the holes G is a constant value and at the same time the surface
recombination rate, L0-the electron free path in p-type recombination rate of charge carriers in the single crystal
semiconductor, VD-the applied to the junction voltage. GaSe:Cd and InSe:Cd lamella is rather low.
It is well known that the electrical conductivity of
III. EXPERIMENTAL RESULTS Ga2O3 films depends on oxygen atoms concentration as a
The elementary packing consisting of the halogen and dopant. At the oxidation at temperatures (450-500)°C Ga2O3
metall atoms planar arrangement of Hal-Me-Me-Hal type in layers of high electrical conductivity are obtained. The
ɛ-GaSe and -InSe crystals have thicknesses of 0,8 -0,85 nm majority charge carrier (electron) concentration is of
[11-12]. The presence of the weak chemical binding between (1017’1018)cm-3 and their mobility of (40’80) cm2/V·s [13].
chalcogenide plans allow obtaining of the lamella with the At the annealing at high temperature (900°C) the dielectric
perfect surface and thicknesses needed for measurements of Ga2O3 film could be obtained.
the absorption coefficient with a constant accuracy with the The open circuit voltage spectral distribution normed to the
value from the units of cm-1 up to 105 cm-1. The absorption number of incident photons for heterojunctions with Ga2O3
spectra of the lamella of InSe:Cd (curve 1) and GaSe:Cd dielectric film and oxide film obtained at 480°C (curve 1)
(curve 2) and of lamella with a native oxide on the surface and 700°C (curve 2) is given in Fig.4.
are given in Fig.1. As one can see the Uoc=f(hν) dependencies for the
In the region of 1,10’1,15 eV in InSe and 1,5’2,0 eV in analyzed structures are in good correlation with the formula
GaSe  (hν) dependencies are determined by the indirect

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(2). The rapid increase of the open circuit voltage in the Fig.3. Photocurrent density spectral dependence in GaSe:Cd lamella with
the thickiness of 14,2 μm (curve 1) and 0,9 μm (curve 2) at room
photons energy (1,85’2,03) eV is due to the exponential
5 temperature.
10
So at the oxidation temperature of 480°C the concentration
of the formed defects in the presence of Ga2O3 oxide does
10
4
not exceed their concentration on a free surface of GaSe
lamella. The open circuit voltage rapid decrease at the
photons energy hν>4,0 eV is due to the increase of the
10
3 reflection coefficient from Ga2O3 layer surface (n≈3,3 [14])
-1
, cm

pZnSe and from Ga2O3-GaSe interface due to the optical transitions

p-GaSe in the X point of the Brillouin zone.
2
pZnSe-In2O3 The open circuit voltage spectral dependence of
10 p-GaSe-nGa2O3
nGa2O3-iGa2O3-pGaSe structure with an oxide film made at
700°C represents a curve with the maximum at hν≈2,5 eV
10
1 and a monotonous decrease for photons energy hν>2,5 eV.
The minority charge carriers free path in the none deformed
1 2 3 4 GaSe lamella, detrmined from the photocurrent relaxation
F h, eV analysis of the illumination of the sample back with the short
ig.1. Absorption spectra calculated according to formula (1) from the pulses of the monochromatic light (by method described in
measurements of transparency of p-InSe:Cd lamella (curve 1), In2O3-InSe [14]) is comensurable with the GaSe lamella thickness in the
(curve3), p-GaSe (curve 2), p-Ga2O3-iGa2O3-pGaSe (curve 4). heterojunction. For the none-equilibrium charge carriers free
increase of the absorbtion coefficient in the region of the path of this value the open circuit voltage Uoc should be in a
fundamental band edge (Fig.1, curve 2). The monotonons direct accordance with  (hν) dependence. The
increase of the open circuit voltage with the photons energy monotonous decrease of Uoc in the region of photons energy
increase in the region of (2,03’4,1) eV in the heterojunction hν>2,5 eV with the tendency of saturation at high energies
fabricated at the 480°C indicates to a low concentration of indicates to the lower values of the generated carriers
recombination centres for the minority charge carriers at diffusion lenght in GaSe lamella.
Ga2O3-GaSe the result which is in a good agreement with From formula (2) one can see that Uoc(h ν) dependence
the photoconductivity spectrum. has a tendency of decreasing with the incident radiation
-1
10 wavelength increase for a constant recombination rate at the
interface it de curvature depth of the bands in GaSe d<Ln.
For  dn<<1 and Sn independent on the photons energy
Ratio photoccurent/phonon, arb. un.

from (2) one can see that the open circuit voltage
10
-2 monotonously decreases along with the [15] factor.

I 0 / Ln  1 (3) 
1 By varrying the monochromatic radiation intensity ΔI0 so
2
that to maintain constant the open circuit voltage value, the
10
-3
minority charge carriers free path could be determined.
The results of measurements of intensity variation ΔI0 of
the incident beam as a function of inversly of the absorption
coefficient at energies from range (3,0’ 4,0) eV are
0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0 presented in Fig.5. The relatively low free path Ln value of
h, eV 0,8 μm indicates that at 700°C at Ga2O3-GaSe interface a
Fig.2. The photocurrent normed to the number of incident photons as a native structural defects and new phases (Ga2Se3, GaO) are
function of the photons energy for InSe:Cd lamella of the thickness of 7,3 formed which serve as dissipation and recombination centres
μm (curve 1) and 0,8 μm (curve 2).
of non-equilibrium charge carriers on GaSe lamella surface.
The band diagram of nGa2O3-iGa2O3-pGaSe:Cd
-1
10 heterojunction calculated on the base of absorption and
photoconductivity spectra and measurements of charge
carriers concentration in GaSe and Ga2O3 lamella is brought
Photocurrent density, arb. un.

1
in Fig.6. The band curvature value in the pGaSe-iGa2O3
-2
10 1 contact region was determined in [14] from the
2 measurements of C-V characteristics.
2
IV. CONCLUSION
By decreasing the GaSe and InSe single crystal lamella
-3
10 thickness one can control the transmission band of them.
The absorption fundamental band edge of InSe and GaSe
single crystal lamella is determined by the indirect optical
1,5 2,0 2,5 3,0 3,5 4,0 4,5 transitions with the absorption coefficient  <100 cm-1.
h, eV By varrying the GaSe and InSe lamella thickness in the
submicron range one can fabricate the radiation detectors
with a sensitivity in the UV-region of the spectrum.

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1 The recombination centres and surface states density in

the oxide-GaSe region depends on the surface oxidation
1 temperature. The surface defects concentration does not
change at the heat treatment at 480°C. At the GaSe surface
Open circuit voltage, arb. un.

2 oxidation temperature of 700°C in the oxide-GaSe contact

region structural defects which diminishes the minority
0,1
charge carrier free path up to 0,8 μm are created.

1
REFERENCES
2
[1] Naoya Okamoto, Tsuyoshi Takahashi, Hitoshi Tanaka,
0,01 Nonalloyed ohmic contact to n-GaAs with GaS/GaAs
quasi-metal-insulator-semiconductor structure, Appl.
Phys. Lett., vol. 73, no. 6, 1998, p. 794-796.
1,5 2,0 2,5 3,0 3,5 4,0 4,5 [2] Naoya Okamoto, Hitoshi Tanaka, Characterization of
h, eV molecular beam epitaxy grown GaS film for GaAs
Fig.4. Open circuit voltage spectral distribution of pGa2O3 iGa2O3 – nGaSe surface passivation, Materials Science in Semiconductor
heterojonctions with a layer of native oxide obtained at 480 ºC (curve 1) Processing, vol.2, no.1, 1999, p. 13-18.
during 90 min and at 700 ºC (curve 2) during 90 min in a normal
atmosphere. The GaSe lamella thickness is of 11,5 μm [3] Dai Z.R., Chegwidden S.R., Rumaner L.E., Ohuchi F.S.,
Microstructure evolution of GaSe thin films grown on
GaAs(100) by molecular beam epitaxy, J. Appl. Phys.
3.5
vol. 85 , no. 5, 1999, p. 2603-2608.
[4] Jonathan A.A., Aaron A.B., Fumio S.O, Marjorie A.O.,
3.0 Chemical passivity of III-VI bilayer terminated Si(111),
Illumination intensity, arb. un.

Applied Physics Letters., vol. 87, no. 17, 2005, 171906,

2.5 6 pages.
[5] Бакуменко В.Л., Ковалюк З.Д., Тишин Е.А., Чишко
2.0 В.Ф., Влияние ―старения‖ поверхности
моноселенидов галлия и индия на работу выхода и
1.5 фотоэлектрические свойства // Физ. электроника.
1979. № 19. С. 123–126.
1.0 [6] R.H. Williams, A.J. McAvej, S. Vac. Science
Technology, 2 (1972), 867.
0.5
[7] Драпак С.И., Гаврилюк С.В. , Ковалюк З.Д., Литвин
О.С., Собственный окисел, возникающий на
поверхности скола селенида галлия в результате
0.0
-2 0 2 4 6 8 10 длительного хранения , ФТП , том. 42, вып. 4 , 2005,
1/, m
c. 423-430.
0.8m [8] O.A.Balitskii, J.M.Stakhira, Thermal oxidation of cleft
Fig.5. Determination of diffusion free path in nGa 2O3 iGa2O3 – pGaSe with surface of InSe single crystal , Materials Science and
a native oxide layer made at 700ºC during 90 min in a normal atmosphere.
Engineering: B, vol. 56, no.1, 1998, p. 5-10.
[9] N.N. Berchenko, O.A. Balitskii, R.V. Lutsiv, V.P.
Savchyn and V.I. Vasyltsiv, Mater. Chem. Phys. 51
(1997), p. 125.
[10] I. Marfaing, Photoconductivity photoelectric effects.
In.Handbook on Semiconductors. Ser.ed.T.S.Moss
volume ed.701 M. Balkouschi: 1994-Elsevier p.758.
[11] Terhell S.C., Lieth R.M., Phys Stat Sol A 10 (2), (1982)
529.
[12] С.А.Семилетов. Кристаллография, 3 ( 1958 ) 288.
[13] N. Suzuki,S. Ohira, M. Tanaka,T. Sugawara,K.
Nakajima, T. Shishido, Phys Stat Sol , Vol.4 ( 7), (2007)
2310-2313.
[14] Sergiu Vatavu, Petru Gaşin, The analysis of current
flow mechanism in CdS/CdTe heterojunction, Thin
Solid Films, vol. 515, no. 15, 2007, pag. 6179-6183.
[15] A.M. Goodman, J.Appl.Phys.32 (1961)2550.

Fig.6. Band diagram of nGa2O3-iGa2O3-pGaSe:Cd heterojunction

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Approximation of MOSFET Transistor

Characteristics in Micro- and Nanoelectronics
1
Alexandr PENIN, 2Anatoli SIDORENKO
Institute of Electronic Engineering and Nanotechnologies "D. Ghitu ",
Academy of Sciences of Moldova
1
[email protected], [email protected]

Abstract – The base approach, giving a wide class of functions convenient for engineering practice for the
formal description of I-V characteristics of the MOSFET transistors, is developed. The similarity of I-V
characteristics of semiconductor devices and the quasi-resonant converter of voltage is an approach basis.
The offered functions have certain physical sense that allows modifying purposefully them for the flexibility
of their form.

Index Terms – approximation, I-V characteristic, model, transistor.

models are convenient for the analysis of an operating

regime of the transistor and the concrete equipment (the
I. INTRODUCTION
amplifier, generator, and modulator) and which can be
Circuit simulation is an important component by working
specified under the problem and transistor passport data.
out and research of semiconductor devices and equipments
The limited number of functions is available in an arsenal
on their basis. Let us result a number of the problems
of modern mathematics, which can be used for construction
considered in the book [1].
of compact models. Among them there are no smooth
In connection with transition of semiconductor technology
functions which could give the simple and exact description
in nanometer area (is more exact, at topological norms less
of the transistor in all regimes of its work. Therefore, for
0,18 µm), a set of new parasitic electric effects has appeared,
smoothness maintenance it is necessary to use
which were observed earlier only in analog integrated
Smoothing functions have no physical sense and can be used
circuits (IC). For this reason, the urgency of exact (SPICE-
only for formal adjustment of model to object.
like) circuit simulation has sharply increased.
Here are some examples.
Physical processes in the MOSFET transistors are
For modeling of area of moderate inversion, the
described by difficult system of the equations. It is used only
interpolation by smooth function between modes of strong
for device-technological modeling of semiconductor devices.
and weak inversion is used. Using smoothing function
 
Therefore, compact models are created by use of the 2
assumptions, which simplify system of the equations to F (v)  Ln(1  e v / 2 ) ,
receive the analytical solution, simple enough for use in it is possible to receive uniform expression of the
programs of circuit simulation characteristic. But the received equations can not be
Physical compact models are synthesized by analysis of inverted analytically for obtaining the explicit dependence of
various areas of semiconductor structure for the purpose of a currents from voltage as it is required in circuit simulation
substantiation of simplifying assumptions which would programs.
allow receiving the analytical solution of the equations of a
continuity, transport and Poisson. Such approach allows to
establish physically well-founded assumptions and to
establish connection of parameters of model with the
geometrical and technological transistor‘s parameters.
Requirements of simplicity and computing efficiency
compel modelers to move on the brink of its reliability.
Therefore, the model of transistors is developed for
technology of 0,25 µm, is already unsuitable for a 0,18 µm.
The model, intended for circuit simulation, should be simple
and have simple procedure of the parameter extraction.
The opposite method of synthesis consists that physical
processes in the device are not analyzed at all. Instead, the
equations of the two-port network are chosen by an expert
way, which behave concerning external terminals precisely
how the real MOSFET transistors. Such models are called as Fig.1. Example of smoothing function with various values of parameter ε of
formal. smoothing
Synthesis of the formal models for modeling IC is not
For adequate modeling of analog and radio-frequency
considered now perspective, as it does not allow establishing
circuits, the smoothing functions should provide smoothness
the connection of parameters of model with technical
not only characteristics, but also their derivatives.
process parameters. But it is possible to notice that formal
Smoothing functions of a kind

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
X ( x)  0,5 x  x 2  4 2 ,  I D (VDS )  C  M (1  VDS ) th (VDS )
Four parameters of this equation (С, Μ, λ, α), are defined by
are most extended. Where ε is the parameter, defining
smoothness of transition from asymptote Х(х) = 0 to an means of a straight extraction technique for each value of
asymptote Х{х) = χ, as is shown in Fig. 1 voltage VGS . Then each of parameters is interpolated by a
For smoothing of linear area with saturation area, the
smoothing function is used, as is shown in Fig. 2 voltage VGS polynom, factors of which are stored in the
x x0 table. For example, for a template
y ( x)  ,
I D  I pk (1  th( )) (1  VDS ) th (VDS )
2m
x 2 m  x02 m
the equation parameters  ,  ,  are tabular functions
from voltage VGS , VDS . The I pk is a drain current at which
the maximum of transfer conductivity is observed. However,
this way does not allow receiving approximation of high
accuracy because of insufficient flexibility of a template
In connection with stated, interest represents a finding of
functions for construction of compact models as smoothing
functions and templates. And, these functions should have
certain physical sense that would allow modifying
purposefully them for the flexibility of their form. In the
present message some results [2] which develop the
approach [3, 4] are presented.
Fig.2. Example of smoothing function with various values of parameter m II. РАЗРАБОТКА БАЗОВОГО ПОДХОДА
of smoothing
Similarity of the load characteristics of the quasi-resonant
Presence of smoothing functions is one of essential converter of voltage with the characteristics of transistors is
limitations of modern compact models used as a basis of the offered approach. The received well-
For radio-frequency circuits, SPICE - like methods of founded expression of characteristics of the quasi-resonant
modeling have appeared unsuitable. converter, having physical sense, allows describing the
First, at performance of the small-signal analysis SPICE symmetric and asymmetrical transitive characteristic of the
program carries out a linearization of nonlinear elements, transistor.
and, thus, nonlinear distortions or transformation of spectra The equivalent generator of the quasi-resonant converter
of signals at once drop out of area of applicability of such contains the nonlinear internal resistance Ri1 ,which
analysis
Second, if for this purpose to use the analysis of transients dependence corresponds to a straight line 1 is shown in Fig.
in a mode of the big signal, the problem becomes almost 3.
unrealizable as the integration step should be much less
period of carrier frequency, and at the same time the
possibility of modeling of the several periods of modelled
fluctuations is necessary. Thus, total number of steps of
modeling becomes unacceptably large-scale.
Therefore, convenient analytical approximations of the
transitive characteristic by one function represent an interest.
Models on the basis of the hyperbolic tangent function,
focused on the analysis of the intermodulation distortions in Fig.3. Equivalent generator - a) and dependences of internal resistance of
radio-frequency circuits, are known. Its feature is absence of typical energy sources (1- quasi-resonant converter, 2-voltage source, 3-
current source-) - b)
necessity for smoothing functions. A shortcoming is that the
model is based on empirical dependences and adjusted Let us receive uniform expression of the characteristic for
parameters. all area of change of the load voltage. For this purpose,
Alternative approaches to modeling, as tabular models, linear dependences in the form of two straight lines 1 for
are known also. Their basic appointment is the modeling areas are replaced by the hyperbole equation that is shown in
of electric circuits with devices for which analytical models Fig 4,a.
are not developed yet. For reduction of the size of tables, the In case of hyperbolic dependence Ri1 (u i ) , the equation
templates are used in particular, because it is enough to store
parameters of scaling of a template instead of storage of of the I-V characteristic will become:
points of the curve. Difference of a template from a formal i1 (u i ) u i / AEr
 .
1  u i / AEr 
compact model consists that a template uses only the scaling I1 A 2
and shift for adjustment to experimental data and does not
contain other parameters. The template is chosen in advance The plot of this curve has a typical appearance on Fig. 4,b.
with necessary properties (differentiability, monotony,
absence of oscillations of the highest derivatives).
The next function can be a template example:

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approximation of the transfer characteristic I D (U GS ) of the

transistor. Then, in initial system of coordinates I D 0 DS U GS
whith the actual curve, the system of coordinates i 0 u i is
restored.Example: the transitive characteristic of the
transistor STE26NA90 is resulted on fig. 6, 7.

Fig. 4. Dependence of internal resistance as a hyperbole-a) and the

symmetric characteristic in all area of change of voltage-b).

The form of the received curve is closed to the typical

I D (U GS ) of the field transistor in
transfer characteristic
system of coordinates I D 0 DS U GS . Let us consider the
base approach to the description of transistor characteristics.
At first, the asymmetrical characteristic in the first and the
third quadrantis is considered. In this case, the
hyperbole Ri1 (u i ) will be asymmetrical relative to
voltage u i in Fig.5,a. Fig.7. Actual values –crosses,offered symmetric approximation - continuous
line,offered asymmetric approximation- rhombuses

III. CONCLUSION
The carried out analysis of variety of known
approximating functions of characteristics of transistors
shows that:
- their formal character and absence of physical sense of the
entering parameters does not allow to modify them
purposefully,
-difficult enough expressions complicate analysis, lead to the
solution of the transcendental equations,
The base approach and the whole class of convenient
Fig.5. Asymmetrical arrangement of a hyperbole of internal resistance – а) expressions for approximation of characteristics of semi-
and asymmetrical I-V characteristic in the first and the third quadrantis -b) conductor devices are offered. The presented examples
show possibility of direct analytical calculations of operating
Asymptotes 0 y, 0 x form the rectangular system of regimes of transistors.
coordinates turned on a corner  relative to the system of
REFERENCES
coordinates Ri 0 ui . [1] V.V. Denisenko, Compact SPICE models of MOSFET
transistors in micro- and nanoelectronics. Moscow,
Physmathlit, 2010.
[2] Penin A. Modeling of electronic characteristics of
power transistors and photo-electric converters in
linearly-hyperbolic approximation. Thesis of doctor of
the technical sciences, Chisinau, Moldova, 2011,160 p.
Available: http://www.cnaa.md/ru/thesis/18230/
[3] Penin A. A., Sidorenko A. S. «A convenient model for
I-V characteristic of a solar cell generator as an active
two-pole with self-limitation of current». International
Journal of Electrical and Information Engineering,
2009,vol.3, nr.4, p.214-218. Available:
[4] http://www.waset.org/journals/ijeie/v3/v3-4-37.pdf.
[5] Penin A., Sidorenko A. «Generalized hyperbolic model
for I-V characteristic of semiconductor devices». The
Fig.6. Symmetric approximations:actual values –crosses, hyperbolic tangent
6th International Conference on Microelectronics and
- 1,offered approximation – 2
Computer Science. Chishinau, october1-3, 2009, vol.1,
Then the quadratic equation turns out: pp. 69-72.
a12u i2 a11u i2
i2  2 i   0.
a 22u i2  a33 a 22u i2  a33
Let this asymmetrical curve in Fig.5 would be used for

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Electronic Hydrostatic Transducer with Digital

Output
V. SMYSLOV, V. YAKUNIN, I. BELOTSERKOVSKII, and A. YAKUNIN
Institute of Electronic Engineering and Nanotechnologies "D. Ghitu"
E-mail: [email protected], [email protected]

Abstract – The TPH-485-0,06 submersible level transducer of hydrostatic pressure is a general-purpose

sensor for measuring the level of fresh water or other mildly corrosive liquids.
The TPH-485-0,06 submersible level transducer can be used to measure the water level in reservoirs, lakes,
open flow channels, and weirs as well as the groundwater level of boreholes.
Relatively low water levels can be measured using the TPH-485-0,06 submersible level transducer despite
its diameter of 24 mm. This is possible by incorporating a highly sensitive miniature silicon diaphragm with
a very thin isolation membrane back filled with silicone oil.

Key words – hydrostatic pressure transducer, groundwater level of boreholes, RS-485 interface

I. INTRODUCTION
The urgency of measuring changes in the level and
temperature of liquids in wells and tanks has led to the
necessity to develop a high-precision hydrostatic transducer.
Hydrostatic level transducers are devices that can monitor
and control the level of liquid (water, oil, fuel, etc.).
A long-term monitoring of water level and temperature in
reservoirs, water storage basins, lakes, rivers, and
geotechnical boreholes is of greatest interest for Moldova.
II. MAIN BODY
At present, pressure transducers that use integrated
sensing elements based on single-crystal silicon are the most Fig. 1. Physical configuration of the TPH-485-0,06 transducer.
in demand. This is caused by the fact that silicon converters The hydrostatic pressure exerted on the isolation
have an order of magnitude higher temporal and temperature membrane of the pressure module and the temperature of the
stability, low hysteresis, high sensitivity and repeatability as case are converted to analog electrical signals. Further, the
well as high dynamic characteristics, which make it possible signals are transmitted to a precision multichannel analog-
to respond to rapidly changing pressure at a high rate. digital converter with a built-in instrumentation amplifier
Therefore, to design a highly sensitive hydrostatic that provides a high degree of resolution. After the
transducer, we selected a Honeywell excess pressure module amplification and conversion to digital code, the signals
as a sensing element. The module has a passive from the ADC come to the microcontroller. The
compensation for zero drift and output signal in the range of programming of the microcontroller and the program
operating temperatures of 1 to 80°C. correction are performed through a separate access
A transducer design was developed, and a prototype was connector.
prepared. The transducer is a leakproof construction that Below, we represent the electronic circuit diagram of the
consists of a sensitive pressure module, a measuring unit, transducer.
and a metal case. The measuring unit includes an analog- Here DD is the pressure transducer; Dt is the temperature
digital converter (ADC), a microcontroller, and an RS-485 transducer; ACD is the precision multi-channel analog-
interface driver. Via a four-wire flat cable, the pressure digital converter; Mp is the microcontroller; RS485 is the
module is connected to a circuit of amplification and RS-485 interface converter; Uref is the reference-voltage
processing of electric signals. An access hole is made in the source; St is the voltage stabilizer; Con1 is the connector for
base of the module for the interaction of the back side of the power supply and digital data transmission; Con2 is the
transducer's membrane and the atmosphere. Via a leakproof access connector for programming the microcontroller; and
inlet, a special cable is connected to the outlet of the P atmosfer is the air-operated channel for the interaction
electronic unit. The cable contains wires for connection via with the atmosphere.
the RS-485 interface, wires for supplying power, a screen, The microcontroller provides an additional compensation
cores for suspending, and an air-operated channel for for temperature zero drift and measurement range using
equalizing the pressure of the nonoperating side of the information from the temperature transducer, which is in
sensitive element with atmospheric pressure. A cable with a contact with the case of the transducer.
length of 20 m was used. In addition, using the developed program, the
microcontroller performs the linearization of the calibration

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characteristics of the pressure module, the normalization of

measured signals, and the output of data in different units of
measurement: in kPa and mm of water column for pressure
and in degrees centigrade for temperature. Corrected data are
further transmitted via a noise immune RS-485 interface in
the format of the Modbus RTU industrial communication
protocol for devices of the collecting and recording of
measured environmental parameters.

Fig. 3. TPH-485-0,06 transducers with a cable and a coil.

TABLE 1. COMPARATIVE SPECIFICATIONS FOR THE PROTOTYPE

OF THE TPH HYDROSTATIC TRANSDUCER AND THE DL/N LEVEL
CONVERTER
Units of
Parameters TPH DL/N
meas.
Measured excess 0 ’ 10
kPa 0 ’ 100
pressure kPa 0 ’ 2500
0 ’ 1000
Water level mm H20 22’10000
0 ’ 250000
Operating
5 ’ 50 -5 ’ 50
temperatures
°С
Measured
1 ’ 85 -5 ’ 50
temperatures
Interface Digit. RS-485 RS-485
Li-bat. 3,6
≤100m – 1
DC supply voltage V 4’6 b.
>100m – 2
b.
Power
mW ≤ 120 -
consumption
Current
mA ≤ 20 -
consumption
Basic percentage
% /FS ≤ 0.02 0.1
pressure error
Basic temperature
°С ≤ 0.2 +/- 0.25
error
Communication Modbus
- -
protocol RTU
Zero drift in the
range of operating Pa ≤ 20 -
temperatures
Absolute pressure
Pa ≤ 10 -
error
Absolute level
mm H20 ≤1 -
error (10 to 40°С)
Pa ≤2 -
Resolution
mmH20 ≤ 0.2 -
Dimensions mm Ø 32х185 Ø24×205
Fig. 2. Electronic circuit diagram of the transducer. Weight kg ≤ 0.45 0.56
This protocol is open and has already become a de facto Cable m Order ≤ 300
standard for the industry of digital devices. According to Protection class - IP68 IP68

experts, more than 40% of the applications of industrial

data exchange use the Modbus protocol for the
communication between objects. In addition to this, it should

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be noted that almost all modern SCADA-systems support III. CONCLUSIONS

this communication protocol. In conclusion, we can note that the developed TPH
Engineering tests of the prototype of the TPH-485-0,06 hydrostatic transducer is more precise in comparison with
transducer with a cable and a coil were performed; the counterparts; this will make it possible to study changes in
results are shown in Table 1. The table also lists the water level in wells and reservoirs and to use this transducer
specifications of one of the best analogues, i.e., a DL/N in water level observations in wells for finding hydro-
high-precision hydrostatic transducer (STS, Switzerland). geodynamic earthquake precursors in the republic.
Comparing and analyzing the engineering data of the TPH
REFERENCES
and DL/N transducers, we can state for certain that the basic
[1] Smîslov V., Iacunin V., Scutelnic E., Beloţercovschii I.,
percentage pressure error for the developed transducer is
Parhomenco V., Traductor de presiune excedentară şi
almost 5 times less than that of the DL/N transducer. This
temperatură cu ieşire digitală TPSM-10. Simpozion
will make it possible to determine the change in the water
Internaţional 17.09.2005 AŞ Moldova.
level in boreholes with an accuracy better than 1-2 mm H2O.
[2] Smîslov V., Iacunin V. Gauge pressure transducer TP-
The exchange of data on water level and transducer
12E2-10, 4th International conference on materials
temperature with the information system is carried out via an
science and condensed matter physics, abstracts, 23-26,
RS485 interface (Modbus RTU protocol). Using a system of
Septembrie 2008, p. 194, Chisinau, Moldova.
data collection and transmission via the GSM network, it is
[3] Данные об уровне подземных вод на картах и
possible to monitor the condition of wells and reservoirs in
графиках. Гидрогеология. Курс лекций
real time scale, which will give the possibility to rapidly
Стэндфордского университета.
respond to changes in the level and temperature of
[4] Копылова Г. Н. Оценка сейсмопрогностической
groundwater.
информативности данных уровнемерных
наблюдений на скважине Е1, Камчатка (по данным
наблюдений 1996-2007 гг.). Труды Камчатского
филиала Геофизической службы РАН.

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Wave Model as a Physical Basis of an Algebra

of Bio- and Nano- structures
Bettin MIRONOV
Technical University of Moldova
[email protected]

Abstract – Bio- and nano- structures have a feature in common – both display a long-range order over the
distances significantly larger that the dimension of atom. While this cannot be explained on the basis of the
Bohr atom model or quantum mechanics, the formation of complex long-range order structures can be
explained in terms of wave model - waves spread all over the universe and can form complex interference
structures. The set of waves can be considered as a universal algebra’s generating basis, and the long-range
structures can be regarded as elements of this algebra, generated by the set of waves. However, the wave
model presupposes the existence of a carrier wave medium. To resolve the apparent contradictions with
modern physics, it is shown that the wave model is consistent with the theory of relativity and Maxwell's
equations. The last part is devoted to discussion of the stability mechanism of spherical waves and pathways
formation of complex ordered structures.

Index Terms – bio-structures, carrier of waves, long-range order, nanostructures, wave model.

of harmonic functions is termed Fourier decomposition or

I. INTRODUCTION Fourier analysis. The signal processing theory is based on
Bio- and nano- structures share a common property – the Fourier analysis and, as a matter of fact, Fourier analysis is
long-range order over the distances significantly greater than the theoretical basis of Radio and TV domain. The benefits
the dimension of atom. So, for example, a snowflake is from the application of Fourier analysis are that it is
gigantic as compared with an atom, but it has a strikingly sufficient to explore the behavior of one sinusoidal
regular form. Even more amazing are the biological component in order to draw conclusions about the behavior
structures where the nature manages to pack up the of functions of arbitrary complexity. The inverse process is
information about a very complex organism into a tiny cell. also possible: by selecting an appropriate sum of sinusoidal
The phenomenon of long-range order cannot be components, it is possible to synthesize practically any
understood within the realm of Niels Bohr‘s model of atom. function of time.
Neither quantum mechanics can offer a satisfactory Similarly, any function which depends on spatial
interpretation of this phenomenon. On the other hand, the coordinates can be decomposed in harmonic functions.
wave model produces amazing results in the explanation of Mathematically, a hologram represents such a
the complex order structures formation. The reason for this decomposition of an image into harmonic functions. By
is that the waves, spreading over all the Universe and lasting means of a hologram, it is possible to obtain a visual image
forever, can really form complex interference structures. of an object indistinguishable from the object itself. The idea
Also, the ―primary elements‖, making up the ―generating to combine the decomposition into harmonic functions of
basis‖ of these structures are waves, which are described in time with the decomposition into harmonic functions of
terms of simple functions, and the interaction between which spatial coordinates comes up naturally. Such a combination
can be described in terms of certain rules. This approach would result in moving images which, ideally, would be
allows us to describe objects with complex structure, identical with their originals.
proceeding from the most simple postulates and rules of Thus, an image of reality can be synthesized out of
inference and such a method is a manifestation of reduction sinusoidal functions which depend simultaneously on
of complexity. Engineering disciplines have accumulated temporal and spatial coordinates. These functions of space
rich experience how to build complex systems based on and time represent the waves. It is appropriate to say that
simple elements. harmonic functions, i.e. waves, represent a set out of which
Thus, the world of computers and computer programs is it is possible to synthesize any function of space and time.
based on operations over only two logical entities, unity and On the other hand, from a formal point of view, the objects
zero (or true and false), and this apparatus is sufficient to surrounding us are also functions of space and time, as they
manage information of unlimited complexity. Boolean are characterized by positions and dimensions which change
algebras are sufficient for modeling the World, but they are in time. In other words, harmonic waves can be described as
not the only ones to offer a modeling framework. The a certain set on the basis of which it is possible to simulate
information we receive by phone, radio or TV, no matter the world.
how complex, can be mathematically represented as a In study of the fundamental fields, quantum mechanics, or
function of time. Any function of time can be represented as the theory of relativity, we easily come to understanding that
a sum or as an integral of a set of simple functions of time, all physical phenomena are related, in a way or another, to
where the most convenient for this purpose are the harmonic the wave processes. That is, wave processes are not just a
functions. The representation of a function of time as a sum tool for the formal description of the World similar to that by
the Boolean algebras; wave processes have a much more

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fundamental and intimate link with the physical reality. serve as a carrier for waves said to be ―aether‖ was that, due
The central issue arising in the use of such models is the to such a medium, it would be possible to select a
existence of a carrier for the wave set. In case of Boolean distinguished frame of reference, and this would contradict
algebras, this issue is resolved easily - everyone knows that to the principle of relativity and the relativity theory based
this carrier is the computer, and without a computer no on this principle. I will show below, that the existence of a
program can run. However, if we imagine that an artificial wave medium-carrier or continuum does not contradict to
intellect residing in a computer attempted to solve the special theory of relativity.
question of the existence of the carrier of Boolean algebra, For description of physical processes, it is common to use
such an intellect could not establish the existence of the a frame of reference, which is a system of spatial and time
computer. This is certainly true if the computer carries out coordinates, with respect to which the behavior of bodies is
only the operations of Boolean algebra and other parameters, described. A preferential role is played by the inertial
such as the times of operations, are not provided. The idea systems of reference and one of the reasons for this is that
stated here can be formulated the following manner: an the equations of motion in such systems are the most simple.
intelligent agent residing on the carrier of the Boolean A frame of reference must contain scales for measuring
algebra would not be able to determine whether the carrier time and length. Such scales consist of repeating intervals of
exists. time and length. A standing wave has the property of
Reformulating the said above into the terms of wave periodicity in both space and time and is described by an
functions, we can say that it is impossible to detect the equation of the form
carrier medium of the waves by using tools which, by their
nature, are waves in the same medium. The electromagnetic a  A cos kx cos t . (1)
waves and the fundamental particles can be transmuted into Here, A is the amplitude of a parameter describing a wave
one another and those particles have wave properties. This (pressure, density, etc.), k is the wave number, and ω is the
raises the suspicion that both types of entities are waves in circular (cyclic) frequency. By choosing such a wave, we
the same carrier medium. Hence, it is impossible to detect choose a metric, namely:
the carrier medium of the waves of matter by using tools - The direction of the x-axis coincides with the direction
built out of particles with undular properties. This is exactly of the wave propagation;
the reason why the experiments aiming at the detection of a - The spatial scale is defined by the wavelength
carrier for electromagnetic waves failed. But also, these   2 / k;
experiments failed to prove the lack of a carrier medium of - The temporal scale is defined by the period of the wave
the waves in which we are concerned (including the T  2 / .
electromagnetic waves). Actually, what such experiments
In other words, standing waves play the same role as
could have demonstrated is the impossibility to detect the
rulers and clocks. If in a medium there is a wave-object
medium from within the medium.
described by the equation
a0  A cos k0 x cos0t 
The source of problems created by a medium-carrier is
due to taking over the methods of hydrodynamics and (2)
acoustics into the theoretical considerations and practical then the measurement of its length in the frame defined by
experiments for detection of a medium-carrier. The tools equation (1) consists in defining a number equal to the ratio
used in hydrodynamics and acoustics are heterogeneous with of the length of the wave-object to the wave scale:
respect to the medium. But such a method is not adequate for n  0 /  , (3)
a medium of wave particles and fields, because both such Similarly, a measurement of the period of the wave object
particles and fields are also waves in the same medium. This consists in the definition of the ratio of the period of the
idea will not appear crazy if we recollect that the wave object to the wave scale:
fundamental particles of which we are made are also of a n  T0 / T . (4)
wave nature. Thus, it becomes obvious that, in order to work
The wave object (2) can be decomposed into two waves
with a medium serving as the carrier of waves and fields, it
running in opposite directions:
is necessary to abandon the idea about "solid" tools and treat
A
objects and tools on equal basis. a01  cos(0t  k0 x ) , (5)
In order to overcome the difficulties which appeared in 2
physics due to inappropriate treatment of tools as residing A
a02  cos(0t  k0 x ). (6)
outside the phenomena, I have used a wave model [1], which 2
is both an approach and a vision, according which the If in the expressions (5) and (6), the frequencies and the
Universe is regarded as populated only by waves, so that the wave numbers differ, so that that the correlations
tools for measuring the attributes of one wave are other A A
waves. The wave model implies consecutive development of a01  cos(01t  k01x ) , and a02  cos(0t  k0 x ),
2 2
methods allowing to use the waves as tools for examination
of waves. Below we will try to explain these methods in where  01   0 and k 01  k 0 , the wave-object can be
brief and some of the results obtained by these methods. described by the equation:
   0 k  k01 
II. WITHIN THE WAVE MODEL THE EXISTENCE OF a0  a01  a02  A0 cos 01 t 0 x 
MEDIUM-CARRIER FOR WAVES OF MATER DOES  2 2 
(7)
NOT CONTRADICT TO SPECIAL THEORY OF  01  0 k0  k01 
RELATIVITY cos t x .
One of the objections against the existence of a medium to  2 2 
This equation describes a standing wave in which the

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maxima move with time. We shall term such a wave ‗quasi- an attempt was made to detect the velocity of the motion
standing‘. Thus, the parameters relative to the aether. If such an experiment would give a
  k k positive result, then this would allow to find the ―true wave
 '  01 0 and k '  01 0 frame‖, in which the velocity of motion relative to the carrier
2 2
can be perceived as the frequency and wave number of the medium is equal to zero. Such a system would be privileged
moving wave-object (7). in relation to other wave frames. In this case, the principle of
relativity would not be fulfilled for the wave systems. Let us
 
The term   01 0 t in the first factor defines phase prove that this is not true.
2 Theorem: the velocity c of a traveling wave has the same
displacement of wave-object along the spatial coordinate x, value in all wave frames.
k k We suppose that we have two wave frames, described by
and   0 01 x in the second factor, defines a retardation
2 the following equations:
or phase displacement along the temporal coordinate. Then a  A cos kx cos t . (10)
the displacement of the wave-object along the coordinate x and
for the interval Δt will then be
   k  k1   1   k  k1 
  a'  A cos 1 t x  cos t x  (11)
x  01 0 t.  2 2   2 2 
k0  k01
The velocity of relative motion of these systems is given
Hence, the velocity of displacement of the wave-object is by the equation:
equal to
  T  T1
x  01   0 v 1  c2 . (12)
v0   . (8) k  k1 1  
t k 0  k 01
Let us suppose that some wave-object is at rest in the
Since system defined by equation (11) and described in that system
2 2   by:
 , k and   c,
T  T k a0 '  A0 cos k0 ' x'cos0 ' t '. (13)
the equation (8) can be rewritten equivalently as: The same wave-object will be described in a system
  T T T T k k defined by equation (10) as
v0  0 01 0 01  c 2 0 01  c 2 0 01 . (9)
T0T01 01  0 01  0 0  01    0 k  k01 
a0  A0 cos  01 t 0 x 
Recall that v0 is the velocity of points with same phase  2 2 
move such as, for example, the maxima of a quasi-standing (14)
 01  0 k0  k01 
wave. The velocity v0 defined by the equations (8) and (9) is cos  t x .
related neither with the motion of the continuum, nor with  2 2 
respect to the continuum. But, in the absence of tools other Let us rewrite equation (14) taking the equation (12) into
than undular nature, only this velocity can characterize the account:
motion of the wave-object (7). k k     01 v 
a0  A0 cos 0 01 (vt  x )  cos 0 (t  2 x ) . (15)
If an observer moves with a velocity defined by equations  2   2 c 
(8) and (9), then from his/her point of view, the wave (7) The equations (15) and (13) describe the same wave-
will be a standing wave, and it will be described by an object. In equation (15), the value of (vt  x ) represents the
equation of the form (2) or by an equation of the form (1) if
n = 1. Hence, in the system of a moving observer, this wave instantaneous coordinate of the wave-object, as well as x'
can be used as the wave which defines the frame. Thus, does in the equation (13). The transformation of lengths of
within the scope of our model, there can be a set of frames of line segments parallel to this coordinate should take place
reference that move relative to each other with different according to the same law as the transformation of this
velocities, but all of them equal in rights. coordinate. Hence, the length of the moving wave-object
Definition: a wave frame of reference is a frame of (15) becomes 0 '  0  vT0 , and its wave number becomes:
reference in which the period of a standing or quasi-standing 2
k0 '  . (16)
wave at a fixed point serves as the scale of time, and the 0  vT0
scale of length is the distance between two points with same
By applying similar reasoning for the frequency, we
phase.
obtain:
As noted above, in an unlimited homogeneous medium no
2
wave system offers any advantage above others. In other 0 '  . (17)
words, the principle of relativity is valid for the wave v
T0  2 0
frames. However, there is one circumstance which can cast c
doubt on this statement. The velocity c of propagation of The ratio of the circular frequency  to the wave number
traveling waves described by the equations (5) and (6) is k is equal to the velocity of the traveling wave c. Thus, the
determined by the properties of the medium. Naturally, this proof of the theorem formulated above is reduced to the
suggests the idea to use a standing wave as a tool for demonstration of the relation
determining the velocity c of a traveling wave. Then,  '
knowing the velocity c, it is possible to determine the c  0  0  c'.
k0 k0 '
velocity of a wave frame relative to the medium. In fact,
such an experiment would be similar to the experiment By using equations (16) and (17), we have:
performed by Michelson and Morley in 1887 [2-4], in which

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0 ' 0  vT0 - If there existed a medium-carrier for electromagnetic

c'   c2 . waves (the aether) it would be possible to relate with it a
k0 ' c 2T0  v0
distinguished frame of reference, and this contradicts to the
With the help of equations (3), (4) and (12), we finally principle of a relativity and relativity theory based on this
obtain: c'  c . principle;
We have now proved that in a wave frame, the velocity c - The experimental attempts to find a material carrier of
of a traveling wave does not depend on the choice of frame. electromagnetic waves failed.
Hence, the velocity of a traveling wave cannot be used for On the basis of the arguments above, the point of view of
the definition of a velocity relative to the carrier medium, [9] was accepted which sounds: ‗The electromagnetic fields
and all wave reference frames are equal in rights. are not states of a medium, and are not bound down to any
Thus, the use of wave frames leads us naturally to bearer, but they are independent realities which are not
statements which serve as postulates for a special theory of reducible to anything else, exactly like the atoms of
relativity [5], namely: ponderable matter‘. This point of view was canonical until
- the relativity principle is valid: all inertial frames, i.e. recently and it can be encountered practically in all
systems which do not change their velocity, are equal in textbooks on physics. However, such a vision does not reply
rights; to some questions, namely:
- the velocity of propagation of traveling waves in all - There should exist a common approach to all types of
inertial frames is the same. waves irregardless of their nature, and it is certainly known
From these postulates follow the Lorentz transformation that elastic waves are states of a medium and not
laws which relate the length of a moving segment x' and ‗independent realities which are not reducible to anything
an interval of time t ' in its own frame of reference to the else‘;
length x and an interval of time t in the laboratory - If the light gets from empty space into a certain
system with respect to which it moves: transparent medium such as glass, it continues motion with
x'  x (18) smaller velocity, and it returns to previous velocity when it
and exists such medium. Hence, there should be a mechanism
t '  t , (19) due to which the velocity of electromagnetic waves in
vacuum has a constant value and it does not depend on the
1 v
Here   and  . parameters of the electromagnetic waves, on their source, or
1  2 c on their history;
- To explain inertia and the effects of general relativity
The deductions of these expressions within the scope of
theory, it is necessary to assume that the vacuum is filled
wave model are given in the articles [6, 7] as well as, in a
with some media (currently, this is supposed to be fields)
more elaborated manner, in the book [1]. From the given
[10];
proofs, it follows that the Lorentz transformation laws are
- According to general relativity theory, the values of
not related to the presence or absence of a carrier medium.
length and time depend on the magnitude of the gravitational
Hence, presence of a medium-carrier of waves does not
field. The change of the scales of length and time in a
contradict to the special theory of relativity. Thus, it is
gravitational field is referred to by the term ‗curvature of the
possible to draw the conclusion that if also light and all the
space–time continuum‘. From this it again follows that the
fundamental particles are waves in the same medium, then
vacuum cannot be empty. The supposition arise that the
the existence of such carrier medium does not contradict to
electromagnetic fields and gravitational fields have
the theory of relativity. One more important consequence of
something in common, i.e. that the ‗gravitational aether‘ is
the given reasoning is the conclusion that in different frames
somehow linked to the ‗electromagnetic aether‘;
of reference the wave objects will look differently.
- The general relativity theory admits the possibility to create
III. THE ELECTRICAL AND MAGNETIC FIELDS IN a relativistic propulsion device [11], which implies that
WAVE MODEL vacuum is capable of exerting force and having inertia;
The second serious argument against the existence of a - Within the scope of accepted model of empty vacuum it is
medium-carrier for waves of matter emerged due to the possible to understand the mechanism of repulsion, but the
failure of the attempts to get compliance between the mechanisms of attraction are unimaginable.
properties of the electromagnetic fields and the properties of Thus, the banishment from physics of a carrier for
any medium. Maxwell used in his deductions a certain electromagnetic waves, did not solve the contradiction, but
artificial model of the medium [8] which was too complex raised a series of new questions instead. In the book [7], I
and improbable to be taken in serious. Here are the problems explained how it is possible to find answers to these
which arise in selecting a medium-carrier for the questions and how to solve the problem about the wave
electromagnetic waves: medium-carrier in compliance with the Maxwell equations. I
- The phenomena of polarization and other facts determine succeeded to prove within the scope of wave model, that the
that light is transversal waves, but it is impossible to figure electromagnetic field is a property of an elementary
out a simple model of a medium with only transversal waves medium-carrier. I proceeded from the following premises:
and no longitudinal waves; no longitudinal electromagnetic - There exists a continuous medium, which I termed
waves have ever been found; continuum, in which there can be fluctuations in the form of
- The velocity of electromagnetic waves (the light) is drops in pressure and velocity;
greatest possible; but from the theory of waves it is known, - The only tool for examination of these fluctuations is the
that it is the longitudinal waves which have the greatest wave-tool representing a domain with a pressure (density)
velocity; different from the pressure (density) within unperturbed

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continuum. 1.0
py
On the basis of these premises it has been found out, how
some wave-tool representing a surplus or a deficit of a 0.5

continuum, will interact with drops in pressure and velocity

in the medium. It turned out that the redundant quantity of a -5 -4 -3 -2 -1 1 2 3 4 5
continuum in a wave-tool can be associated with an rx
-0.5
electrical charge, the pressure gradient - with an electric
intensity, and the magnetic intensity – with the drop in Fig.1. The diagram of function (23)
-1.0
velocity. It is shown, that the magnetic field is an effect of
the relativistic contraction of the continuum from the point In case of the central symmetric wave the distinguished
of view of a moving wave-tool. The proofs of these frame is the system bounded to the center of wave. The wave
statements are not trivial; they can be found also on my site (22) can be rewritten in the trigonometric form:
p
[12]. The relation between electric intensity E and magnetic pS  A sin kr sin t , (23)
intensity B is determined by Maxwell equations. The kr
deduction of Maxwell equations, proceeding from the where pA is the amplitude of pressure in the center of the
offered model, is also is given in my monograph [7]. It is spherical wave. The diagram of function (23) at sinωt=1 is
necessary to emphasize, that Maxwell equations define the presented on fig. 1.
correlation between a pressure gradient and a drop in py 0.9

velocity of the medium, and not between pressure and 0.8

0.7

velocity of medium as in the equations of acoustics. 0.6

0.5

0.4

IV. WAVES AS A BASIS FOR AN ALGEBRA OF THE 0.3

0.2
REALITY PHENOMENA 0.1

In the formula (1) we did not impose any requirements on -5 -4 -3 -2 -1

-0.1
1 2 3 4
r 5
x
the amplitude and, thus, the obtained deductions will be -0.2

valid for any amplitude, including the case when the Fig.2. The diagram of function (23) at attempt to upset the balance
amplitude is some function of spatial coordinates and time. between frequency and energy of a wave
The wave equation in spherical coordinates for a central-
This solution is unique among those, which do not have
symmetric wave looks like this:
peculiarities at r = 0, while the oscillatory velocity is
 2 rp  1  2 rp  continuous and becomes zero in the center. The
 0
r 2 c 2 t 2 amplitude p A / kr in the expression (8.15) defines the energy
The solution of this equation is, in particular, the of a spherical wave, the factor sin kr defines a spatial
harmonic (traveling), waves with the amplitude of pressure distribution, and sint - the time dependence, while
in the center pA which can be described by expression:  / k  c . It means, that the expression (23) rigidly relates
p  p Aei t  kr  , (20) the energy of a spherical wave with its frequency. Any
where the upper sign ―plus‖ corresponds to the wave attempt to change one of these parameters leads to
moving along the r, and the lower sign ―minus‖ corresponds divergence (Fig. 2). This property of the function (23) is a
to a wave moving in the opposite direction. This solution key to the quantification riddle. According (23), the
coincides with the formula of the associated waves, which argument of sin and the denominator should be similar and
describe in quantum mechanics a free moving particle such similarity should be absolute. The smallest difference
 r, t   Cei t  kr  . (21)
conducts to divergence of the function pS.
It is rather interesting, that this phenomenon is observed
The explanations regarding the physical sense of a wave in technology as the cavitation phenomenon which destroys
function and the amplitude can be found in any textbook on the screws of a ship. It is wrongly deemed, that cavitation is
quantum mechanics and we will not go deeper into this caused by bubbles formed due to a rupture of the medium,
topic. We will refer only to the quantum-classical i.e. the consequence is taken as the cause [15, 16].
correspondence principle [13, 14], according to which the If two such stable spherical waves interact, the correlation
physical phenomena in quantum mechanics are described by between the argument of sin and p A / kr are broken. The
equations similar to classical mechanics with the only
difference that classical parameters are exchanged with those divergence is eliminated, if the interacting spherical waves
of quantum mechanics. We will apply this principle in "to reorganize so, that in their own frames of reference the
the contrary" manner. We consider a fundamental particle- correlation between the amplitude and the frequency is
wave (say, an electron) to be described by the sum of two recovered. If with such reorganization a part of energy is
traveling waves in continuum. These waves are harmonic radiated in the form of a traveling wave the resultant system
and central-symmetric: becomes stable. For destroying such a system it is necessary
the energy radiated at its formation to be returned. Thus, two
ei t  kr  spherical stable waves can form a stable system which,
p  pA , (22)
r getting into a field of the third wave, or in a field formed by
where the upper ―plus‖ sign corresponds to a divergent a collective state of several particles, can form a more
wave, and lower ―minus‖ sign – to a converging wave. complex stable state, and so on. We come to the conclusion
that, the stable spherical waves form a set from which can be
formed other stable states which also belong to set of stable
waves. Out of these new states, other stable states which

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belong to the same set can form and so on, ad infinitum. REFERENCES
The formulation above brings us to the idea that the waves [1] Bettin Mironov, Mechanisms of Electromagnetic and
can serve as elements of a carrier of a universal algebra. A Gravitational Fields. Virtualbookworm US. (2007) 228
universal algebra A = (A, O) is an ordered pair, where A is a p. ISBN 978-1-60264-105-1.
set termed carrier of the algebra, and O is a set of operations [2] Albert Michelson, Edward Morley. J. Sci., 31, 377
of various arity (or, rank) over A with respect to which the (1886).
operations is said to be ―closed‖. Thus, the concept of [3] Albert Michelson, Edward Morley. J. Sci., 34, 333
universal algebra allows constructing a ―closed world‖ of (1887).
unlimited complexity. Within the context of this research, [4] Loyd S. Swenson, The ethereal Aether: A History of the
the term ‗closed‘ means, that to build up a world of arbitrary Michelson – Morley – Miller Aether – Drift
complexity it is enough to proceed from elements of a Experiments 1880 – 1930. Austin (Тех.), (1972).
chosen set, and this is the set of waves, which make up the [5] Albert Einstein, Zur Elektrodinamik der bewegter
set of generators of a universal algebra. Körper. Ann. Phys., 891–921 (1905). (An English
Similarity of the expressions (20) and (21) allows us to version available:
identify the fundamental particles with monochrome stable http://www.fourmilab.ch/etexts/einstein/specrel/www/).
spherical waves in a continuum described by these [6] Bettin Mironov. On the metric of waves interactions.
expressions. It is known, that as a result of particles Meridian ingineresc. 2, 54–59 (2001).
interaction, oscillatory systems are formed, which have [7] Bettin Mironov, Kinematics of waves interactions in
spectrums of higher complexity. Even the atom of hydrogen undular frames. Moldavian Journal of the Physical
consisting of three particles, i.e. proton, neutron and Sciences, 4, No. 3, 367–380, Chişinău (2005).
electron, already has a rather complex spectrum. The Plank [8] James Clerk Maxwell, Treatise on Electricity and
constant serves as a coefficient in the relationship between Magnetism. Dover Publications; 3rd edition (1954),
energy and frequency. It is important to mention, that in the ISBN 978-0486606361.
interaction of stable standing waves not only the amplitudes [9] Albert Einstein, Äther und Relativitätstheorie. Verlag
and frequency play a role, but also their phase, and this leads von Julius Springer, Berlin (1920).
to indeterminacy of the relation. [10] Max Born, Einstein’s Theory of Relativity (written with
It is necessary to remark, that in the formation of complex the collaboration of G. Leibfried and W. Biem). Dover
wave systems there exists a certain energy hierarchy: for Publications, New York (1962).
creating or destroying complex wave systems, it is necessary [11] http://www.sphere.ad.jp/force/relativity/pro/forpro-
less energy. The spectrums of simple oscillatory systems, e.html.
atoms and molecules, are well studied. The offered algebraic [12] http://www.mironovbettin.narod.ru/English/index.html.
approach is of interest at examination of the complex [13] Niels Bohr, Collected Works, Volume 3, The
oscillatory systems in which the binding energy becomes Correspondence Principle (1918–1923), 3, Amsterdam:
comparable with the energy of fluctuations caused by North-Holland, (1976).
thermal processes. The combination of stability of wave [14] Alexander Stotland, Doron Cohen, "Diffractive energy
systems and fluctuations is a key to understanding of self- spreading and its semiclassical limit", Journal of
developing systems lying in the basis of life. Physics A 39 (10703): 10703, doi:10.1088/0305-
There is one more important circumstance related to wave 4470/39/34/008, ISSN 0305-4470 (2006).
systems, namely that the waves, basically outreach to the [15] Robert T. Knapp, James W. Daily, Frederick G.
infinity. This means, that the wave systems can interact Hammitt, Cavitation. New York: McGraw-Hill, (1970).
between themselves remotely, defining the structure of each
687 p.
other. This creates the probability of the reproduction
[16] Christopher E. Brennen, Cavitation and Bubble
(replication) of the wave systems in result of such actions. In
Dynamic, Oxford University Press, Oxford, UK, (1995)
my opinion, it is exactly this process which bears the key in
304 p. ISBN10: 0-19-509409-3.
the emergence of nanostructures and biological objects.
[17] Ioachim Drugus, Universics - A Common Formalization
Framework for Brain Informatics and Semantic Web,
Web Intelligence and Intelligent Agents, INTECH,
(2010).

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Two-Photon Coherent Fields and its

Application in Communication
Marina ŢURCAN
Institute of Applied Physics, Academy of Sciences of Moldova
[email protected]

Abstract – It is examined the coherence properties between the Stokes and anti-Stokes fields and its
application in Communication. It is proposed novel two-photon entangled sources which take into account
the coherence and collective phenomena between these fields. The quantum propriety of realistic sources of
powerful coherent bi-boson radiation (coherent entanglement of Stokes and anti- Stokes photons) is analyzed.
The possibility of experimental applications of coherence between the Stokes and anti-Stokes photons in
quantum communications and cryptography is proposed.

Index Terms – Coherence, correlation function, generation, non-liner optics, quantum-computing.

between these fields are considered as potential algorithms

I. INTRODUCTION in cryptography and are expressed through the lasing
Quantum Information Science is an emerging field with parameters of the source (e.g. [5]).
the potential for revolutionary advances in fields of science This manuscript reports the review of the
and engineering involving computation, communication, transmission of information through entangled photons,
precision measurement, and fundamental quantum science. obtained in parametric down conversion (e.g. [6, 7]). In this
The property of entanglement between the emitted articles it is proposed the new method of transmission of
photons in the processes of light generation has a great information taking in to account the two-field coherent
impact towards applications dealing with quantum states. The main difference between Ekert model (e.g. [8])
computing, and information security (e.g. [1]). The modern and new possibilities which include the second order
investigations connected with the manipulation of quantum coherent effects is given. It is considered that such coherence
fluctuations of the generated light and there application in between the photon of two fields can be conserved in the
transmission and detection of information with high degree process of propagation bimodal field through different fibers
of security play an important role in the modern defense over long distances after the focusing. The information
problems. The problem of quantum fluctuations and the encapsulated into coherent bi-boson light can be destroyed in
generation of non-classical electromagnetic fields in multi- the dispersive medium and restored over a certain distance.
photon processes have been the subject of extensive In both methods of transmission bimodal coherent field, the
theoretical and experimental studies in recent years, more nature of the quantum communication between two points A
specifically two-photon coherent generation of light has led (Alice) and B (Bob) does not allow eavesdropper, E (Eve), to
to many experimental and theoretical studies recently An know the transferred information. Below we shall discuss
interesting behavior of Stokes (e.g. [2]) and anti- Stokes the cryptographic aspects bvon the basis of two
generated modes in the Raman processes (e.g. [3]) can be entanglement photons obtained in parametrical down
observed for the small number of the pumped photon in conversion and our model based on the two-field coherence
nonlinear media. effect between the Stokes and anti-Stokes fields. These
In this article it is proposed the new type of models are described in the section A and B.
generation of coherence states of biboson field and its II. PROTOCOLS WITH ENTANGLEMENT EFFECT
application in comunication, biophotonics. This field can be BETWEEN PHOTONS
regarded as two coherent fields generate in the lasing The transmission of information through entangled
process of Stokes and anti-Stokes modes in nonlinear photons is based on he the Ekert‘s protocol (e.g. [8]). This
medium. Such a quantum correlations can be obtained in the protocol is encoded by its physical nature. The system based
processes of Raman scattering (e.g. [4]). In this article it is on the entanglement effect between the photons consists in
obtained new coherent states between Stokes and anti-Stokes the following: Alice receives one of the photons of the pair
fields and it is proposed to use such a fields in quantum and Bob the second. Alice and Bob have de same detection
communication, holography and biotehnology. It is basis and for every particle pair everyone choose
demonstrated that these collective scattering phenomena take independently an accidentally axis and measure the
place due to information transfer between the photons of two polarization along the axis. After that a series of photons pair
cavity modes. Studying the quantum fluctuations of the are transmitted, they announce what axis of polarizer were
number of photon the new proprieties of the Stokes and chosen in the process of measurement and analyze in which
Anti-Stokes fields have been found and proposed for cases they obtained the particles simultaneously (e.g. [8]).
communication with hair degree of security of information. So, the channel is established. This system is encoded
The new peculiarities of second order correlation functions

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automatically. A detailed description can be found in the necessary because in a bi-boson lasing effect (e.g. [10]), the
works (e.g. [8]). The pulses formed from pairs of entangled photon statistics depend on the statistics of the ignition field
photons can be applied in quantum communication and (e.g. [11]). Of course, the start up from vacuum fluctuations
cryptography using the great investigations of quantum preserves the entanglement character of the generated Stokes
optics. It was demonstrated that in the process of and anti-Stokes coherence state. This effect is very
transmission of correlated two photons which were obtained interesting in quantum communication.
with parameter down-conversion effect through two optical This manuscript propose an interesting effect that takes
fibers, the correlation between the photons pairs is conserved into account the classical method of registration of
at a very big distance (30 km), and for more than 6 km in information. As Π(t) plays the role of electromagnetic field
free-space (e.g. [9]). For the distance that is mach than 20 intensity strength for the two-fields Stokes and anti-Stokes,
km in free space Chinese physicist realizes (e.g. [9]) it today. at the detector can be considered as a classical field
He thinks that simultaneously with an output to described by (t )  0 (t ) cos[~t  (ka  ks ) z  0 ] , where  0 is the
geostationary satellites the communication through quantum envelop of cooperative two-photon interaction in scattering
cryptography will be possible for distance around 10 processes. A large number of modes in the coherent states
thousands km. In other words, the humanity will have give as the possibilities of the increase the security of
cryptographic channels that cannot be listened by information storages in bimodal field (e.g. [9-11]). In this
eavesdropper (Eve), because the nature of the approximation, the classical information may be introduced
communication through pairs of photons does not allow this. in the amplitude  0 (t ) . Such registration of information may
Below we give the scheme that describes this process of
transmission at the distance of 13 km (e.g. [9]). The have nothing to do with the traditional method. If the bi-
generator of pairs of photons (probably the nonlinear crystal boson pulses pass through a dispersive medium, the anti-
without a inversion centre (MgO:LiNbO3) is situated in Stokes and Stokes photons from the field change their
Chinese place Dashu. The flux was expanded using a optic directions. Focusing the anti-Stokes and Stokes photons into
telescope. The signal was compressed with telescopes of the different optical fibers we are totally dropping the coherence
same type at the detectors Alice and Bob situated in USTC among the photons. However, after a certain time interval,
(University of Science and Technology of China) and the anti-Stokes and Stokes photons from the field are mixed
place Taouhua. The protocols Alice and Bob coincided, that again, and we can observe that the coherence is restored (see
means a high efficiency in the process of transmission of the Fig. 1).
information.
III. NEW ARHITECTURE USING THE COHERENCE
BETWEEN STOKES AND ANTI-STOKES FIELDS

It propose a novel architecture for quantum

communication. The amplitude of a simple block of coherent
Stokes and anti-Stokes photons obtained after two-photon
interaction in scattering lasing effects can be described by
the square value of electrical vector
Fig. 1.
ˆ
(t )  g S g A b aˆExp[0 t  (k a  k s ) z   0 ]

. (t )  EA ES ,.
The coherent state obtained in two-photon coherent
emission   exp      0 , takes into account not only
representing these amplitudes through
 ˆ
EA  b exp[i(At  kz z)]g A and ES  aˆ exp[ i(S t  kS z)]gS ,
 
entanglement between the pair photons but the coherence

where b̂  and â are creation photon operators in the anti- between the fields too, and can be used in mixed processing
problems in which the quantum entanglement between the
Stokes and Stokes fields respectively, b̂ and â are Stokes and anti-Stokes photons is used simultaneously with
annihilation photon operators in these fields. In the quasi- classical coherence (e.g. [6]) between the fields. Of course
classical limits the amplitude  0 (t )  g S g A bˆ aˆ , has the the probability of experimental realization of logic gates for
quantum circuits in this case increase.
same proprieties as amplitude of coherent laser field. In this The coherent states between Stokes and anti-Stokes fields
approximation a nice idea is to use the classical of two wave can be realized in cooperative scattering effects (e.g. [11]).
modulation of this square amplitude for transmission of In order to obtain the cooperative generation of the
information. At first glance, it is observed that this method coherences states between Stokes and anti-Stokes fields we
does not have a substantial differences in comparison with consider a stream of atoms (e.g. [10,14,15]) with two levels
classical methods of information processing, but if we send travelling through the cavity. The total Hamiltonian which
this information in dispersive media, which separates anti- describes the interaction of the atoms with Stokes and anti-
Stokes and Stokes photons from coherent entanglement Stokes fields of the cavity can be represented through the
fields, the information is drastically destroyed, because b̂  atomic and field operators
 
N N

and â take zero values. The possibility of restoration of HT   0 Rzj  a a  a  bbb  i G(ka , kb ) R j (t ) J   J  R j (t ) (1)
j 1 j 1
information on the square amplitudes  0 (t ), is interesting
problem of many particle coherent states, formed from where the last term represent the interaction Hamiltonian.
blocks of Stokes and anti-Stokes photons. These studies are Here Rzj is the population inversion of atom j; Rˆ j and Rˆ j

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represent the operators which describe the transitions from with the minimum in point z min  ~1 /( 2~2 ) , where
g - ground state to e - excited state and from e - z  J   J  . The dependence of this potential V(z) as
excited state to g - ground state, respectively (e.g. [10]). function of the amplitude z decrease achieving z min and

The operator a (a) is the creation (annihilation) of Stokes after that increase. As follows from the expression (4), the
photons and b  (b) is the creation (annihilation) of anti- amplitude value of two-photon coherent fields z is
proportional with the ratio between scattering rate and
Stokes field operators. The interaction constant G(k a , kb )
diffusion coefficient  2 and increases with increasing of
describes the effective nonlinear coupling of atom j with
scattering rate, 1 , This steady state solution describes the
cavity modes with the energies  a and  b . In
ka and kb
stabilization process in the resonator.
order to describe the scattering processes, let us introduce We are interested in the behavior of quantum fluctuations
the collective operators for Stokes and anti-Stokes modes,
of this bi-field intensity, Jˆ (t ) Jˆ (t ) , in the process of time
 
   
J  ab and J  ba (e.g. [12]). The operator evolution to steady state:
 
J  ab describes the simultaneously process of creation 2  G2 (t )  G12 (t ) where G1 (t )  Jˆ  (t ) Jˆ  (t ) 
of anti-Stokes and annihilation of Stokes photons. The and G2 (t )  Jˆ  (t ) Jˆ  (t ) Jˆ  (t ) Jˆ  (t ) , are the intensity
inverse process is described by operator: J   ba  . As the and square of intensity of bi-boson field consisted from
full number of photons in the cavity, in the small time Stokes and anti-Stokes fields. Following the method
moment the interaction is conserved, we shall introduce the proposed in paper (e.g. [11]) let now found the behavior of
operator of photons inversion between the Stokes and anti- correlation functions G1 (t ) and G2 (t ) . Taking in to account
Stokes photons: J z  (b  b  a  a) / 2 and energy the solution of quantum equations (2), in the Fig. 2 it is
~
difference   b  a . plotted the dependece of correlation function G1 (t ) on the
Taking into account, that the lifetime of atoms in the relative time t/(21) for the following relative expression for
cavity are shorter than the time of scattering processes and parameters 1 =0.1, 2 =0.01 and 1/22 =5. This plot (see
considering that the atomic system is prepared in excited Fig. 2) demonstrated the good stabilization of second order
state, let us eliminate the atomic operators Rˆ j and Rˆ j from coherence between the Stokes and anti- Stokes photons.

Heisenberg equation of arbitrary field operator. By

representing the operators Rˆ j and Rˆ j through the field
 
operators Ĵ and Ĵ in according with Hamiltonian (1).
After consecutive elimination of free parts of these operators
the master equation for Stokes and anti-Stokes field can be
represented in the forth order on the interaction constant
G j (k a , k b )

d  d  d  G1 (t ) on the relative time
J (t )  2~1 J z (t ) J  (t )  4~2 J z J  J  J  , J (t )   J  (t )  (2) Fig. 2 The dependece of correlation function
dt dt  dt  t/(21) for the following value of parameters 1 =0.1, 2 =0.01 and 1/22
The behaviour over time of the mean value of operators =5.
J  (t ) and J  (t ) can be found in accordance with the
As follows from the Fig. 2 with increasing of time
generalized equation propose in paper (e.g. [12]). In semi moment the correlation function achieved the maximal
classical approximation, when the fluctuations of these value, which corresponds to steady state stabilization. In Fig.
operators are neglected 3 we have plotted the time dependence of square
J  (t )  Jˆ  (t )  and J z (t )  Jˆ z (t )  , the equations fluctuations  . It is observed the time decreasing of
2

  quantum fluctuations of coherent amplitudes proposed in

(2) for mean values of these operators Ĵ and Ĵ take the
folowing simple expression communication with Stokes and anti-Stokes photons. As
d  follows from the Fig. 3, with the stabilization of lasing
J (t )  2~1 J z J  (t )  4~2 J z J  J  J  . (3) process the square fluctuation becomes negative.
dt
Considering that, at initial stage of ignition of generation IV. CONCLUSION
the inversion operator can be aproximate with Jz   j ,
The recent advances in quantum communication by using
quantum optical proprieties of light are reviewed. The
and following the idea proposed in paper (e.g. [11]), the quantum communication protocols are carefully discussed.
equation (3) can be represented by the generalized potential On the basis of these protocols many laboratories work for
 
function, V ( J  , J  ) , d  J (t )  / dt  V /   J  . development and implementation of quantum optics devices.
In accordance with this definition, we obtain the following It is proposed a new method of quantum communication,
potential function which takes in to account the coherence between the
entangled photon fields and the application of this effect in
V ( z )  2~1 j z  2~2 j z
2 4
(4) quantum communication. Considering coherent and

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corpuscular properties of light, consisted of photon fields, [3] B. Balko and I.W. Kay, Phys. Rev. B 48 (14) 1993.
the new scheme for quantum communication has been [4] S.K.Y. Lee and C.K.Law, ‗‘Collective photon-atom
offered for the quantum communications. states by Raman coupling inside a cavity: A dynamic
field-mode approach‘‘, Phys. Rev. A 76, 033809, 2007.
[5] D. Gauthier, Q. Wu, S.E. Morin and T.W. Mossberg,
Phys. Rev. Lett. 68, 464, 1992; D.J. Gauthier, ‗‘Progress
in Optics‘‘ 45, Chapter X , 2003; G. Ribordy, J.
Brendel, J.D. Gauthier, N. Gisin, H. Zbinden, Phys. Rev.
A 63, 012309 2001.
[6] R.H. Dicke, ‗‘Coherence in Spontaneous Radiation
Processes‘‘, Phys. Rev. 93(1), 1954.
[7] P.D. Drummond and C.W. Gardiner, ‗‘Generalized P-
Fig. 3 The dependences of square fluctuations,  , as function of relative representations in quantum optics‘‘, J. Phys. A13, 2353-
2

time t/(21), for the same parameter as in Fig. 2. 2368, 1980; C.W. Gardiner, ‗‘Quantum Noise‘‘
Springer-Verlag New York 1996.
This effects have many analogies with anti-bunging
[8] A.K. Ekert, Phys. Rev. Lett. 67, 661, 1991; A.K. Ekert,
behavior of Stokes and anti-Stokes fields, described by Ĵ  G.P. Massimo, J. Mod. Optics, 41, 2413, 1994.
[9] S.-X. Yu, J.-W. Pan, Z.-B. Chen, and Y.-D. Zhang.
and Ĵ  operators of SU (2) group (e.g. [11,16]). Perfect Test of Entanglement for Two-level Systems.
Phys. Rev. Lett. 91, 217903 2003;
[10] N.A. Enaki, M. Turcan and A. Vaseashta, J. Opto. and
ACKNOWLEDGMENTS Adv. Mat., 10 (11) – P. 3016, 2008.
The author would like to acknowledge stimulating [11] N. Enaki and V. Eremeev, ‗‘Two-Photon Lasing
discussions with Professor Nicolae Enaki. I would like to Stimulated by Collective Modes‘‘, Optics
thank all my colleagues from the Laboratory of Quantum Communications 247, P. 381-392, 2005.
Optics and Kinetic Processes, for friendly atmosphere. This [12] N. Enaki and M. Turcan, Proc.SPIE, 7469, p 746905,
paper was supported by the projects of the Academy of 2009.
Sciences of Moldova: No. 10.820.05.05/BF and No. [13] R. Miller, T.E. Northup, K.M. Birnbaum, A. Boca, A.D.
11.819.05.11F. Boozer, and H.J. Kimble, J. Phys. B: At. Mol. Opt. Phys. 38
REFERENCES S551, 2005.
[1] M. Aspelmeyer, H.R. Böhm, T.Gyatso, T. Jennewein, [14] O. Pfister, W.J. Brown, M.D. Stenner and D.J. Gauthier,
R. Kaltenbaek, M. Lindenthal, G. Molina-Terriza, A. Phys. Rev A 60, p.R4249-R4252, 1999.
Poppe, K. Resch, M. Taraba, R. Ursin, P. Walther and [15] Z.C. Wang and H. Haken, Z. Phys. B-Cond.Matter 55
A. Zeilinger, Science 301, 621, 2003; A. Zeilinger et all. p.361-370, 1984; ‗‘Quantum theory of the two-photon
Nature 390, 575-579, 1997. laser‘‘, ibid. 71, 253-59 1988.
[2] G.S. Agarwal and R.R. Puri, Phys. Rev. A 43, 3949, [16] N. A. Enaki, V. Eremeev, M. Ţurcan., ‗‘Two-Photon
1991. Lasing Controlled by Resonator Losses‗‘, Proc. of the
2nd International Conf. on Optics and Laser
Applications, ICOLA’07, p.98-102, 2007.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Ignition Method of Corona Discharge with

Modulation of the Field in Ion Source of Ion
Mobility spectrometer
Evgeniy GROMOV
National Nuclear Research University «MEPhI», Moscow, Russia
[email protected]
Abstract – The new method for the ignition of the corona discharge has been developed, which improves the
stability of the ion mobility spectrometer and the resolution of the instrument. The system of forming a corona
discharge without additional electrodes, which are used in a number of known structures for the pre-ionization,
has been developed. This simplifies the design of the proposed source and an electronic control circuit. IMS
technology is widely used in different civil and military fields for vapor-phase detection of explosive, narcotics,
chemical warfare agents, biology molecules and so on. There are set of methods whose are used for the ionization
of molecules under analysis. They are the following: radioactive ionization, ultraviolet photoionization, laser
ionization, electric field ionization, coronaspray ionization, electrospray ionization, roentgen ionization, and
surface ionization. All these methods has their own advantages and disadvantages. A comparing of ion mobility
spectra of non-polar hydrocarbons for photoionization, corona discharge ionization and 63Ni ionization, had
carried in. In our work we have investigated four types of IMS spectrometers whose use different sources for
molecules under analysis ionization. They use radioactive ionization, ultraviolet photoionization, laser ionization,
and roentgen ionization. The traditional explosives had investigated in experiments. In electricity, a corona
discharge is an electrical discharge brought on by the ionization of a fluid surrounding a conductor, which occurs
when the potential gradient (the strength of the electric field) exceeds a certain value, but conditions are
insufficient to cause complete electrical breakdown or arcing.

Key words – a ion mobility spectrometer, a corona discharge, a ignition of corona, a gate, additional
electrodes.

I. INTRODUCTION
Ion mobility spectrometry (IMS) is an analytical region, the detecting unit, data processing system.
technique [1-3] for gas phase analysis of chemical The ion mobility spectrometers use radioactive radiation,
compounds in laboratory environments; more recently, this corona discharge, the laser radiation, ultraviolet or X-rays to
method has been used in field applications to rapidly detect ionize air samples. Ionization source is an important part of
chemical warfare agents, explosives, and narcotics. Common the system responsible for the stability, resolving and
structure (Figure 1) of the device includes the ionization sensitivity of the spectrometer. Sources can operate in
region for inlet probe, gate for ion clusters forming, drift continuous or pulsed mode

Fig. 1. Common structure of ion mobility spectrometer with electrostatic gates.

The choice of a corona discharge to ionize air samples is connected with the following advantages:

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 lack of radioactive materials; A corona is a process by which a current, perhaps

sustained, develops from an electrode with a high potential
 the possibility of generating both in a neutral fluid, usually air, by ionizing that fluid so as to
positive and negative ions; create a plasma around the electrode. The ions generated
eventually pass charge to nearby areas of lower potential, or
 simplicity and low cost of recombine to form neutral gas molecules. When the potential
manufacture; gradient is large enough at a point in the fluid, the fluid at
that point ionizes and it becomes conductive. If a charged
 low power consumption. object has a sharp point, the air around that point will be at a
much higher gradient than elsewhere. Air near the electrode
II. CORONA IONIZATION SOURCE can become ionized (partially conductive), while regions
Ionization source by a corona discharge (Figure 2) more distant do not. When the air near the point becomes
consists on a conductive substrate, called a pusher electrode conductive, it has the effect of increasing the apparent
with thin sharp electrodes, between which at high voltage
corona discharge produced plasma. Limiting (ballast)
resistors R are used to align the current burning corona.
]

Fig. 2. The ionization source by a corona discharg

size of the conductor. Since the new conductive region is If the geometry and gradient are such that the ionized
less sharp, the ionization may not extend past this local region continues to grow instead of stopping at a certain
region. Outside of this region of ionization and conductivity, radius, a completely conductive path may be formed,
the charged particles slowly find their way to an oppositely resulting in a momentary spark, or a continuous arc.
charged object and are neutralized. Corona discharge usually involves two asymmetric
electrodes; one highly curved (such as the tip of a needle, or
a small diameter wire) and one of low curvature (such as a
plate, or the ground). The high curvature ensures a high
potential gradient around one electrode, for the generation of
a plasma.
Typically, ionization chamber design is such that the
ignition electrodes locate in a region of high electric field, so
that the generated ions are carried out from the ionization
region to the gate. In this case ions of natural origin
continuously carried out from the area between the electrode
tips of the corona source, this complicates ignition of the
corona. This leads to the instability of the discharge and the
need to increase the duration and amplitude of the voltage
pulse ignition. One of solution ways is proposed in
American patent № 6407382 [5], which suggests the use of
corona ionization source with additional firing electrode
(Figure 3). First additional electrodes are initiated to
following provide with ions the main electrodes.
In this work the corona discharge ignition system is
proposed, in which the ignition is divided on two phases:
preliminary and basic. During the preliminary phase an
Fig. 3. The ionization source with two additional firing electrodes (1 – the electric field in the ion source set to zero, and the generating
additional electrodes, 2 – the main electrodes, 3 – the pulse generator for "initiating" ions remain near the fire electrodes after end of
ignition corona discharge between the main electrodes, 4 – the pulse the discharge. To the moment of a start of basic ionization
generator for ignition corona discharge between the additional electrodes).
phase the field in the ion source is restored to the nominal

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level, with the "initiating" ions do not have time to leave the REFERENCES
region of ignition due to the low mobility. This ensures the
[1] V.V. Beliakov, A.V. Golovin, V.S. Pershenkov,
stability of ignition of a corona discharge due to the presence
Experimental studies of ion mobility spectrometer with
of ions in the discharge gap staying since the preliminary
the corona discharge ionization source, // Sensors and
phase of discharge. The proposed system provides
Systems, 2009, №2, pp. 12-17.
manufacturability and preserves the ionization source
[2] Eiceman G.A., Karpas Z., Ion Mobility
dimensions without resorting to the use of the additional
Spectrometry(Second edition) // CRC Press. – 2005.
electrodes.
[3] Tabrizchi M., Abedi A., A novel electron source for
negative ion mobility spectrometry, International
Journal of Mass Spectrometry, v. 218, pp.75-85, 2002.
[4] Discharge ionization source, Patent No. US 6407382,
Date of Patent: 06/18/2002

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Calibration Method for Ion Mobility

Spectrometer
Valery VASILIEV
National Nuclear University “MEPhI”, Moscow, Russia
[email protected]

Abstract –The new method for the calibration of the ion mobility spectrometer has been developed. This
article describes the working principle, advantages and disadvantages of the calibration method operating in
the mode of explosives detection. This method is most suitable for use in portable detectors, due to the small
weight, small size parameters and low power consumption.

Key words – ion mobility spectrometry, IMS, calibration, detection of explosives, corona discharge

Investigation of the reaction products of corona discharge

I. INTRODUCTION
was carried out on a specially designed layout. Layout
Ion mobility spectrometry is a widely recognized global
consists of two electrodes made of stainless steel with a
standard in detecting trace quantities of substances [1].
thickness of 0.5 mm using the technology of laser cutting.
Devices based on the ion mobility spectrometry principles
Tip electrodes are placed at a distance of 2mm. Burning
used in international airports and customs for detection of
source of corona discharge is shown in Figure 1.
narcotics, explosives and warfare agents.
The principle of operation is the selection of samples from
the surface or from the air, ionization and drift of ions
through a constant electric field in the drift tube.
Output spectrum characterizes the composition of the
sample. Ion of each substance has a definite mobility,
therefore the measurement time-of-flight characteristics of
the ions to determine their type.
As a result of changes in ambient temperature, humidity
and pressure the output spectrum is changed. This fact
requires periodic calibration of the spectrometer, so that the
influence of external factors did not affect the results of the
analysis. Calibration is carried out using previously known
substances, which are periodically introduced into the
ionization chamber.
The new calibration method by using the reaction
products of corona discharge (nitrogen oxides) described in
this paper. This method is most suitable for use in portable
detectors, due to the small weight, small size parameters and Fig.1. Corona discharge
low power consumption. It has a very good opportunities for
constructive integration in the portable IMS device [2]. In the transition from the regime of detection into the
calibration mode, the device suspends the detection of
II. CALIBRATION METHOD USING A CORONA explosives. The combustion products of corona discharge
DISCHARGE inputed into ionization chamber. Spectrum changes as shown
The possibility of chemical transformations under the in Figure 2.
influence of an electric discharge was discovered almost a The system detects the peak of the calibration substance
hundred years ago . Since then, detailed studies of the and on the basis of known data on the time-of-flight
processes occurring during combustion of corona discharge characteristics of detected explosives builds markers of these
in air [3-5]. substances relative to the calibration peak.
Chemical products resulting from combustion of corona Analysis of the calibration peak showed that the
discharge, such as nitrogen oxides, compete with analyte in experimental data given in [6], the gauge corresponds to the
electron capture reactions. The concentration of nitrogen substance nitrogen oxide. Spectrograms show the presence
oxides can be quite large and must be taken into account in a sample of large amounts of information generated
when dealing with the corona discharge ionization sources. during the discharge of the substance.
These substances have a high oxidative properties and By varying the voltage applied to the electrodes can
impede the detection of explosives. However, due to the change the amount generated by the combustion products, as
stability of a corona discharge nitrogen oxides can be used as illustrated in Fig. 3.
calibration substances.

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mobility spectrometer), this value is 2 eV,which confirms

the observed during the experiment, the charge transfer.
By varying the voltage applied to the electrodes, the
configuration of needles and the distance between them, we
can achieve stable combustion of corona discharge, provide
the required burning time of the corona. The developed
system allows to change the amount of combustion products
generated by varying the voltage applied to the electrodes. In
addition, the pulsed nature of the corona discharge provides
the kalibrant reliability and extends the lifetime of needles.
The proposed calibration method was successfully used in
a portable ion mobility spectrometer, which weight is a
2.9kg (without battery). Designed built-in ion mobility
spectrometer calibration system based on corona discharge.
It‘s control system integrated into the control system of the
spectrometer.
III. CONCLUSION
Calibration technique using a corona discharge is a very
Fig. 2. Change in the spectrum in the calibration mode suitable for use in portable detectors, due to the small
weight, small size parameters and low power consumption.
It has several advantages, allowing to embed kalibrant in a
portable ion mobility spectrometer. The developed
ionization source control system implements the possibility
of changing the parameters of corona discharge combustion
(duration of burning and discharge voltage).
Further research is needed in the area of embedded
kalibrant for positive mode of the IMS (detection of
narcotics).
ACKNOWLEDGMENTS
I owe my deep gratefulness to Dr. Pershenkov V.S., PhD
Belyakov V.V. and all of our team-mates.

REFERENCES
[1] Eiceman G.A., Karpas Z., Ion Mobility Spectrometry
(Second edition) // CRC Press. – 2005.
[2] Belyakov V.V. Ion Mobility Spectrometer // Utility
patent № 035034. – Russian Federation, 2006.
Fig. 3. Calibration spectrum for different discharge voltages [3] Hickling A. // Modern Aspects of Electrochemistry. L.:
Butterworths. 1971. № 6. P. 329.
[4] Lunin V.V., Popovich M.P., Tkachenko S.N. Physical
The figure shows that the number of outgoing material is chemistry of ozone. M.: MSU. 1998. 480 p.
directly proportional to the corona discharge voltage. [5] Andreev D.N. Organic synthesis in electrical discharges.
However, from a certain level the spectrum changes only USSR. 1953.
slightly. [6] M. Stano, M. Sabo, M. Kucera etc. IMS study of
At high voltages applied to the source of the corona Negative Corona Discharge in N2/O2 Mixtures in N2
discharge, the calibration substance pulls all the charge from Drift Gas Asta Physica Universitatis Comenianae Vol.
the peaks of background signal. This suggests that the L-LI, Number 1&2 (2009-2010) 77-83
calibration material has strong oxidizing properties. This [7] Achmetov N.S. Topical Issues Course of Inorganic
corresponds to the theoretical data [7]. Chemistry. — М.: Education, 1991. — 224 p.
In most cases, the electron affinity is less then 1 eV, but in
the case of NO2 value exceeds 3 eV. In turn, the group OH
(intermediate reactant ion in the negative mode ion

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

The Fitting Parameters Extraction of

Conversion Model of the Low Dose Rate Effect
in Bipolar Devices
Alexander BAKERENKOV
National Research Nuclear University (MEPhI), Moscow, Russia
[email protected]

Abstract - The Enhanced Low Dose Rate Sensitivity (ELDRS) in bipolar devices consists of in
base current degradation of NPN and PNP transistors increase as the dose rate is decreased [1]. As
a result of almost 20-year studying, the some physical models of effect are developed, being
described in [2] in detail. Accelerated test methods, based on these models use in standards [3, 4]. In
[5] the conversion model of the effect, that allows to describe the inverse S-shaped excess base
current dependence versus dose rate, was proposed. This paper presents the problem of conversion
model’s fitting parameters extraction.

Index Terms – Enhanced Low Dose Rate Sensitivity, ELDRS. bipolar devices, hardness assurance.

I. THE CONVERSION MODEL OF LOW DOSE RATE 

base current degradation increases is 10 2  1 D  D
.
EFFECT
The conversion model is based on the assumption that the At very low dose rates or in other words at very large
positive charge accumulated by ionizing radiation is irradiation time, all deep traps have time to be converted, so
converted to interface traps. The shallow and deep positive base current degradation reaches some constant value again.
charge traps are supposed to exist. During short period of This increase in base current degradation is greater than that
high dose rate irradiation only shallow traps are converted. for high dose rate by the value of KDD. The total excess base
An additional conversion of deep traps occurs during long current at very low dose rate is determined by total
period of low dose rate irradiation. This leads to increase of contribution of shallow and deep traps conversion.
base current degradation. Conversion process operates like a Thus the conversion model has three fitting constants: K S,
pump, pumping radiation induced trapped holes charge into KD and τD. Knowledge of these constants allows to evaluate
interface traps continuously. Mathematically base current full inverse S-shaped characteristic and to predict the base
degradation dependence versus dose rate is described by the current degradation for any dose rate at given total absorbed
following expression: dose.

 D 
I B  К D  К S   D    К D   D  e   D  1 ,
II. HIGH TEMPERATURE POST-IRRADIATION
(1) ANNEAL
  The dependence of excess base current versus time at the
where ΔIB is excess current, KD is excess base current per stages of irradiation and 40ºC, 60ºC, 100ºC post- irradiation
unit absorbed dose at low dose rate, K S is excess base anneal is presented in . 2.
current per unit dose at high dose rate, D is total absorbed
dose, γ is a dose rate, τD is deep traps conversion time.
Relationship (1) has an inverse S-shaped form (fig. 1).
During high dose rate irradiation shallow oxide traps have
time to be converted into interface traps only, because of
small time of irradiation. Therefore, excess base current is
determined by accumulation and conversion of shallow traps
at high dose rates. At such conditions the value of excess
base current is KSD.
Since some values of dose rate (mean times of irradiation)
the base current degradation starts to increase. This is
associated with the deep trap conversion with increase of
irradiation time the density of interface traps increases due to
additional conversion of deep traps. Transition time interval
is about 3  5 D . The range of dose rates, where excess
Fig.1. Schematic representation of the dependence of the excess base
current versus dose rate.

These dependences are typical for investigated NPN and

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PNP discrete transistors and input transistors of operational

amplifiers. The surface recombination component of the
base current depends on interface states density Nit at the
SiO2/Si interface, positive charge in oxide Qot and interface
traps charge Qit at forward bias of emitter junction. Energy
diagram of the SiO2/Si interface is presented in fig. 3, where
neutral interface states Nit, positive oxide charge Qot and
interface traps charge Qit (formed due to capture of carriers
injected into base by interface traps) are designated. It is
supposed that interface states located above middle of
forbidden gap are acceptor like, i.e. they are negatively
charged (Qit<0), being located below quasi-Fermi level for
electrons EFn, (fig.3, a). Interface states located below the
middle of forbidden gap donor like, therefore they are
charged positively (Qit>0) if they are free, being located
above quasi-Fermi level for holes EFp, (fig. 3, b). Effective
charge at the interface is Qeff = Qot + Qit.
The surface recombination current of NPN transistor is a)
directly-proportional to interface states density and increases
with the increase of effective interface positive charge
(positive charge attracts the injected electrons, that leads to a
recombination loss increase).

b)
Fig.2. Excess base current versus time (0-1000s – irradiation; more 1000s –
annealing) for SWB99 PNP transistor. Fig.3. Energy diagram SiO2/Si interface on forward bias emitter junction.

Therefore a decrease of the base current on the stage of post- The annealing time constant is described the Arrhenius law

 D   D0 Exp WkT  ,
irradiation anneal may be associated with decrease of Q ot or
increase of Qit, because Qeff = Qot - Qit in NPN transistors. At A
elevated temperature stress charge Qot is annealed and (2)
charge Qit may grow due to conversion of the annealed
charge. In case of PNP transistor surface recombination where τD0 is a pre-exponential constant, WA is an
current is also proportional to interface states density, but it activation energy of deep traps anneal.
decreases if the interface effective charge increase (positive Pre-exponential constant τD0 and activation energy W A in
charge repulse injected holes away from the surface, that (2) are derived from the data for two different temperatures
leads to a recombination loss decrease). Base current of elevated temperature post-irradiation anneal.
decrease during post-irradiation anneal in that case may be Only insignificant part of radiation induced trapped
associated with increase of interface states charge Qit only (in positive charge is annealed during elevated temperature
effective charge Qeff = Qot + Qit component Qot decreases, but post-irradiation anneal following high dose rate irradiation
component Qit increases). In both cases the increase of (fig.2). This may be associated with the absence of
interface states density plays a secondary role, not leading to photoelectrons on the post-irradiation phase or space charge
surface recombination current increase. effect on at high dose rate irradiation (more detail in full
The general feature of NPN and PNP transistors is that base version of paper). The small part annealed charge leads to
current decrease at elevated temperature post-irradiation impossibility to estimate a total value of deep trapped oxide
anneal is associated with the annealing of trapped positive charge and extract the constant KD. For extraction of KD we
charge. Therefore an investigation of base current behavior need some conditions, when deep trapped charge participates
during post-irradiation anneal allows to estimate activation in the process of annealing. For that we suppose to use
energy of this process and to measure deep traps conversion elevated temperature irradiation, when the annealing of all
time τD (shallow ones are annealed during the irradiation). accumulated charge occurs.

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III. ELEVATED TEMPERATURE IRRADIATION

High temperature irradiation leads to significant increase of It is desirable that this irradiation temperature corresponds to
base current degradation and it is used for accelerated tests on the maximum base current degradation at elevated
ELDRS [3, 4]. The contributions of deep traps charge to base temperature irradiation.
current degradation is estimated in this work rely on the results Constant KD is derived from (1), where the constant τ D for
of irradiation at several different temperatures. using elevated temperature is calculated from (2) (values of
Temperature elevation leads to a shift of the inverse S- τD0 and activation energy W A are determined on stage 2).
shaped curve to the direction of greater dose rates as illustrated
V. CONCLUSION
on fig. 4.
The technique for extraction fit parameters of ELDRS

Fig. 4. Inverse S-shaped curve of a device for room and elevated temperature.

It is clear from fig. 4, that irradiation temperature conversion model in bipolar transistors was proposed.
elevation is equal to the dose rate decrease. Thus if we want Presents of dip and shallow positive charge traps in silicon
to model low dose rate irradiation we have to irradiate a dioxide is assumed. ELDRS is explained by conversion of
device at certain elevated temperature. Knowing τD0 and WA dip traps. Extraction technique is based on employment
we can calculate this temperature. In turn we can derive the elevated temperature post-irradiation annealing for
values of τD0 and WA from the annealing at different determination of dip traps conversion time constant.
temperatures. Parameter relevant with deep traps concentration obtains
from elevated temperature irradiation experiment.
IV. FITTING PARAMETER EXTRACTION
Description of ELDRS S-spare characteristic is the result of
TECHNIQUE
fit parameters extraction. It provides way to prediction
Fitting constants extraction was performed by the following
radiation-inducted base current degradation at dose rate that
way:
actual in space environment.
1. Constant KS determining the contribution of shallow
trapped charge conversion to base current degradation is REFERENCES
estimated as a ratio of base current degradation to the [1] E.W. Enlow, R.L. Pease, W.E. Combs, R.D. Schrimpf,,
specified absorbed dose at 400 rad(SiO2)/s irradiation. R.N. Nowlin. Response of advanced bipolar processes
2. The deep traps conversion time or constant τD is to ionizing radiation. IEEE Trans. Nucl. Sci., 1991, vol.
estimated from data of post-irradiation anneal following NS-38, no.6, pp.1342-1351.
high dose rate irradiation to the specified absorbed dose. [2] R.L. Pease, R.D. Schrimpf, D. M. Fleetwood. ELDRS in
Pre-exponential constant τD0 and activation energy WA bipolar linear circuits: a review. IEEE Trans. Nucl. Sci.
in (2) are derived from the data for two different 2009, vol. NS-57.
temperatures of elevated temperature post-irradiation [3] Method 1019.
anneal. [4] Method EC
3. Constant KD determining the contribution of deep [5] V.S. Pershenkov, D.V. Savchenkov, A.S. Bakerenkov,
trapped charge conversion to base current degradation at V.N. Ulimov , A.Y. Nikiforov, A.I Chumakov, The
low dose rate is estimated from elevated temperature conversion model of low dose rate effect in bipolar
irradiation data. transistors. RADECS 2010.

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The Controlling of Nanoparticles by the

Polarization Methods
V.ANGELSKY, C.Yu. ZENKOVA
Chernivtsy National University, Chernivtsy, Ukraine
[email protected]
Abstract – We present the results of computer simulation of spatial distribution of the Poynting vector and
illustrate motion of nano and microparticles in spatially inhomogeneously polarized fields. The influence of
phase relations and the degree of mutual coherence of superposing waves in the arrangements of two-wave
and four-wave superposition on the characteristics of microparicle’s motion has been analyzed.

Index Terms – Poynting vector, spatial modulation of polarization, optical currents.

II. TWO-WAVE SUPERPOSITION FOR CHANGEABLE

I. INTRODUCTION DEGREE OF COHERENCE OF ONE COMPONENT
One of the most actual tasks, connected with the Superposition of two plane waves of equal amplitudes
appearance of laser, is to control microparticles of different polarized at the incidence plane (Fig. 1a) results into
nature by the help of laser irradiation. The object of distribution of the averaged over the oscillation period
controlling may be a colloid particle, a molecule, an atom, a Poynting vector shown in Fig. 1b. Such distribution arises
cell, including a bioobject, e.g. a DNA molecule, an when the interference angle equals to 90°, and the only
organelle cell. It can be said, that the technology of particle periodical polarization modulation of a field (in absence of
manipulating is a powerful tool for the work with intensity modulation) takes place at the observation plane.
microobjects of different nature. The process of trapping and Analysis of the spatial distribution of the averaged
controlling the particles depends on the properties of the Poynting vectors shown in Fig. 1b reveals periodicity of this
laser beam. One of the basic conditions of particle distribution, where the absolute magnitudes of vectors are
manipulation by the help of these laser beams is their full proportional to the lengths of lines shown in the figure. The
coherence. lines corresponding to singularities of the Poynting vector
Experimental study and computer simulation of behavior are also shown in this figure by the set of points [7-9].
of small spherical conducting particles embedded in optical Comprehensive notion on the mechanisms of formation of
fields provides deeper understanding of the role of the such distribution follows from the consideration of them
Poynting vector for description of optical currents in various both in statistics and in dynamics with the corresponding
media [1]. Accounting the modulation of waves polarized at comments, which we formulate below in thesis.
the incidence plane in forming desirable spatial distributions
of the averaged Poynting vector is the step to creation of
polarization micromanipulators and tweezers. On the other
hand, it is the step to finding out of optimal experimental
investigation of optical currents in vector fields [2-5].
Besides, the study of spatial and temporal peculiarities of
motion of particles embedded into optical fields with various
spatial configurations and with various scale distributions of
the Poynting vector inherent in both completely coherent and
partially coherent fields leads to new techniques for
estimating temporal coherence of optical fields [6].
Computation of the spatial distribution of the averaged
Poynting vectors determining the forces affecting on
microparticles and moving them is performed in this paper
Fig. 1a. Superposition of plane waves of equal amplitudes linearly polarized
following the algorithm proposed by M. Berry [1] who has at the incidence plane, with the interference angle 90°. Periodical spatial
shown that the force affecting a small particle in optical polarization modulation takes place at the incidence plane.
field is proportional to the Poynting vector. On the other
1. Light energy transfer is undulate in time and in space
hand, it is shown that the study of motion of microparticles  
in inhomogeneously polarized fields provides reconstruction (Fig. 2). Here the vectors E and H are shown in blue and
of the spatial distribution of the averaged Poynting vectors violet, correspondingly, and the Poynting vector is shown in
(optical currents). black. The directions of oscillations of this vector are the
The dependence of the force value influencing the direction of light energy transfer.
particles upon the degree of coherence of interacting waves
is shown.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

the observation plane is caused by superposition of the E x

and E z field components with changing from point to point
phase difference (Fig. 1a). Photodetector registers only
intensity I  E x2  E z2 . The sum of the squared amplitudes
of the electrical fields is constant at the observation plane,
though the state of polarization changes. The Poynting

vector is defined by the vector product S 
c  
4
E  H . One  
can see the dependence of the result (viz. the vector
magnitude and its direction) on the phase relation between
 
vectors E and H . This relation changes from point to point
at the observation plane that manifests itself in polarization
modulation. Obvious explanation follows from consideration

of the product of the components of vector E ( E x and E z
Fig. 1b. Spatial distribution of the averaged Poynting vectors resulting from 
superposition of two orthogonally linearly polarized waves with the components) with vector H . Both the magnitudes of
interference angle 90°.
projections E x and E z and their phases change from point
to point at the observation plane. As a consequence, the
vector product as well as the Poynting vector also change.
The simulation of motion of conducting particles of
diameter from 0.2 µm to 0.3 µm embedded in the field of the
considered distribution of the Poynting vector has been
carried out. It was concluded that in the case of the
distribution resulting from superposition of completely
mutually coherent waves, velocities of particle motion along
the lines of maxima and zeroes of the Poynting vector are
considerably different. Particle size is comparable with a
half-period of the corresponding distribution, however the
resultant force (Fig. 3) inducting particle motion along the
lines close to the Poynting vector maxima exceeds the
resultant force for the lines with vanishing and close to zero
Poynting vector magnitudes.
If the degree of mutual coherence of superposed waves
equals 0.2, the spatial distribution of the averaged Poynting
Fig. 2. It is illustrated wave-like light energy transfer in 2D field resulting
from superposition of plane orthogonally polarized waves of equal vectors becomes more homogeneous Fig.4, the deep of
amplitudes with the interference angle 90°. Energy transfer takes place modulation of such vector decreases considerably, and
along the bisectrix of the propagation directions of two waves at the velocities of motion of microparticles become almost the
incidence plane: the distribution of Poynting vector is presented in black same.
 
color, of vector E in blue and H in violet.

2. Spatial distribution of the averaged over oscillation

period Poynting vectors (Fig. 1b) is the map of the directions
(trajectories) of energy transfer.
3. The points at the map of the averaged Poynting vectors
(Fig. 1b) correspond to the areas through which energy
transfer is absent:
- there are the points of singularities of the Poynting
vector;
- there are the points forming the lines along which light
energy is non-vanishing, but is conserved, no being
transferred;

- there are the points where the vector H vanishes by
interference, while in this arrangement (90°-superposition of
 Fig.3. Illustration of the averaged Poynting vectors distribution, which
plane waves) superposition of strictly coaxial vectors H of forming in arrangement Fig. 1 for completely mutually coherent waves and
equal amplitudes associated with two superposing plane the formation of the resulting force (green novertical line) inducting particle
waves takes place. motion.
4. Homogeneous intensity distribution and periodical
When the degree of mutual coherence equals 0.5, relative
spatial modulation of the Poynting vector simultaneously
velocities of motion of microparticles along the same
realized at the observation plane find out explanation within
trajectories differ twice in comparison with velocities for
the framework of [10,11]. Spatial polarization modulation at
completely mutual coherence of superposed waves. One can

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see the dependence of velocities of motion of microparticles the Poynting vector, i.e. singularities of the Poynting vector.
of constant size and form in media with constant viscosity on In simulation, diameters of conducting particles are changed
coherent properties of superposed waves. These differences be comparable with a half-period of the corresponding
in velocities of motion of microparticles may be explained spatial distribution of the Poynting vector.
physically in the following manner. Increasing share of
incoherent radiation in the resulting field distribution causes
in decreasing of the modulation depth of the Poynting
vectors spatial distribution (Fig. 5), as well as in decreasing
of the resultant force magnitude along the lines of energy
transfer which causes microparticle‘s motion [12, 13].

Fig.6a. Arrangement of the superposition of four plane waves

Fig. 4. Illustration of the averaged Poynting vectors distribution in

arrangement Fig. 1 for the degree of mutual coherence of the components
0.2 and the formation of the resulting force (green novertical line) inducting
particle motion.

Fig. 6b. 2D distribution of the averaged Poynting vectors resulting from the
superposition of four waves shown in Fig. 6a.

For the sake of qualitative comparison of temporal and

spatial parameters of motion of micoparticles, we have
analyzed the maps of the averaged Poynting vector in the
arrangement of four plane waves superposition over a large
area. The dependence of microparticles motion velocities on
the phase difference of the superposing beams has been
Fig.5. Illustration of the averaged Poynting vectors distribution in
arrangement Fig. 1 for the degree of mutual coherence of the components
proved. So, in the case of pair-by-pair four opposite-in-phase
0.5 and the formation of the resulting force (green nonvertical line) superposed beams, particles become motionless. Here,
inducting particle motion. oppositeness-in-phase presumes the situation when two sets
III. THE SUPERPOSITION OF FOUR WAVES FOR of mutually orthogonal in space standing waves are
characterized by the fact, that their nodes strictly coincide.
CHANGEABLE DEGREE OF COHERENCE
OF ONE COMPONENT It follows form the presence of the minimum of the
In the case of superposition of four plane waves involving modulation depth at the spatial distribution of the Poynting
two sets of counterpropagating plane waves of equal vector. Gradual decreasing of the degree of coherence of one
intensities, linearly polarized at the incidence plane and of the superposed beams causes revival of particle motion
oriented at the angle 90° to each other, the spatial with increased velocity as the degree of coherence of one of
beams decreases.
distribution of the averaged Poynting vectors is formed, as it
is shown in Fig. 6b. If the phase relations of four superposed beams is such
One can see periodical 2D distribution of the Poynting that the modulation depth of the spatial distribution of the
vectors. As in the previous case, the lengths of the averaged Poynting vector is maximal, velocities of moving of
Poynting vectors are proportional to their magnitudes. The microparticles also depend on the degree of mutual
coherence of superposed beams. This situation is realized
points at this distribution correspond to zero magnitudes of
when two orthogonal systems of standing waves are such as

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their maxima coincide. This case we refer to as co-phasing Poynting vector (depending on the degree of mutual
of waves. The change of the degree of coherence of coherence of superpose waves) show some new feasibilities
interacting waves causes the change of the modulation depth of the use of such field characteristics and the parameters of
of the averaged Poynting vector and, correspondingly, the microparticles motion for estimating the temporal coherence
change of the movement velocity of particles. of the tested field. Initial experimental results prove these
There is exists two points, which can explain the conclusions.
superposition of four waves. At the first, the dependence of
REFERENCES
the depth of modulation at the distribution of the averaged
[1] M.V.Berry, ―Optical currents‖, Journal of Optics A:
Poynting vectors on the phase relation of superposing waves.
Pure and Applied Optics, vol. 11, 2009, pp. 094001.
It is assumed that changing the phase relation of superposed
[2] O.V. Angelsky, N.N. Dominikov, P.P. Maksimyak, T.
waves causes transition (at the observed pattern) from the
Tudor, ―Experimental revealing of polarization waves‖,
situation when the maxima of two systems of mutually
Appl. Opt., vol. 38, no.14, 1999, pp. 3112-3117.
orthogonal standing waves coincide - to the case when the
[3] T.Tudor, ―Polarization waves as observable
nodes of two such systems coincide. Thus, the velocities of
phenomena‖, J. Opt. Soc. Am. A, vol. 14, no. 8, 1997,
particles in such fields are dependent on the depth of
pp. 2013-2020.
modulation of the distribution of the averaged Poynting
[4] M.V. Berry, K.T. Donald, ―Exact and geometrical optics
vector. Secondly, the superposition of four waves linearly
energy trajectories in twisted beams‖, Journal of Optics
polarized at the incidence plane results in forming so-called
A: Pure and Applied Optics, vol. 10, 2008, pp. 035005.
―cellular‖ structure in the resulting field distribution, which
[5] M.V. Berry, M.R. Dennis, ―Polarization singularities in
can be used for transfer (transporting) as a whole of the set
isotropic random vector waves‖, Proc.R.Soc., vol.
of periodically positioned microparticles to the desirable
A456, 2001, pp. 2059-2079.
zone, see Fig. 7.
[6] O. V. Angelsky, S. G. Hanson, C. Yu. Zenkova, M. P.
Gorsky, N. V. Gorodyns‘ka,‖On polarization metrology
(estimation) of the degree of coherence of optical
waves‖, Optics Express, vol.17, no. 18, 2009, pp.
15623-15634.
[7] R. Khrobatin, I.Mokhun, ―Shift application point of
angular momentum in the area of elementary
polarization singularity‖, Journal of Optics A: Pure and
Applied Optics, vol. 10, 2008, pp. 064015,.
[8] R. Khrobatin, I. Mokhun, J. Victorovskaya,
―Potentiality of experimental analysis for characteristics
of the Poynting vector components‖, Ukr.J.Phys.Opt,
vol. 9, 2008, pp. 182-186.
[9] A.Y. Bekshaev, M.S. Soskin, ―Transverse energy flows
in vectorial fields of paraxial light beams‖, Proc. SPIE,
6729, 2007, pp. 67290G.
[10] O.V. Angelsky, S.B.Yermolenko, C.Yu. Zenkova,
Fig. 7. ―Cellular‖ distribution of the potential traps for microparticles in the
case of the superposition of four waves A.O. Angelskaya, ―Polarization manifestations of
correlation (intrinsic coherence) of optical fields‖,
Applied Optics, vol. 47, no. 32, 2008, 5492-5499.
We consider as prospective the deeper investigation of [11] O.V. Angelsky, C.Yu. Zenkova, M.P Gorsky, N.V.
peculiarities of motion of microparticles at the considered Gorodyns‘ka, ―On the feasibility for estimating the
here fields to reveal the regularities of dynamics of their degree of coherence of waves at near field", Applied
motion as a function of the coherent characteristics of the Optics, vol. 48, no.15, 2009, pp. 2784–2788.
waves constituting certain spatial polarization distributions. [12] O. V. Angelsky, M. P. Gorsky, P. P. Maksimyak, A. P.
Such investigations put in evident the prospectives of Maksimyak, S. G. Hanson, C. Yu. Zenkova,
experimental investigations of light coherence. ―Investigation of optical currents in coherent and
IV. CONCLUSIONS partially coherent vector fields‖, Optics Express, vol.
Motion of microparticles at the field in absence of 19, no. 2, 2011, pp. 660-672.
intensity modulation, only due to polarization modulation [13] C. Yu. Zenkova, M. P. Gorsky, P. P. Maksimyak, A. P.
causing the spatial modulation of the Poynting vector makes Maksimyak, ―Optical currents in vector fields‖, Applied
obvious the feasibilities for creating on this base pure Optics, vol. 50, no. 8, 2011, pp.1105-1112.
polarization micromanipulators and tweezers. Temporal and
space peculiarities of particle‘s motion in optical fields with
spatial modulation of the averaged

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Preparation and Characterization of N-doped

TiO2 with Enhanced Photocatalytic Activity
C. PĂSTRĂVANU1, M. IGNAT1, E. POPOVICI1, I. CRETESCU2*
*
Mail correspondent author: [email protected]
1
“Al. I. Cuza” University of Iasi, Romania
2
“Gheorghe Asachi” Technical University of Iasi, Romania

Abstract – TiO2 is the most frequently employed photocatalyst in realising complete mineralization of organic
pollutants in water treatment. Its large bandgap energy necessitates though UV excitation to induce charge
separation within the particle. Nitrogen doped into substitutional sites of TiO 2 has shown bandgap narrowing
and photocatalytic activity in the visible light. N-doped and non-doped mesoporous titania were synthesized
using hydrothermal and ultrasound methods. Titanium-tetraisopropoxide was used as Ti precursor. UV-VIS
and N2 adsorbtion-desorbtion techniques were used to investigate the structure, morphology and optical
properties of these photocatalysts. The photocatalytic activity of mesoporous titania was studied by different
dyes photoreactions.

from 500 to 1000 °C [13]. Low temperature processing is

considered valuable, as it affords low energy operations, and
I. INTRODUCTION
an ability to use a wider variety of substrates.
The use of TiO2 photocatalyst for the degradation of
In the environmental technology sector, industrial organic pollutant has been studied extensively. However the
wastewater treatment is gaining importance for the removal large band gap of TiO2 requires higher energy artificial UV
of organic pollutants [1]. Large amounts of organic light for activation [14].
pollutants consumed in the industries are being released into Doping of TiO2 with either anion, cation or codoping with
the eco-system over the past few decades and they constitute different dopants was found to be an effective method to
a serious threat to the environment [2]. As chemical and achieve efficient photocatalysts in the visible-light range
agricultural wastes, these contaminants are frequently [10].
carcinogenic and toxic to the aquatic system because of their There is an increasing interest in the synthesis of N-doped
aromatic ring structure, optical stability and resistance to TiO2 photocatalysts and related areas as these narrow band
biodegradation [3]. gap semiconducting materials can be used for visible light
Catalytic technologies are gaining recognition in the field photocatalysts [9]. Asahi et al. [15] reported that
of environmental protection [4]. In past decades, the substitutional doping TiO2 with nitrogen could narrow its
traditional physical techniques for the removal of organic band-gap by mixing of N 2p and O 2p states in the valence
pollutants from wastewaters have included adsorption, band and consequently induce the absorption edge red-
biological treatment, coagulation, ultrafiltration and ion shifted to lower energies (longer wavelengths, especially in
exchange on synthetic resins. Those methods have not the visible region), enhancing its visible-light responsive
always been effective and they may not actually break down photocatalytic activity. Some studies [16,17] however
the pollutants in wastewater. For example, adsorption proposed the appearance of intragap localized N 2p states,
technology does not degrade the contaminants, but related to the photothreshold energy decrease, facilitating the
essentially transfers the contaminants from one medium to formation of oxygen vacancies.
another, hence, contributing to secondary pollution [2]. Many of the dyes used in industry are toxic and
Heterogeneous photocatalysis becomes an elegant carcinogenic, and this poses a serious hazard to aquatic
alternative for dye degradation. Many photocatalysts have living organisms. The toxicity and impact of dyes released to
been used to degrade organic pollutants: ZnO, Nb 2O5, TiO2 the environment have therefore been extensively studied
[5-7]. [18]. Furthermore, because of the increasingly strict
Photocatalytic oxidation in the presence of restrictions on the organic composition of industrial
semiconducting materials such as TiO2, of organic effluents, it is essential to eliminate dyes from wastewater
compounds with environmental concern (e.g. pesticides, before they can be discharged into the environment [19].
dyes, etc.), have been studied extensively during the last 20 Rose Bengal (Acid Red 94) is a tetraiodo-substituted dye
years [8]. TiO2 is interesting due its range of applications: of the xanthenes class of dyes. It exhibits unusual
ability to split water into H2 and O2 [9] and use in dye spectroscopic and photochemical properties including a large
sensitised solar cell (DSSC) or Graetzel cells [10] being very absorption coefficient in the visible region and a high
topical. tendency for intersystem crossing to produce a
Anatase is a metastable low temperature form of TiO2 and photochemically active triplet excited state. Despite the
generally accepted as the most suitable for photochemical numerous applications of Rose Bengal dye in various areas,
devices [11,12]. When processing TiO2 precursors there is a information on its photolytic decolorization is not available
limit to the upper processing temperature. This limit is in the literature [20]. The molecular formula for this dye is
process dependent e.g. direct oxidation or sol–gel, and varies C20H4Cl4I4O5 and the molar mass is 973,67 g/mol.

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II. MATERIALS AND METHODS

Mesoporous titania was synthesized using hydrothermal
and ultrasound methods. Different blockcopolymers, such as
Pluronic P123 and F127, and titanium-tetraisopropoxide as
Ti source were used for the TiO2 synthesis. Different types
of N-doped and non-doped mesoporous titania were
synthesized by varying composition of the surfactant.

F
ig. 3. UV-VIS spectra of some synthetised samples

TABLE 1. SAMPLES NOTATION

Sample 2c 3c 7c 8c
Method A+A A+US REF+U REF+US
S
Surfactant P12 F127 P123 P123
3
A – autoclave
US – ultrasound
REF – reflux
Fig.1. The synthesis procedure for the non-doped mesoprous TiO2 P123 – Pluronic P123
F127 – Pluronic F 127
The obtained mesoporous TiO2 was used next in the
doping step of the synthesis. This involved mixing In Fig.4. the isotherms for samples 3c, 7c and 8c have
calculated quantities of TiO2 and urea such that the Ti: Urea been displaced with 50, 150 and 250 cc/g STP.
ratio in the final solution was 1:2. This solution was then All the four isotherms can be considered as type IV,
filtrated. The dry residue was transferred to calcination which is typical for mesoporous materials.
furnace and heated at 400°C for 4h to obtain the final The large amount of pores of 3 – 7 nm in diameter and the
sample. BET surfaces values of 200 – 290 m2/g demonstrate also the
fact that the synthesized samples are mesoporous materials .

Fig. 2. The synthesis procedure for the N-doped mesoprous TiO2

III. RESULTS

UV absorption spectrum and N2 adsorbtion-desorbtion

techniques have been used to investigate the structure,
morphology and optical properties of these photocatalysts.
The UV–vis spectra of the samples are shown in Fig. 3. Fig.4. N2 adsorption - desorption isotherms
The TiO2 7c sample shows single sharp edges with the band-
gap absorption onset at 387 nm (characteristic for TiO 2) The photocatalytic activities of both mesoporous titania
,while the sample containing N exhibits a slight deviation, and N-doped mesoporous titania were studied for the
which indicates the absorption edge extending into the photodegradation of the dye Rose Bengal.
visible region. The experiments were conducted using 300 mL dye
solution prepared with pure water. The solutions were
magnetically stirred in the dark for 30 minutes after adding

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the catalyst to ensure the adsorption / desorption

equilibrium. Samples consisting in three milliliters of the
suspension were taken at specific time intervals and were
immediately centrifuged at 2500 rpm for 5 min to
completely remove the catalyst particles. Zero time reading
was considered to be when the lamp was turned on.

Fig. 7. Photocatalytic activity of N-doped and non-doped mesoporous

titania under visible light

IV. CONCLUSIONS
We synthesized N-doped and non-doped mesoporous
titania via hydrothermal and ultrasound methods using
blockcopolymers (Pluronic P123 and F127) as surfactants
and organic sources of Ti.
After the samples characterization it was concluded that
all the obtained samples are mesoporous materials, having a
large amount of pores of 3 – 8 nm in diameter and BET
surfaces values of 200 – 290 m2/g.
Synthetized mesoporous titania (N-doped and non-doped)
Fig. 5. Pore size distribution (BJH method) were used as heterogeneous catalysts for the treatment of
textile wastewater containing dyes. We found that N-doped
TABLE 2. DIMENSIONAL PROPERTIES OF THE SYNTHESIZED anatase titania could be prepared by a simple method using
MATERIALS titanium tetraisopropoxide and urea. It was observed that the
2c 3c 7c 8c N-doped mesoporous titania obtained by ultrasound method
BET Surface area 229,6 290 211 243 has proven to have photocatalytic activity in visible light,
(m2/g) unlike the undoped mesoporous TiO2.
Pore diameter 5,341 3,9 5,1 5,35
(nm)
REFERENCES
Pore volume 0,334 0,46 0,424 0,45 [1] M.C. Neves, J.M.F. Nogueira, T. Trindade, M.H.
(cm3/g) Mendonça, M.I. Pereira, O.C. Monteiro,
Photosensitization of TiO2 by Ag2S and its catalytic
From the experimental results it was observed that the N- activity on phenol photodegradation, Journal of
doped mesoporous titania obtained by ultrasound method Photochemistry and Photobiology A: Chemistry, vol.
has higher photocatalytic activity than the undoped 204, no 2-3, 2009, pp 168-173.
mesoporous TiO2 (Fig. 6). Moreover, the N-doped [2] N.M. Mahmoodi, M. Arami, Degradation and toxicity
mesoporous titania also has photocatalytic activity under reduction of textile wastewater using immobilized
visible light, unlike the undoped mesoporous TiO2 (Fig. 7). titania nanophotocatalysis, Journal of Photochemistry
and Photobiology B: Biology, vol. 94, no. 1, 2009, pp
20-24.
[3] C.L. Wong, Y.N. Tan, A.R. Mohamed, A review on the
formation of titania nanotube photocatalysts by
hydrothermal treatment, Journal of Environmental
Management, vol. 92, 2011, pp 1669-1680.
[4] J.G. Yu, G.H. Wang, B. Cheng, M.H. Zhou, Effect of
hydrothermal temperature and time on the
photocatalytic activity and microstructures of bimodal
mesoporous TiO2 powders, Applied Catalysis B:
Environmental, vol. 69, no. 3-4, 2007, pp 171-180.
[5] Aditi & Fernandes, A simple method to synthesize visible
light active N-doped anatase (TiO2) photocatalyst,
Bulletin of the Catalysis Society of India, vol. 4, 2005,
pp. 131-134
[6] G.S. Shao, F.Y. Wanga, T.Z. Ren, Y. Liu, Z.Y. Yuan,
Fig. 6. Photocatalytic activity of N-doped and non-doped mesoporous Hierarchical mesoporous phosphorus and nitrogen
titania under UV light doped titania materials: Synthesis, characterization and

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visible-light photocatalytic activity, Applied Catalysis B: and V5+ transition metal ions: Influence of crystallite
Environmental, vol. 92, 2009, pp. 61–67. size and dopant electronic configuration on
[7] I.K. Konstantinou, T.A. Albanis, TiO2-assisted photocatalytic activity, Materials Science and
photocatalytic degradation of azo dyes in aqueous Engineering B, vol. 166, 2010, pp. 1–6.
solution: kinetic and mechanistic investigations: a [15] R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga,
review, Applied Catalysis. B: Environmental, vol. 49, Visible-Light Photocatalysis in Nitrogen-Doped
2004, pp. 1–14. Titanium Oxides, Science, vol. 293, no. 5528, 2001, pp.
[8] M.S. Secula, G.D. Suditu, I. Poulios, C. Cojocaru, I. 269–271.
Cretescu, Response surface optimization of the [16] H. Irie, Y. Watanabe, K. Hashimoto, Nitrogen-
photocatalytic decolorization of a simulated dyestuff Concentration Dependence on Photocatalytic Activity of
effluent, Chemical Engineering Journal, vol. 141, 2008, TiO2-xNx Powders, Journal of Physical Chemistry B,
pp. 18–26. vol. 107, no. 23, 2003, pp. 5483–5486.
[9] A. Fujishima, K. Honda, Electrochemical Photolysis of [17] T. Linsgren, J.M. Mwabora, E. Arendaño, J. Jonsson, A.
Water at a Semiconductor Electrode, Nature, vol. 238, Hoel, C.G. Granqvist, S.E. Lindquist,
1972, pp. 37 – 38. Photoelectrochemical and optical properties of nitrogen
[10] B. O'Regan, M. Grätzel, A low-cost, high-efficiency doped titanium dioxide films prepared by reactive DC
solar cell based on dye-sensitized colloidal TiO2 films, magnetron sputtering, J Phys Chem B vol. 107, no. 24,
Nature, vol. 353, 1991, pp. 737–740. 2003, pp. 5709–5716.
[11] G. Zhao, S. Utsumi, H. Kozuka, T. Yoko, [18] S. Tsuda, M. Murakami, N. Matsusaka,K. Kano, K.
Photoelectrochemical properties of sol–gel-derived Taniguchi, Y.F. Sasaki, DNA damage induced by red
anatase and rutile TiO2 films, Journal of Materials food dyes orally administered to pregnant and male
Science, vol. 33, no. 14, 1998, pp. 3655-3659. mice.
[12] K.D. Rogers, D.W. Lane, J.D. Painter, A. Chapman, Toxicological Sciences, vol. 61, no.1, pp. 92-99.
Structural characterisation of sprayed TiO2 films for [19] C.M. Teh, A.R. Mohamed, Roles of titanium dioxide
extremely thin absorber layer solar cells, Thin Solid and ion-doped titanium dioxide on photocatalytic
Films, vol. 466, no. 1-2, 2004, pp. 97-102. degradation of organic pollutants (phenolic compounds
[13] Y.U. Ahn, E.J. Kim, H.T. Kim, S.H. Hahn, Variation of and dyes) in aqueous solutions: A review, Journal of
structural and optical properties of sol-gel TiO2 thin Alloys and Compounds, vol. 509, no. 5, 2011, pp.
films with catalyst concentration and calcination 1648–1660
temperature, Materials Letters, vol. 57, no. 30, 2003, [20] C. Pastravanu, I. Cretescu, I. Poulios, E. Popovici, A
pp. 4660-666. case study of textile wastewaters treatment by
[14] L. Gomathi Devi, B. Narasimha Murthy, S. Girish heterogeneous photocatalytic degradation, Annals of
Kumar, Photocatalytic activity of TiO2 doped with Zn2+ „Dunarea de Jos‖ University of Galati: Mathematics,
physics, chemistry, informatics, fascicle II, year III
(XXXII), 2009

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Activities in Nanomedicine in Romania

Prof. Dan DASCALU
National Institute for Research and Development in Microtechnologies (IMT-Bucharest), Romania
[email protected]
The data collected in the project and from other previous
I. ABSTRACT
interactions with the main players in the domain revealed a
IMT-Bucharest coordinated the national project
great capacity, involvement and interest for developing the
―NANOPROSPECT: Nanotechnologies in Romania, a
nanomedicine field in Romania. Approximately 40
prospective study‖ (October 2010 – May 2011), whose
Romanian organizations (research institutes, universities and
objective was to put forward strategic orientations and
SMEs) and 120 specialists are active in nano-biosystems /
recommendations for a national strategy for nanotechnology,
nanomedicine, developing 60 national and 11 international
in correlation with the EU strategy. This strategy, apart from
R&D projects since 2007. They benefit from state-of-the-art
the priority research directions, will suggest measures to
equipments, developing products and technologies and also
accelerate innovation, industrialization of R&D results, full
registered 22 national patents.
use of experimental facilities, multidisciplinary training and
The cooperation between the main active organizations
the responsible development of nanotechnologies. The
started in 2005 in the frame of the Romanian nanomedicine
―nanotechnologies‖ theme was approached in the R&D
network RO-NANOMED, which financed small research
national plans starting 2000, but there was no continuity and
projects devoted to the three priority areas of the European
focus on the viable thematic areas. There is a need for a plan
Technology Platform (ETP) for Nanomedicine: targeted
that would concentrate the research for specific domains
drug-delivery, diagnostics, regenerative medicine. This
with critical mass and interest from industry and society and
network also supported the partial set-up of NanoBioLab, a
also a critical need for a strategy that would cover all the
dedicated laboratory in the clean-room area of IMT-
important aspects for the development of nanotechnologies
Bucharest, which provides an adequate environment and
at national level.
new equipments for the fabrication and testing of
The project developed databases for collecting
microarrays and lab-on-chip devices. Activities in
information related to Romanian potential in the domain (in
nanomedicine are mainly developed at IMT by two
terms of organizations, groups and specialists with expertise
laboratories from the Centre of Nanotechnologies (under the
and results in nanotechnology fields, infrastructures,
aegis of the Romanian Academy). The Laboratory of
projects, equipments, scientific papers, patents, products,
nanobiotechnologies is involved in projects related to the
technologies, courses). These databases, available in
development of microfluidic chips on silicon for
English, assure transparency and information exchange, as
electrophoretic separation of DNA fragments and PCR
they are public, interactive and relational, facilitating
amplification, development of substrates for alternatives
cooperation at national and international level.
methods of diagnosis base on microarray technology,
The analysis of human resources in the domain showed
multifunctional nanoparticles for drug delivery and the
the needs for a multidisciplinary education at various levels
Laboratory of molecular nanobiotechnology develops
and interdisciplinary training by research, the need to
Silicon-based lab-on-chip devices, bio-sensing devices for
support the young researchers and specialists returned in the
real-time detection.
country after performing long term studies or research
Some of the Romanian research organizations are
activities abroad. The interaction between education,
members of the ETP NanoMedicine, contributing to the
research and industry is essential for the improvement of
activities developed in the platform and attending events and
human resources training, in order to assure the
meetings of the working groups they are involved in. IMT-
technological competitiveness.
Bucharest is representing Romania in the Mirror Group of
―NANOPROSPECT‖ inventory showed the existence of
platform, promoting the potential for international
approximately 300 equipments devoted for nanotechnology
cooperation of the Romanian institutions.
at national level and the most efficient way to benefit from
Transnational projects in nanomedicine with Romanian
the equipments could be the set-up up of experimental
participants could be supported by EuroNanoMed ERA-NET
facilities networks.
initiative, where Romania participates as partner. This
A selection for the domains with active and
initiative fosters the competitiveness of European
multidisciplinary communities is necessary and an
nanomedicine players through the support of collaborative
innovative ecosystem can be created, based on a critical
and multidisciplinary Research and Technology
mass and on competitive advantages.
Development (RTD) projects with participants from
One of the key strategic priorities proposed by
academia, clinical/public health communities and industry.
―NANOPROSPECT‖ is ―Nanomedicine‖, the application of
nanotechnology to achieve breakthroughs in healthcare.

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Health Technology Management

Victor ŞONTEA1,4, Petru STRATULAT2,4 Reinhold WERLEIN3,4
1
Technical University of Moldova, 2State University of Medicine and Pharmacy „N.Testemiţanu‖, 3
Swiss Tropical and Public Health Institute, 4 Moldova-Swiss Perinatology Project
[email protected]

Abstract – Maintenance, Verification and Health Technologies Management became priorities in health
policies of many countries, many studies show that coherent policies in this domain may improve the
proportion price – efficiency of utilization of advanced medical technologies, improve the safety of patients
and last not least raise the quality of the medical service. In the framework of reforms in the health system,
and of major investments in medical devices, which took place in the last years in the Republic of Moldova,
the promotion and introduction of a comprehensive health technology management at all levels of the health
system is vital. The importance given to medical devices must be similar to the importance given to drugs
and infrastructure.
Keywords – maintenance, verification, management, medical technologies, medical devices

grave consequences for patients care. This is why the

existence of a national policy regarding management of
I. INTRODUCTION
medical technologies is essential; the policy would include
The worldwide industry of healthcare, with an annual
e.g. appropriate acquisition procedures, rules and regulations
financial value of roundabout $250 billion and an annual
for effective maintenance, control and correct usage of
growth of 7%, is one of the few areas that are expected to
medical technologies, training of specialized personnel and
grow for a long time. Healthcare includes 15 000 registered
creation of a continuing education.
manufacturers, about 10 000 generic devices and over a
Another report, from the American Medical Resources
million of products and brands[1]. About 50% of all
Foundations (AMRF), shows that in most cases hospitals in
diagnosis and treatment methods used today didn't exist 10
low- and middle income countries do not have the means for
years ago. Annual allocations in Medical Technologies
maintenance and repair of the provided medical devices, in
Management are 50-200 Euro per capita in EU. terms of qualified personnel, appropriate devices for testing
Maintenance, control and management of medical and calibration, management structures and financial
technologies have become a priority in the healthcare policy resources. In these circumstances, services offered by
of many countries; many studies prove that usage of representatives of device manufacturers have an extremely
coherent policies in this area, will improve the high price in these countries. An inadequate maintenance of
cost/efficiency ratio of usage of advanced medical medical devices leads to a decrease in the patient's security.
technologies as well as patients' security and the overall AMRF has proven through pilot studies in hospitals from
quality of the medical act [2-3]. several developing countries (where it trained personnel and
World Health Organization uses the term of "Medical provided equipment for testing, calibration and control) that
Technologies", which is defined as "devices, medications, expenses for the above-mentioned services were greatly
medical or surgical procedures – and knowledge associated reduced. These pilot centers became, at the same time,
with those – used in prevention, diagnosis, or treatment of training centers for local personnel. According to the
infections, rehabilitation procedures and organizational European Alliance for Medical and Biological Engineering
systems used for providing attendance". Anyway, the term of & Science, training of specialists in Biomedical Engineering
"Medical Technologies" used within the boundaries of this in 2005 was performed in 195 universities in 28 countries
article refers only to the physical hardware (from WHO's from Europe. While the number of students in engineering
definition), which has to be maintained. Medication is departments was quite constant in the last 10 years, the
usually covered by separate policy initiatives or is controlled number of students in Biomedical Engineering has increased
from different departments. 8 times. Internationally, concepts for training of specialists
and international accreditation and evaluation criteria are
II. THE SITUATION ON NATIONAL AND being developed.
INTERNATIONAL LEVELS The situation in the Republic of Moldova is similar to
Therefore, as shown in a report published on the site of those of other in low- and middle income countries; although
WHO, despite the billions of dollars annually spent on important sums are invested in medical technologies,
medical devices and equipment, the vast majority of maintenance and control of medical devices are not
countries still regard management of medical devices as an provided. At present, there are 250 active medical
acquisition question rather than an integrated part of the institutions, more than 180 enterprises and firms, whose
public healthcare policy [4]. More than 95% of medical occupation revolves around import and installation of
technologies in developing countries are imported; a large medical technologies, and over 35 enterprises and firms
part of these do not match the actual needs of their national licensed for maintenance in medical technologies. Also, as a
healthcare system. It has been estimated that in developing new direction, the scientific-applied domain of elaboration
countries about 50% of medical equipment is non-functional, and manufacturing of new biomedical technologies is being
used incorrectly and is poorly maintained – a situation with developed (the Academy of Sciences of Moldova, research

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and branch production institutes, other private firms and  Operates with them safely;
enterprises). At present, there is a severe lack of specialists  Maintains and repairs equipment;
in the field of biomedical systems and devices, since  Resigns, liquidates and replaces unsafe and obsolete
specialists in the corresponding field have not been prepared. parts;
Among the major problems and difficulties regarding the  Ensures that staff has the skills to use the equipment
management of medical technologies in Moldova can be correctly.
mentioned: Management of Medical Technologies includes several
 A severe lack of specialists in the field of components: (Fig.1).
maintenance, control and diagnostic of biomedical Based on actual information from various soures, causes
devices, including those recently imported; of defects and accidents with medical equipment can be
 Non-existence of a coherent policy regarding classified as follows:
development of activities in this field, including 10% - Technical failures;
conformation, evaluation and preventive/corrective
maintenance; 30% - Inappropriate maintenance strategy;
 Non-existing or weak managerial and technical
competence for control and maintenance of medical 60% - User's fault.
devices on the level of all hospitals, or
A correct implementation of management of medical
insufficiently used competences where actually
technologies allows 80% of problems to be solved by 20%
present;
of the resources.
 Non-existence of regulations for continuous The reference system in the policy for maintenance of
improvement, which is mandatory for specialists medical devices is shown in fig. 2.
who are active in technical service of medical The strategy for maintenance of medical devices implies
devices, inclusively for specialists who are active in the following levels:
the field of marketing and operation of medical Maintenance on user level, which implies competent
devices; users (with good knowledge of medical and technical rules
 Services offered by the providers of medical of use of the device) – information and preceding training of
devices are costly and often late. all users (authorization, accreditation), permanent access to
 No monitoring of timeliness and quality of services information of use of the device (folders which include a
provided summary of functionality, user manual, Internet etc.).
Respecting the norms of control and use, specific norms of
maintenance, cleaning and sterilization are mandatory.
III. ORGANIZATION OF HEALTH TECHNOLOGY Preventive maintenance imply competent technical
MANAGEMENT personnel, accredited according to national norms, and
Health Technology Management involves organizing and maintenance of devices including cleaning and component
coordinating the following activities, which ensures the lubrefiation; of calibration and control of functionality in
successful management of medical devices: terms of safety, of replacing spare partss, accumulators etc.
 Gathers basic information about equipment; Corrective maintenance implies specialists authorized
 Plans technological needs and adequate resources for by medical device manufacturers, repairs in the warranty and
them; post warranty periods, overhauls, upgrades.
 Purchases suitable models and installs them effectively;
 Provides sufficient resources in order to use them;

Fig.1.The structure of Management of Medical Technologies (with courtesy of SwissTPH)

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Fig.2. Reference system in the policy of maintenance of medical devices (with courtesy of SwissTPH)

The implementation of Health Medical Technologies has For a complete objective fulfilment an implementation of
the following objectives: the strategy of mixed medical device maintenance is
1. Framing of activities within national (European) and proposed – basic maintenance by own personnel with
local norms regarding management of medical devices. creation and development of a Department (workshop,
2. Framing of usage activities and service within norms section) of Management of Medical Technologies and
recommended by medical devices manufacturers, within a specific maintenance through authorized firm specialists.
framework of a maintenance adequate to the device; At the first stage, it is necessary to implement an
3. Reduction of inadequate use of modern technologies organizational structure of Management of Medical
and ensuring a continuous and effective availability of Technologies as a component of Quality Management with
medical equipment for services corresponding to the field of defined activities and responsibilities and bonds on each
healthcare; level (fig. 3)
4. Monitoring of the activities of maintenance, correction
of errors, development of specific protocols, and prediction
of costs.

Fig.3 Organizational structure of MMT on a hospital level

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At the second stage, an implementation of norms in MMT maintenance expenses (service, repair of medical
is necessary: devices) towards solving by specialists from the
1. Local norms (at the level of medical unit, medical institution.
department):  The personnel controls the immense financial
 Regulation on organization and functioning of investments in equipment, which leads to a more
Organizational Structure qualitative and efficient service, as well as a
 Rules of Procedure regarding Organizational Structure lowering of financial allocations regarding to
 post descriptions of all personnel from Organizational maintenance of medical devices.
Structure
 Call log V. PROPOSALS REGARDING DEVELOPMENT IN
 Maintenance file of the Medical Device MMT
 User guides 1. Promotion of the profession of biomedical engineer
 Medical device usage log within the national healthcare system in relation to the
 Maintenance report requirements and quality standards of the medical act,
 Medical device service file equalizing the status of a bioengineer with the one of a
 Annual plan of medical device maintenance doctor in the field of healthcare.
 Annual plan for necessity of consumables 2. Development of a policy adequate to the norms of EU,
 Electronic evidence log of the medical device regarding the progress of activities in the domain of
 Electronic registry of medical devices MMT and standards in the field.
 Electronic registry of consumables and spare parts 3. Establishing of a ―Department of Medical
 Maintenance protocols specific to the medical unit Technologies‖ charged with all tasks and problems
2. National norms: connected to management and administration of
 Decree of the Government of the Republic of Moldova Medical Technologies; at the first stage on the level of
nr. 96, from January 26, 2007 "Regarding establishing national, municipal and district (group of districts)
of terms for market placement and usage of medical health institutions,
devices" 4. To reduce expenses of maintenance of medical devices,
 Regulation regarding establishing of terms of market it is necessary to introduce stringent preventive
placement and usage of medical devices in the maintenance (service and repair of medical devices have
Republic of Moldova. to be performed by specialists from the medical
3. European(international) norms: institution), which represent 70% of maintenance
 Active Implantable Medical Devices (AIMDD) . expenses.
Directive 90/385/EEC - OJ L189/ 20.7.90 5. Creation of an information system "Management and
 Medical Devices Directive (MDD). Directive 93/42/EEC administration of Medical Technologies"
- OJ 169/ 12.7.93. 6. Development of a regulation of continuous training,
 mandatory for specialists who woirk in the field,
IV. IN VITRO DIAGNOSTIC DIRECTIVE including specialists active in the field of marketing and
(IVDD). DIRECTIVE 98/79/EC - OJ331/ 7.12.98 operation of medical devices.
Expected results
 Medical institutions can offer all required medical ACKNOWLEDGMENTS
services, and are not limited by non-functional This work was supported by the Swiss Development
technologies; Cooperation (SDC) who financially supported HTM in the
 Equipment is correctly used, correctly maintained frame of the two projects in R. of Moldova.
and verified;
 The personnel use equipment to its maximum
capacity, following written procedures and good REFERENCES
practice; 1. GMDN Agency, ―Medical Technology Brief,‖ 2007
 Health service institutions are provided with 2. Temple-Bird, CL. Practical steps for developing health
adequate information regarding: care technology policy, Institute of Development
1. functional state of the equipment; Studies, University Sussex.UK. 2000
2. Performance of the maintenance services; 3. Raab M. Maintenance strategies. Swiss Centre for
3. requried abilities and experiences of the International Health. 1999
personnel using the equipment; 4. World Bank An Overview of Medical Device Policy
and Regulation, February 2007
 A reduction of medical devices maintenance
expenses, redirection of works connected to
preventive maintenance, which are 70% of all

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Micro-Spectroscopy of Single Erythrocytes

Infected with the Malaria Parasite
1
Silki ARORA, 1Sang Hoon PARK, 2Jennifer MAUSER, 2Debopam CHAKRABARTI, 1Alfons
SCHULTE
1
Department of Physics and College of Optics and Photonics, 2Burnett School of Biomedical Sciences,
University of Central Florida, Orlando, Fl 32816-2385, USA
[email protected], [email protected]
Abstract – The erythrocytic cycle of the malaria parasite Plasmodium falciparum is marked with structural,
mechanical and biochemical modifications to the host red blood cell. The parasite degrades the hemoglobin of
the host cell and hydrolyzes it into hemozoin. We investigate healthy and infected erythrocytes using micro-
Raman and spatially resolved absorption spectroscopy. The electronic absorption spectrum of a single cell is
measured and spectral changes are related to the parasite life cycle. The Soret absorption band in the
trophozoite stage is shifted to higher wavelength by 3 nm. The findings are compared with micro-Raman
spectra that show consistent changes in the heme vibrations. Micro-absorption may offer a potential
diagnostic marker for identifying pathological states accompanying malaria.

Index Terms – Absorption microscopy, diagnostics, erythrocyte, malaria parasite, Raman spectroscopy.

hemoglobin is a complex process which involves transport

I. INTRODUCTION
of hemoglobin from cytosol to the parasite food vacuole,
Red blood cells are relatively simple biological structure
disruption of hemoglobin tetramers, removal of heme,
as they are non-nucleated and lack intra-membrane
detoxification of heme by the formation of hemozoin and the
organelles. They are biconcave shaped disks which
hydrolysis of globin by a number of proteases into amino
optimizes the flow properties in the vessels. They are the
acids.
principle means of delivering oxygen to the organs and
We probe hemoglobin degradation due to the parasite
mainly consist of hemoglobin, a globular protein. The
growth in the erythrocytes employing non invasive optical
malaria parasite Plasmodium falciparum introduces
techniques. Electronic absorption spectrum of healthy
mechanical changes in the host red blood cell [1, 2] making
erythrocytes and cells infected with the parasite are
it difficult for the cells to pass through the vessels. This
presented which can be correlated to parasite multiplication
indeed affects the oxygen transporting capability.
cycle. Micro-Raman spectroscopy was further employed to
Malaria is responsible for over a million deaths every year
investigate changes in the vibrational band with hemozoin
mostly infants, pregnant women and young children in areas
formation.
endemic for the parasites [3]. Close to half of the world‘s
population still lives in areas with high risk of contracting II. MATERIALS AND METHODS
malaria. According to a world health Organization report Parasites are maintained in human A+ erythrocytes at 5%
2009 a child dies of malaria every 30 seconds. According to hematocrit in complete RPMI-1640 (Invitrogen)
the U.S. Center for Disease Control and Prevention, more supplemented with 0.5% Albumax (Gibco). Cultures are
than 1,400 new cases are reported annually in the United split every other day to maintain a parasitemia of 2-5%, as
States in travelers returning from malaria-endemic areas. monitored by Geimsa stained smears, and freshly washed
The human malaria parasite has a complex life cycle that RBCs are added. A+ whole blood was obtained from Florida
requires both a vector body (female anopheles mosquito) and Blood Centers on a monthly basis. Whole blood is washed in
a host body. The sexual reproduction of the parasite occurs incomplete RPMI to remove unnecessary components and
in the mosquito body and the resulting sporozites are RBCs are resuspended in complete RPMI-1640 to 50% (2%
inoculated into the human host when bitten by the infection Dextrose, 15mg/L Hypoxanthine, 0.2% Sodium Bicarbonate,
carrying mosquito. These sporozites infect the liver cells and 25mM HEPES, 25ug/ml gentamycin). Parasites were
mature themselves into schizonts, each containing thousands synchronized on a MACs LD Separation Columns (Miltenyi
of merozites, which are released into the blood stream Biotec) in late trophozoite stage. Columns were placed on a
through rupturing. These merozites invade erythrocytes and magnetic stand and equilibrated with 5ml of complete
media. Parasite cultures were pelleted and resuspended in 5
goes through another round of asexual reproduction in the
ml fresh media and applied to the column. Flow through
erythrocytic cycle.
containing uninfected RBCs, ring and early trophozoite stage
During the intra-erythrocytic stage of the life cycle the
parasites was discarded; late trophozoites remained bound to
malaria parasite degrades the hemoglobin. Hemoglobin
the column. The column was then washed with 5ml of
degradation by the parasite during the intra-erythrocytic
complete media. The column was removed from the
cycle has been studied through experimental techniques and
magnetic stand and parasites were eluted with 5ml complete
mathematical models and simulations. Studies suggest that
media. Freshly washed erythrocytes were added to the
hydrolysis of globin provides the principal source of amino
synchronized culture to obtain 4% hematocrit. The following
acids for erythrocytic development and also provide
day Geimsa stained smears of the culture were prepared to
sufficient space for the parasite growth [4]. Hemoglobin
evaluate parasitemia.
degradation is also essential to maintain osmotic stability of
Raman spectra of individual healthy and parasite infected
the intra-erythrocytic parasite [5]. Breaking down of
erythrocytes were recorded on a LabRam HR 800 setup

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using 632.8 nm excitation from helium neon laser (4 mW). III. RESULTS AND DISCUSSION
The Raman system is coupled with an Olympus BX 41 Optical microscopy images of healthy human RBC and
microscope with a 100x dry objective (NA = 0.9). The RBC infected with malaria inducing parasite Plasmodium
vertically polarized laser is directed internally using a set of falciparum are shown in Fig. 2. The cells are contained in a
mirrors and focused through a lens onto the sample. The micro-capillary of inner bore 50 m. Image on the right
Raman signal collected by the microscope objective in back shows the cell with the parasite in it at 24 hr post invasion.
scattering configuration through the same optical path and Through optical images without stains it is difficult to
through a holographic notch filter to the 100 m confocal discern between healthy and infected cells and to correlate
pin hole of the spectrometer. Spectra were recorded between them to parasite multiplication cycle. The results that follow
1800 and 650 cm-1 with a resolution of 1.5 cm-1. A fused show the micro-absorption as a potential diagnostic marker
silica micro capillary with an inner bore of 50 m and outer for different stages of parasite multiplication cycle.
diameter 350 m was used a nano liter sample holder. An Micro-Raman spectra of a healthy red blood cell and a cell
optical window was created by burning the outer coating and
wiping the capillary through ethanol. The sample was loaded
in a micro capillary by dipping one end in the sample culture
allowing capillary action to draw the cells up. The small
volumes and small optical window allows us to investigate
individual cells without interference from the neighboring
cells.
Fig. 2 Erythrocytes in a micro capillary: healthy (left) and infected
(right). The diameter of a single cell is ~ 7 m.

infected with Plasmodium falciparum are shown in Fig. 3

(left panel). The excitation wavelength was 633 nm. The
bands in the spectra mainly arise from porphyrin vibrations
[7]. The Raman scattering enhancement observed at 632.8
nm may result from excitonic coupling between aligned
porphyrins due to the close proximity of heme moieties [8].
The vibrational bands are indicative of hemoglobin, the
major protein in the cell. They can be grouped into the
following regions: 1500 – 1650 cm-1: core size or spin state
marker band region. 1450 – 1300 cm-1: pyrole breathing
mode region, 4. 1300 – 1200 cm-1: methine C-H
deformation region. 1450 – 1300 cm-1: pyrole ring breathing
mode, 15. The peak positions are dependent on oxidation
Fig. 9. Schematics of the micro-spectroscopy setup. Raman state. While a band at 1545 cm-1 is the most intense peak in
scattering is excited by a He-Ne laser and the signal is collected in deoxygenated cells, the spectra show clearly two different
a back-scattering geometry. Micro-absorption spectra are measured
in transmission geometry.
peaks at 1548 cm-1 and 1565 cm-1. The 13 mode of the
oxygenated heme has a frequency of 1224 cm-1 compared to
Confocal absorption microscopy was employed to measure
1211 cm-1 in the deoxy state. These peaks are representative
optical absorption spectrum with spatial resolution at the
of those seen in oxygenated cells as these bands are
micron scale [6] to investigate the changes in the electronic
dependent on oxidation state and on whether the heme has
absorption bands of host red blood cells after parasite
bound oxygen [8]. The 1500 - 1650 cm-1 region is dominated
infection. It couples confocal microscopy with broadband
by the core size (or spin state marker band). There are clear
illumination in transmission geometry. It enables the
differences between Plasmodium falciparum infected and
measurement of the absorption spectrum of a single
uninfected cells in this region, and in the broadening of the
erythrocyte between 350 and 700 nm with a lateral
peaks near 1210-1230 cm-1 (C-H methine deformation band)
resolution better than 1.5 m. and 755 cm-1 (pyrrole ring breathing mode). The spectral
Micro-absorption spectra were measured on red blood changes are in agreement with those reported by Wood and
cells immobilized on a coverslip using standard procedures. co-workers in independent experiments [9]. As the
The coverslip was rinsed with 70 % Ethanol followed by 1X hemoglobin is broken down by the parasite, the protein chain
Phosphate Buffer Saline (pH 7.4). Sufficient 1mg/ml poly-L- fragments are transported away for further digestion. The
Lysine HBr was applied to coat the coverslips which were remaining toxic heme is then oxidized to a ferric state. The
then kept at room temperature for 15 minutes. Coating release of the heme from the protein is the first step in the
solution was removed and the coverslips were rinsed with formation of hemozoin. The changes in the spectra could be
1X PBS. The erythrocytes suspended in 1 X PBS were the result of this degradation and the changes in the
added to the coverslips and were allowed to adhere at room vibrational modes of the now free heme. As the heme rings
temperature for 20 minutes. Excess liquid was drained from are no longer bound within the pocket of the protein the
the coverslip. The transmittance of an individual red blood constraints on the various bonds will be much more random
cell was measured with a spectral resolution of 0.5 nm. which accounts for the broadening of the bands.
Micro-absorption spectra were recorded of erythrocytes The right panel in Fig. 3 shows the micro-absorption
immobilized both on coverslips and in micro-capillaries and spectrum of individualerythrocyte in the healthy and infected
found to be in agreement. state. An individual live erythrocyte under physiological
condition was illuminated using broadband excitation and

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the transmitted light intensity was collected using the the National Academy of Sciences, vol. 105, pp. 13730,
spectrometer with 5 seconds acquisition time. The spectrum 2008.
was obtained over the visible range from 350 to 700 nm. [2] S. Suresh, "Mechanical response of human red blood

Fig. 3 Micro-Raman (left) and micro-absorption (right) spectra of single erythrocytes. The top spectrum in each panel is from a healthy erythrocyte.
The spectra at the bottom are from erythrocytes infected with malaria parasite Plasmodium falciparum.

The electronic absorption spectra of porphyrins feature cells in health and disease: some structure-property-
two weak visible transitions near 555 nm and the intense function relationships," J. Mater. Res, vol. 21, pp. 1871,
Soret transition near 400 nm [10]. The intense absorption 2006.
bands result from to  to * transitions and can be [3] "US Department of Health and Human Services
distinguished from the weak bands due to charge-transfer National Institutes of Health National Institute of
transitions. The spectra depend on the electronic Allergy and Infectious Diseases NIH Publication No.
configuration of the iron cation and can be correlated to the 02-139," 2002.
spin state [10]. The absorption spectrum of the healthy red [4] I. W. Sherman, Molecular approaches to malaria: Amer
blood cell is indicative of oxygenated hemoglobin with the Society for Microbiology, 2005.
Soret band at 415 nm and - and -bands at 541 and 577 [5] V. L. Lew, T. Tiffert, and H. Ginsburg, "Excess
nm, respectively. The ratio of relative intensities of - and hemoglobin digestion and the osmotic stability of
-bands was calculated to be 0.87 as compared to the Plasmodium falciparum–infected red blood cells,"
literature value of 0.92 [11]. Blood, vol. 101, pp. 4189, 2003.
Changes in peak positions and relative peak intensities [6] S. Arora, J. Mauser, D. Chakrabarti, and A. Schulte,
were observed in the case of cells in pathological conditions. "Spatially resolved micro-absorption spectroscopy with
The Soret band was weaker than in uninfected sample and broadband source and confocal detection," to be
submitted.
was shifted to 418 nm. The - and -bands moved to 543
[7] B. R. Wood, B. Tait, and D. McNaughton, "Micro-
and 576 nm, respectively. The ratio of the relative intensities
Raman characterisation of the R to T state transition of
of the two bands decreased to 0.67. The peaks were broader haemoglobin within a single living erythrocyte,"
and less intense in the infected sample. Biochimica et Biophysica Acta (BBA) - Molecular Cell
Understanding the structural changes in the degradation of Research, vol. 1539, pp. 58, 2001.
hemoglobin may opens new targets for anti-malarial drug [8] B. Wood, D. McNaughton, "Raman excitation
treatments. Observing the cells in a native-like environment wavelength investigation of single red blood cells in
facilitates the transfer of new diagnostics for faster detection vivo, " J. Raman Spectrosc., vol. 33, pp. 517, 2002.
of the parasite‘s presence in the human body. [9] B. R. Wood, S. J. Langford, B. M. Cooke, J. Lim, F. K.
Glenister, M. Duriska, J. K. Unthank and D.
IV. CONCLUSION
McNaughton, "Resonance Raman Spectroscopy Reveals
Micro-Raman and micro-absorption were combined in a
New Insight into the Electronic Structure of β-Hematin
comparative analysis of healthy RBCs and RBCs invaded
and Malaria Pigment," J. Am. Chem. Soc., vol. 126, pp.
with the malaria parasite. Both techniques are sensitive to
9233, 2004.
heme degradation occurring during the multiplication cycle
[10] M. W. Makinen, A. K. Churg, A. B. P. Lever, and M. B.
of the parasite. The spectral changes observed in the micro-
Gray, "Iron Porphyrins Part 1," Addison-Wesley
absorption spectra may enable a diagnostic probe at the
Publishing Co., Mass, 1983.
single cell level.
[11] E. Antonini and M. Brunori, Hemoglobin and
V. REFERENCES Myoglobin in their Reactions with Ligands: North-
[1] Y. K. Park, M. Diez-Silva, G. Popescu, G. Lykotrafitis, Holland Pub. Co., 1971.
W. Choi, M. S. Feld, and S. Suresh, "Refractive index
maps and membrane dynamics of human red blood cells
parasitized by Plasmodium falciparum," Proceedings of

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Ultra Violet Radiation Regulates Wettability

Property of Prosthetic PMMA.
Yuri DEKHTYAR, Linda LANCERE, Nataliya POLYAKA, Alexander SUDNIKOVICH, Fyodor
TYULKIN
Riga Technical University, Str.Ezermalas 6, LV-1014
[email protected], [email protected], [email protected], [email protected],
[email protected]
Abstract – Prosthetic poly (methyl methacrylate) is widely used for medical applications like lenses and eye
prostheses. For prosthetic products biocompatibility is essential, different methods have been developed to
control it by controlling surface wettability property. This article is targeted to describe a possible simple
solution how to influence alterations of PMMA wettability by non-ionizing UV radiation in range of 200-
400nm. Processed material was examined by means of detecting contact angle, electron work function and
absorption spectra to find correlation between wettability and other surface properties. Results show non-
linear tendency of surface wetting alteration and peculiarities in electron work function and absorption
spectras. UV radiation could be used to functionalize PMMA surface by not influencing its structure with UV
exposures under 60 minutes.
Index Terms – Poly(methyl methacrylate), wettability, UV radiation, surface properties, electron work
function

project drop to the PC. Optical microscope was used to

I. INTRODUCTION
define the drop of physiological solution (~10mm in
Poly (methyl methacrylate) is a widely used material in
diameter). Measurements were repeated 15 times, contact
various fields. Because of its good biocompatibility, PMMA
angle each time was applied in the Photoshop software
is used for prosthetic applications, the ways to enhance
(CS3). Before measurements each sample was cleaned with
surface properties of PMMA are being searched. Basically
distilled water.
surface properties are the ones that influence interaction
The hand-made spectrometer [6] ensured induction of
between polymer and environment and the ones to be
photoelectron emission from the PMMA material to measure
modified [1]. Surface wettability is of high importance in
electron work function that is directly proportional to a
oral prosthetics [2], eye lenses [3], etc.
surface charge.
Wettability depends on material‘s surface energy that, in
To reveal possible reconstruction of the chemical couples
turn, could be influenced by the electrical charge, deposited
optical absorption was measured in a range of 200 – 400nm
on to the surface. Evaluating material‘s electron work
with a step 0.5nm Helios photo spectrometer was used. The
function, connected with surface charge and surface
data of the spectra were collected with VISIONlite (Scan
potential, may show regularity between the described above
Version 2.1) software, after that digital data were imported
and might be used to control wettability.
to Excel for further processing. PMMA specimens before
Ultraviolet (UV) radiation has already been used for
and directly after each irradiation session were measured.
surface charge modification [4-5], though more
To evaluate alterations of surface morphology and
unsophisticated method and insufficiently investigated
distribution of the charge/potential over the surface at the
wavelength range 200 – 400 nm to be employed is described
nano/micro scale, the specimens were scanned using Solver
in this article.
P-47 Pro atomic force microscope in semi – contact
II. METHODS AND MATERIALS topography and Kelvin probe modes. The NSC01 platinum
The specimens were prepared in identical manner as eye coated conducting tip was applied.
prostheses. To characterize local electrical charges distance influence
After polymerization of commercial powder ―Stoma‖ on the electrical potential the autocorrelation function of the
mechanical treatment was applied (slipping and polishing) to several potential distributions realizations over the surface.
reach the specimens with diameter of ~1cm. The specimens When the autocorrelation function reached the zero value,
were cleaned with 96% ethanol to remove foreign bodies. the distance (correlation length) was assumed as the
After that irradiation process was implemented in room air localized charge distance length.
(+ 200C +/-20C) by means of Hamamatsu Spot Light Source
III. RESULTS
equipped with Hg-Xe lamp with intensity 3.5W/cm2 at
UV influences contact angle (Fig.1). When the exposure
365nm. Specimens were placed at 0,4 m distance to avoid
increased until 60 min, the contact angle decreased.
overheating and ensure room temperature on the PMMA
However, at the exposure > 60 min the angle increased.
surface. Irradiation was amassed by different exposure
At the same time the contact angle value positively
sessions (15, 30 or 90 minutes of exposure was
correlated with an radiation induced increment of the
accumulated).
electron work function (Fig. 2 ) that characterized the
Wettability was tested before and after UV irradiation
alteration for the surfaced charge density (higher value of the
using Axisymmetric Drop Shape Analysis-Profile (ADSA-P)
electron work function relates to the greater value of the
method. This method was adjusted to use in set with optical
negative charge) .
microscope MMI-2 and CCD camera (Imaging Source) to

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electrical charge factor contributes wettability. Absence of

the absorption minimum at > 60 min signals that UV
reconstructs the PMMA surface layer.

Fig.1. Contact angle increment dependence on UV exposure

Fig.4. Correlation length depending on contact angle value

Perhaps both structural alterations and deposition of the

electrical charge influences the correlation length.

IV. CONCLUSIONS
1. UV radiation supplied from the Hg-Xe lamp with
intensity 3.5W/cm2 at 365nm to the PMMA surface
located at the distance 0.4 m from the UV source
supplies the surface with both structural alteration and
Fig.2.Correlation between angle and electron work function increment
electrical charge, when the exposure was > 60 min.
However, if the exposure < 60 min the structural
The absorption spectra demonstrated a minimum at about alteration were not observed.
3.25eV or 380nm (Fig.3) when the UV exposure was <60 2. The deposited electrical charge is characterized with
min. However at the exposure > 60 min the minimum decreasing of the correlation length when the contact
disappeared. . angle > 55 o.
3. The contact angle depends on UV exposure.
4. The UV radiation could be employed to functionalize
PMMA wettability, the structure uninfluenced
radiation mode being available at exposure < 60 min.
5.
REFERENCES
[1] Y.Wang, J.Robertson, W.Spillman et al., ―Effects of the
Chemical Structure and the Surface Properties of
Polymeric Biomaterials on Their Biocompatibility‖,
Pharmaceutical Research, Vol.21, p.1362, Aug.2004
[2] O.Etienne, C.Picart, C.Taddei et al., ―Polyelectrolyte
Multilayer Film Coating and Stability at the Surfaces of
Oral Prosthesis Base Polymers: an in vitro and in vivo
Fig. 3. Absorption data. Derivative dependence on photon energy value Study‖, J Dent Res, Vol.85, p.44, Sept.2005
The morphology of the surface was not influenced by [3] N.Lee, S.Moon, S.Kang et al., ―The Effect of
radiation. However the surface electrical potential Wettability of Nickcl Mold Insert On the Surface
demonstrated connection with radiation exposure. The Quality of Molded Micro lenses‖, Optical Review,
correlation length correlated with the contact angle vol.10, p.240, June 2003
influenced because of UV radiation (Fig.4). [4] J.Deng, L.Wang, L.Liu et al., ―Developments and new
applications of UV-induced surface graft
DISCUSSION polymerizations‖, Progress in polymer science, Vol.34,
Alteration of the contact angle influence by UV radiation p.156, Oct.2008
can be stipulated because of radiation induced reconstruction [5] X.Lu, Y.Jin, S.Tan et al., ―A Simple Approach for
of the PMMA surface layer or deposition of the electrical Fabricating a Superhydrophobic Surface Based on
charge. The latter could be provided because of the emission Poly(Methyl Methacrylate)‖, J Adhes Sc Techn, Vol.22,
of the electrons escaped from PMMA due to the UV p.1841, 2008
photons. Unchangeable absorption spectra minimum at [6] RJ. Akmene, A.Balodis, Y. Dekhtyar et al.,
exposure > 60 min gives a possibility to assume that such ‖Exoelectron emission specrometer complete set of
exposures do not have an influence on the PMMA surface surface local investigation‖, Phys Chem Mech Surface,
layer structural peculiarities. However, the alteration of the Vol.8, p.125, 1993
contact angle at exposure < 60 min evidences that the

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Optical Dosimetry for Controlling the

Efficiency of Laser Phototherapy
M.M. ASIMOV 1, R.M. ASIMOV 2, A.N. RUBINOV 1, A.I. GISBRECHT3
1
Institute of Physics National Academy of Sciences of Belarus, Minsk, Belarus
e-mail: [email protected]
2
"Sensotronica Ltd.", Minsk, Belarus
e-mail: [email protected]
3
Institute of Electronics Bulgarian Academy of Sciences, Sofia, Bulgaria
e-mail: [email protected]

Abstract. – The results in vivo investigation biophotonics of laser-induced photodissosiation of oxyhemoglobin

in cutaneous blood vessels and its role in biomedical processes are presented. New method for determination
an individual response to the effect of laser radiation is presented. It is shown that in order to make the
phototherapy as well as laser therapy methods really efficient one has to control the oxygen concentration in
tissue keeping it at the necessary level. Novel method of optical "dosimetry" based on using the changes
oxygen concentration in tissue as feedback signal for optimization therapeutic effect of low intensity laser
radiation is developed.

Keywords – hemoglobin, oxyhemoglobin, tissue oxygenation, hypoxia, phototherapy, photodissociation.

efficiency of the therapeutic effect of low intensity laser

I. INTRODUCTION
radiation (optical ―dosimetry‖) is not correct and reliable.
Biophotonics of "laser-tissue" interaction and the effect of
In this paper new method of optical "dosimetry" based on
laser radiation on oxyhemoglobin in cutaneous blood vessels
using the changes of oxygen concentration as feedback
and capillaries is considered as one of the interesting aspects
signal for optimization of therapeutic effect of laser radiation
of modern photomedicine and photobiology. Application of
is presented. It is shown that photodissociation of
low intensity laser radiation in treatment of a variety of
oxyhemoglobin; whose main biological function is the
diseases has been developed extensively during the last five
transportation of molecular oxygen, gives unique possibility
decades.
of additional oxygen supply and allows develop laser-optical
Biostimulation and therapeutic effect of laser radiation is
method of tissue hypoxia elimination for restoring normal
well-established fact and currently widely uses in clinical
cell metabolism.
practice. At the same time the mechanism of therapeutic
effect of laser radiation is not yet clearly understood and II. THE PHENOMENON OF LASER-INDUCED BLOOD
considered to be very complex that involves anti- OXYHRMOGLOBIN PHOTODISSIATION
inflammatory, analgesic and anti-edematous effect on tissue Since 1997 new technology of laser-induced
[1-4]. Most exiting effect of laser therapy could be seen in photodissociation of oxyhemoglobin (HbO2) in cutaneous
wound healing were process of fast epitelization clearly blood vessels and its biomedical applications is developing.
demonstrate its efficiency. Unique possibility in selective and local increase of the
The mechanism of therapeutic effect of laser radiation is concentration of free molecular oxygen in tissue is obtained
still remains unclear that make difficult to develop correct [7-10]. The efficiency of the interaction of laser radiation in
method for controlling the efficiency of laser therapy - different wavelengths on HbO2 in cutaneous blood vessels is
correct ―dose‖ of delivered average energy of laser radiation. studied. Mathematical model for calculating optimal
In present the efficiency of therapeutic effect is controlled parameters of laser radiation to induce an effective
by using an empirical unit based on average power density photodissociation of hemoglobin (Hb) complexes in
of output laser radiation. Experimental study the therapeutic cutaneous blood vessels has been developed.
effect of He-Ne and Argon laser radiation in open skin The temperature dependence of the quantum yield of
wound healing [5] was carried out at power density of photodissociation of HbO2 observed earlier in vitro is proved
45mW/cm2. Maximal therapeutic effect due to significant experimentally in vivo [10]. Unique possibility in selective
increase of collagen synthesis at the total energy density of and local increase of the concentration of free molecular
4J/cm2 has been reached. Similar experimental study [6] oxygen (O2) in tissue is demonstrated.
with He-Ne laser radiation at power density of 4,0mW/cm 2 As it well known the concentration of oxygen is critical in
demonstrated the therapeutic dose (complete heeling of enhancing in vivo wide variety of biochemical reactions
wound) at lower average energy ~1,22J/cm2. including cell metabolism. Aerobic cell metabolism is
Big differences in experimental results in healing two primary mechanism in energy production in tissue.
cases of identical open wounds where therapeutic effect are Controlling this mechanism gives unique possibility of
reached in different output power of He-Ne laser radiation biological stimulation to reach therapeutic effect. This goal
remains not clear. could be reached by the means of laser-induced
Nevertheless the power density of 4J/cm2 is accepted as photodissociation of oxyhemoglobin in cutaneous blood
extreme level ("dose") for reaching maximal therapeutic vessels.
effect. Accepted empirical criterion for controlling the

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Absorption of light by blood Hb and HbO2 allows can be neglected. Thus in practice the value of SaO2 could
consider and discuss the following photophysical and be determine as
photochemical processes. Photophysical process is SaO2 = {[HbO2] /([HbO2]+[Hb])}100
connected with nonradiative dissipation by Hb and HbO2
electronic excitation energy. The heat generated in this Photodissociation of HbO2 induced by laser radiation
process is transferred to the blood capillaries, which has the releases free molecular oxygen. Meanwhile, proportion
characteristic time of thermal relaxation ~ 0.05-1.2 msec. between [HbO2] and [Hb] concentrations is changed that
The mechanism of the laser-tissue interaction is very decrease the value of SaO2.
much dependent on the output laser energy. The effect of
high-energy lasers is quite clear and based on photothermal SaO2 = SaO2 - SaO2h
processes such as selective photothermolysis. 
This mechanism is used in clinical practice, for example, Were SaO2 is saturation without and SaO2hwith laser
in laser surgery, cosmetology, laser correction of vision etc. irradiation.
It is clear that the effect of heating due to absorption of low Amount of oxygen available for cell metabolism delivered
energy laser radiation in a tissue is negligible. Estimate by microcirculation is the function of:
shows that in typical case the local increase of temperature
only by 0.1 - 0.5 0C may be expected. Such a small raise of a  О2 (TcPO2) = f(F(HbO2)*[O2])
local temperature may promote only some improvement in
capillary microcirculation of blood and hardly could Were HbO2 is the value of oxyhemoglobin arterial blood and
stimulate the metabolism of cells. [O2] - is the concentration of oxygen released into plasma.
We suppose that in a case of low energy lasers the most In the case of deterioration of the blood microcirculation
important process is the photodissociation of HbO2, whose extra oxygen supply is critical to provide the demands of cell
main biological function is the transport of molecular for normal metabolism. This could be reached by in vivo
oxygen. The quantum efficiency of the photodissosiation laser-induced photodissociation of HbO2 directly at the zone
[11] of oxyhemoglobin is amazingly high and reaches 10 % were necessary to increase the local concentration of free
in a wide visible spectral range. The molecular oxygen is molecular oxygen.
generated due to laser-induced photodissosiation of HbO2 in As a result we obtain average concentration of oxygen
blood vessels allows control the local increase of oxygen that releasing in conventional way and due to
concentration at irradiating region (fig. 1). O2] = [O2] + [O2h
Thus phenomena of laser-induced in vivo
photodissociation of oxyhemoglobin in cutaneous blood
vessels and capillaries gives unique possibility of optically
increase the local tissue oxygen concentration.
III. REGISTRATION OF BLOOD OXYHEMOGLOBIN
PHOTODISSOSIATION IN VIVO
Experimental study the change of arterial blood saturation
due to laser-induced photodissociation of oxyhemoglobin is
based on registration the variations of its value on the
background natural oscillations of saturation. Specialized
pulse oxymeter spectrophotometer for recording
photoplethysmogram with high accuracy and detailed
numerical signal processing has been applied. Despite of
traditional pulse oxymeter instead of two channels for signal
registration in red and infrared spectral ranges fore channel
that supplied parallel 8 independent signal processing it has
been used [12,13]. As a result the registration of small
Fig. 1 - Illustration of laser-induced tissue oxygenation caused by
photodissociation of arterial blood HbO2
changes of arterial blood saturation for one heart pulse is
reached with accuracy less than 0.5 %.
The possibility of additional oxygen supply allows The measurements of the value SaO2 was carried out with
develop a new method of tissue hypoxia elimination that the high sensitive pulse oxymeter sensors in transmitting
restores normal cell metabolism. Investigation of light with accuracy better than 0.5 %. The sensor was placed
photodissociation of hemoglobin complexes in vivo could be on the first of the two phalanxes of the finger and measuring
carried out using arterial blood saturation parameter. elements were in the region of the first phalanx (fig. 2).
In case of HbO2 the value of saturation SaO2 in arterial The effect of laser radiation on arterial blood oxygen
blood vessels is defined by the concentration of HbO2 taking saturation has been observed using He-Ne laser with
into account contribution of Hb, methemoglobin (MetHb) wavelength 632 nm, which is mostly applied in medical
and carboxyhemoglobin (HbCO). practice. Lasers spot on a skin was about 7-8 mm with power
SaO2 = {[HbO2] / density of 20 mW/cm2. The laser radiation was guided to an
([HbO2]+[Hb]+[MetHb]+[HbCO])}100 interior of the third phalanx of a finger.
At normal conditions of gas exchange the concentrations
of MetHb and HbCO are extremely low (0.2 - 0.6 % and 0.8
% correspondingly) so the contribution of these components

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IV. NEW METHOD OF OPTICAL "DOSIMETRY"

Pulse-oxymeter BASED ON CONTROLLING LOCAL TISSUE
OXYGANATION
Signal Laser-induce photodissociation of HbO2 gives a novel and
unique method for optically increasing the local
processing concentration of free molecular oxygen in tissue that is
module significantly enhances cell metabolism. Taking into account
Laser that blood deliver O2 to any cell tissue and metabolism of
radiation cells required consumption of oxygen we suggest to base
He-Ne therapeutic effect of laser radiation based on controlling
summary tissue oxygen concentration.
- Proposed method for optimization therapeutic efficiency
the effect of laser radiation is based on using the change
in oxygen concentration as feedback signal.
Fig. 2 - Experimental setup for investigation of the effect of laser radiation - Oxygen released into tissue is proportional to the energy
on the value of arterial blood saturation of aerobic cell metabolism.
The concept of laser-induced tissue oxygenation allows - Photodissociation of HbO2 increases the level of tissue
understand the mechanism of biological response and oxygenation.
therapeutic effect of laser radiation. Its also gives a unique - Oxygen release rate could be directly measured in vivo
method of selective local tissue oxygenation, that could be through the value of saturation - SaO2
used in wide range of biomedical applications. - Capacity of circulatory system to carry oxygen defined
Using another direct method of oximetry (Fig. 3) based on by hemoglobin concentration [Hb] and also is a function
principle of measuring the oxygen tension РО2 in arterial of how much blood per minute is pumped from the
blood is direct method of registration of gas that dissolved in heart.
blood plasma. Controlling parameters are:
- Aerobic metabolism - (energy production);
- Extra oxygen release into tissue due to
photodissociation of HbO2;
- Ability of blood circulation system to transport oxygen.
Measuring parameters:
- Amount of oxygen released into tissue;
- Changes in arterial blood saturation DSaO2;
- Hemoglobin concentration and heart pulse rate.
In this case we can refer to the pulse volume of heart V H
which is equal to blood volume in liters that pump the heart
at one bit. Then oxygen flux F(O2) through the irradiating
zone of tissue we can describe as

F(O2) = 4[О2]/ ([Hb] + 4[О2]) * C * VH * [Hb]* ( SaO2 /

100),
Fig.3 - Measurement of tissue oxygen tensions due to photodissociation of
blood HbO2: 1 - Clark sensor, 2 - electrolytic cell, 3 - irradiating zone, 4 - Where С – is a coefficient of blood delivery to tissue
monitor TCM - 4, 5 - He- Ne laser. indicating tension in capillary blood vessels and [Hb] – is the
For this usually are used Clark-type polarographic sensor concentration of hemoglobin in gm/l. SaO2 – is the degree of
(―TcPO2 electrode‖, see fig. 3) that consist of silver anode, hemoglobin oxygen saturation in percents, and [О 2] – molar
electrolyte, and an oxygen permeable membrane; heating concentration of oxygen.
section and electronic system for measuring and controlling Than we introduce the notion of ―standard flux of oxygen
the sensor temperature. through the tissue‖
The initial oxygen tension in tissue was measured by
placing TcPO2 electrode on human skin in shoulder area. S(F.O2) = 4 [О2] / ([Hb] + 4 [О2]) * [Hb]n* C * VH
Then He-Ne laser radiation at the power of 1mW was
applied. Kinetics of tissue oxygen tension was ―Standard flux of oxygen through the tissue‖ indicates a
experimentally investigated [14]. Obtained results were flux of oxygen that is necessary for supplying tissue at
normalized to initial oxygen tension value. normal conditions.
These two above mentioned methods allows to measure Normal conditions are related to the concentration of
and control the process of releasing extra oxygen from HbO 2 hemoglobin in blood that corresponds for the given age and
under laser irradiation directly to arterial blood plasma and complete saturation with oxygen.
future it diffusion into tissue. For the estimation of current oxygen delivery through the
tissue we normalize the local flux to the standard one

F(O2) = F(O2) / SF(O2)

Than we obtain

F(O2) = [Hb]/[Hb]n* ( SaO2 / 100)

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It should be noted that involved parameters are objective

This parameter allows us estimate current efficiency of and could be measured by well-known clinical routine.
oxygen delivery in dependence of the concentration of Suggested new method of optical "dosimetry" based on key
hemoglobin and degree of its saturation with oxygen. Now biological parameters and connected with aerobic cell
we can determine the quantity of oxygen that releases into metabolism provides possibility of precise determination of
tissue during elimination with low intensity laser radiation. therapeutic effect of laser radiation.
V. EXPERIMENTAL
FO2 =F(O2) - F(O2 )h
Experimental investigation the phenomenon of laser-
induced tissue oxygenation has been carried out using
Were FO2 - is normalized flax of oxygen without laser
transcutaneous oxygen monitor (TCOM) - "Radiometer‖
irradiation and FO2h - is normalized flax of oxygen during ТСМ-4 (Fig.4).
laser irradiation.
The dose of oxygen that that releases into tissue during
elimination with low energy laser radiation can be
determined from following expression:

[O2] = {F(O2) - F(O2 )h * T * Pr

Were Т – is the time of irradiation and Pr - is pulse rate.

Substituting expressions for FO2 and FO2h we obtain:

[O2] = ([Hb]/[Hb]n* ( SaO2 / 100) - [Hb]/[Hb]n* ( SaO2h /

100)) *T * Pr =
= T * Pr * [Hb]/[Hb]n *( SaO2 - SaO2h) / 100 = T * Pr *
[Hb]/[Hb]n *(SaO2 / 100)
Thus the "dose" of oxygen that that releases into tissue
during irradiation with low intensity laser radiation can be
determined from following expression:

[O2] = T * Pr * [Hb]/[Hb]n *(SaO2 / 100),

Fig. 4 – Experimental setup for controlling local tissue oxygen
Suggested method of determination of therapeutic dose of concentration directly at the zone of laser irradiation
laser radiation correlated with tissue local oxygenation could
Direct in vivo measurements of tissue oxygen tension
be applied in clinical practice. Developed high sensitive
TcPO2 under irradiation by He-Ne laser at the power of
pulse oxymeter completely provides determination of all
1mW has been carried out [14].
parameters for establishing a therapeutic dose for healing a
Using the simple diffusion model we calculated what
huge variety of diseases by laser phototherapy.
amount of oxygen should be released into blood plasma in
Laser induced photodissociation of HbO2 allows extract
order to reach experimentally observed increasing tissue O 2
additional amount of oxygen locally at irradiating zone. This
concentation (fig. 5). The target criteria were kinetic of
phenomenon provides unique possibility using optical
tissue oxygenation in response to laser irradiation.
methods for regulation of local tissue O2 concentration.
The variable parameters were diffusion coefficient of
Additional oxygen release rate is directly measured through
oxygen in tissue and oxygen release rate.
the value of oxyhemoglobin arterial blood saturation
(SaO2). The amount of oxygen released into tissue depends
also from capacity of circulatory system to carry oxygen. h TcPO2 electrode
This capacity mainly defined by contribution of two
following parameters: hemoglobin concentration in blood
[Hb] and its circulation speed. The impact of actual
hemoglobin concentration is described by the ratio of O2
[Hb]/[Hb]n. Were [Hb] n is standard concentration that is O2
normal for particular sex and age. The impact of blood
circulation speed is taken into account through the heart pulse
rate Pr.
Finally, therapeutic "dose" can be determine by the value
of SaO2 = SaO2 - SaO2hwere SaO2 is saturation without O2
and SaO2hwith laser irradiation, heart pulse rate P r, time of O
exposure T, ratio of actual and standard hemoglobin
concentrations [Hb]/[Hb] n. HbO 2 Hb
[ Hb]  SaO2  22
D(O2 )     Pr  T Fig. 5- Simple model of oxygen diffusion in tissue
[ Hb]n  100 

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As it was shown experimentally [10] the response of depended on the time of exposure and the properties of
oxygen release on laser irradiation is relatively fast and tissue.
remains constant during the irradiation. To simulate this The comparison of calculated results with experimental
effect in the model, the oxygen release rate was increased data demonstrates that kinetic of ТсРО2 in dependence of
instantly and remains constant during the time of irradiation. time of elimination by laser radiation gives possibility to
The main aim of the calculation was to reach best fit of determine О2 diffusion coefficient into tissue. This means
the data produced by the model to the experimentally that one could calculate and determine how to reach
measured one. The target criteria were kinetic of tissue desirable level of ТсРО2 in zones with the disturbed blood
oxygenation in response to laser irradiation. The variable microcirculation such as solid tumor, burn or wounds. So it's
parameters were diffusion coefficient of oxygen in tissue and possible to determine optimal parameters of irradiation
oxygen release rate. taking into account the volume that has to be oxygenated and
the time of elimination.
VI. RESULTS AND DISCUSSION
Thus our suggested novel method can eliminate the deficit
The kinetic of oxygen tension in tissue in two cases the
of oxygen until the restoring new vascular net in tissue. This
normal blood circulation and artificially induced ischemia
result could be applied in the case of those pathologies
was investigated. Obtained results were normalized to initial
where elimination of tissue hypoxia is critical.
oxygen tension value.
Supplemental oxygen can lead to increased rate of
In fig. 6 the results of cold laser induced tissue
collagen deposition, epithelialization and improved healing
oxygenation in the case of artificially induced ischemia are
of split thickness grafts. Increased subcutaneous TcPO2 has
presented. As it seen we still can extract extra oxygen from
also been shown to improve bacterial defenses. Thus unique
arterial blood and optically supply the demand of cell
possibility in selective and local increase of the
metabolism as long as needed.
concentration of free molecular oxygen into tissue that
As it seen from fig.6 during laser irradiation the value of
enhances metabolism of cells is developed. Laser-induced
tissue oxygenation is increases exceeding its initial level
enrichment of tissue oxygenation stimulates cell metabolism
about 1.6 times (curve 1) after ten minutes of illumination.
and allows develop new effective methods for laser therapy
In the case of induced ischemia additional extraction of
as well as phototherapy of pathologies where elimination of
oxygen also is observed. This result clearly demonstrates
local tissue hypoxia is critical.
that laser-induced tissue oxygenation could be applied in
Laser-induce photodissociation of HbO2 may serve as a
clinical practice for restoration of normal cell metabolism in
unique method in laser therapy for optically increasing the
tissue with damaged microcirculation.
local concentration of free molecular oxygen in tissue that is
The results of calculations demonstrate that in order to
significantly enhances cell metabolism.
reach experimentally observed the rise of ТсРО2 by 1, 6
It is valuable that even at the case of ischemia we still can
times at the surface of tissue, the calculation indicates the
extract extra oxygen from arterial blood and optically supply
increase of oxygen release rate from arterial HbO2 into blood
the demand of cell metabolism as long as needed. Thus
plasma should increase about 4,3 times.
laser-induced tissue oxygenation allows optically eliminate
Photodissociation of HbO2 induced by laser radiation and
the deficit of oxygen until the restoring new vascular net in
release rate of free molecular oxygen into blood plasma has
tissue.
been measured experimentally in vivo using high sensitive
Obtained results gives an experimental argumentation to
pulse oxymeter. The oxygen released from HbO2 primarily
consideration of primary mechanism of biostimulation and
increases the PO2 of blood plasma and then O2 diffuses into
therapeutic effect of low energy laser radiation that could be
a tissue.
based on increasing tissue local oxygen concentration
directly wt the zone of irradiation.
This phenomenon allows to develop an objective method
1,7
of control the efficiency of treatment by laser phototherapy.
1,6 Now in clinical application the parameters of laser radiation
1
can be tuned to optimal wavelength, power and exposition
1,5
time in depends of optical characteristics of the patient skin
skin oxygenation, a.u.

1,4 tissue.
1,3
The obtained results also shows the way of increasing the
efficiency of biostimulation and therapeutic effect of low
1,2
energy laser radiation based on combination it with method
2
1,1 of oxygen hyperventilation therapy.
An important conclusion can also be drawn from the
1,0
obtained results. In interpretation of the biostimulating and
0,9 heeling effect of laser radiation the phenomenon of induced
0 2 4 6 8 10
irradiation time, min
photodissociation of blood oxyhemoglobin should be taken
Fig. 6 - The kinetics of laser-induced tissue oxygenation during laser
into account.
irradiation in norm blood microcirculation -1, and in artificially induced VII. CONCLUSION
ischemia - 2
New optical method of elimination the local tissue
It is exiting that the value of PO2 in blood plasma reached hypoxia is developed. The value of tissue oxygen
by laser-induced photodissociation of HbO2 is comparable to concentration increases significantly during the laser
that one typically reaches by the method of HBO. The irradiation.
distribution of ТсРО2 in the volume at the irradiation zone is

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It is shown that therapeutic dose of laser radiation could Experimental approaches in animal models and in
be based on adjusting the local concentration of free oxygen fibroplast cultures, J. Dermatol. Surg. Oncol. Vol.3,
in tissue by laser-induced photodissociation of blood 1987, p.p. 127-133.
oxyhemoglobin. [7] M.M. Asimov, R.M. Asimov, A.N. Rubinov,
To make the phototherapy as well as laser therapy Investigation of the efficiency of laser action on
methods really efficient one has to control the oxygen hemoglobin and oxyhemoglobin in the skin blood
concentration in tissue keeping it at the necessary level. This vessels, SPIE Proceedings Laser - Tissue Interaction 1X.
goal could be reached by the use of laser-induced 01.27 - 01.29. 98. San Jose. CA. USA, vol. 3254, 1998,
photodissociation of oxyhemoglobin in tissue blood vessels. p.p. 407 - 412.
Method of determination of oxygen diffusion coefficient [8] Asimov M.M., Asimov R.M., Rubinov A.N. Action
into tissue based on kinetics of tissue oxygenation under the spectra of laser radiation on hemoglobin of skin blood
laser irradiation is developed. vessels, Journal of Applied Spectroscopy. 65 (6), 877-
It is shown that the efficiency of laser-induced 880 (1998).
oxygenation is comparable with the method of hyperbaric [9] M. Asimov, R. Asimov, M. Mirshahi, A. Gizbrebrecht,
oxygenation (HBO) at the same time gaining advantages in Effect of laser induced photodissosiation of
local action. oxyhemoglobin on biomedical processes, 11th
Novel method of optical ―dosimetry‖ based on using the International School on Quantum Electronics: Laser
changes in tissue oxygen concentration as feedback signal physics and Applications, Proceedings of SPIE, vol.
for optimization therapeutic effect of low intensity laser 4397, 2001, p.p. 390-394.
radiation is developed. [10] [10] M.M. Asimov, Laser-induced Photodissosiation of
Photodissociation of oxyhemoglobin, whose main Hemoglobin Complexes with Gas Ligands and its
biological function is the transport of molecular oxygen Biomedical Applications, Proceedings of "LTL Plovdive
gives unique possibility of additional oxygen supply and 2005", IV International Symposium Laser Technologies
allows develop laser-optical method of tissue hypoxia and Lasers, October 8.10 - 11.10. Plovdive, Bulgaria.
elimination that restores normal cell metabolism. 2005, p.p. 3-11.
[11] Wilma A. Saffran, Quentine H. Gibson,
REFERENCES
Photodissosiation of Ligands from Hem and Hem
[1] S.Takas, S. Stojanovich, Diagnostic and biostimulating
Proteins: Effect of Temperature and Organic
lasers. Med. Pregl. vol. 51, no. 5-6, 1998, p.p. 245-249.
Phosphate. J of Biol. Chem., vol. 252, 1977, p.p. 7955-
[2] G.D. Baxter, Therapeutic lasers: Theory and Practice,
7958.
Edinburgh; New-York, (1994)
[12] Ed. A. Bakaj, V.I. Kravchenko, S.A. Mamilov, O.N.
[3] J. Tuner and L. Hode Laser Therapy: Clinical practice
Minov, Yu. S. Plaksiy, A.B. Rikberg, Multichannel
and scientific background, Prima Books AB (2002).
optical measurements for in vivo determination tissue
[4] V.A. Mostovnikov, G.R. Mostovnikova, V.Yu. Plavski,
indices, Optical & Biological Engineering &
L.G. Plavskaya, "Biophysical principles of regulatory
Computing. Vol.35, Suppl. Pan 1, 1997, p.p. 98-101.
action of low-intensity laser irradiation," Proc. SPIE,
[13] V.I. Kravchenko, S.A. Mamilov, O.N. Minov, Yu. S.
vol. 2728, 1996, p.p. 50-62.
Plaksiy. Investigations of correlation of optical signals
[5] J.S. Kana, G. Hutschenrieter, D. Haina, W. Waidelich,
during measuring an arterial blood oxygen saturation,
Effects of low power density laser radiation on healing
The Ukrainian Journal of Medical Technique and
of open wounds in rats, Arch. Surg. Vol.116, 1984, p.p.
Technologies vol.1, 1999, p.p. 59-61.
293-296.
[14] M.M. Asimov, A.N. Korolevich, E.E. Konstantinova,
[6] R.A. Abergel, R.F. Lyons, J.C Castel, et all.
Investigation of the kinetics of tissue oxygenation under
Biostimulation of wound healing by lasers:
the effect of low intensity laser radiation, J of Appl.
Spectr., vol.74, 2007, p.p.120-125.

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Electro-acoustical and Electrophysiological

Examinations in Diagnostics of Otitis Media in
Infants
I. ABABII, S. DIACOVA, M. MANIUC, P. ABABII, L. DANILOV
SMPhU “N. Testemitanu” Department of ORL
Abstract
Introduction .Acute Otitis Media is extremely common in infants, often asymptomatic.
Material and methods
Several hundred children in the first year of life were evaluated and treated for a variety of diseases. Seven
sets of measures were used in the study: 1. Background characteristics; 2. Otological questionnaires; 3.
Otoscopical examination; 4. Impedance audiometry; 5. Brainstem Electrical Response Audiometry; 6. Results
of surgery (tympanotomy, antrotomy); 7. Results of Otoscopical examination and Impedance Audiometry in
dynamics.
Results This results were compared with cytological and histology examination of surgical findings. High
correlation of type A with reducing compliance indexes and proliferation were found. We propose that
pathogenesis of otitis media in infants develop in two ways.
Discussion Algorithm of SOM – diagnostics was elaborated. SOM - diagnostics is based on a few steps. The
first step is the SOM prognosis in infants. The second step is the otoscopy examination of the infants of the
risk group. The third step is the audiometric investigations - impedance audiometry and ABR. Impedance
audiometry data are used for information of middle ear pathology character. BERA data give us possibility
to estimate the profound of middle ear pathology and degree and character of hearing impairment.
Conclusion We present an algorithm of the management of SOM in infants on the basis of our analysis. This
algorithm was also verified in patients from the control group. We were able to correctly-diagnose this
disease and prognosticate its course in over 97% of cases.

III. MATERIAL AND METHODS

I. INTRODUCTION Several hundred children in the first year of life were
Otitis media in children is one of the oldest problems in evaluated and treated for a variety of diseases including
pediatric otology. Acute otitis media is the most common intestinal, respiratory tract and neurological disorders. They
disease of early childhood characterized by fever, were evaluated and cared for in the Republic Intensive Care
sleeplessness, irritability, manifestations of intestinal and Unit for infants in the Republican Hospital for Children. The
respiratory disorders. Local changes could be evident or most frequent complaint was restlessness or sluggishness.
silent what complicates precise diagnostics and sufficient 728 infants (432 males and 296 females) with silent
timely treatment, leads to severe complications; impact on otitis media were examined using special sets of measures.
hearing, speech and development is significant, long term The majority of infants were younger than 6 months (654 -
sequelae such as chronic suppurative otitis media with and 89 %). Meningitis was observed in 12 % of cases, septicemia
without cholesteatoma, retraction pockets, etc, causes in 29 %, pneumonia in 35 %, intestinal disorders in 64 %.
disability of child, multiple complications, stipulates long For comparison, infants with classical manifestations of
term treatment and surgery. (1, 2, 3) middle ear inflammation were included in a second group. A
Undetected and undetectable middle ear pathology occurs third group, the control group, included infants without
in any patient age. But during early infancy there are some middle ear pathology (200 infants, in this category different
special anatomical and functional reasons for SOM groups of 50 patients were studied every three months).
development.
IV. METHODS
Clinical manifestations of SOM include hearing loss as
Seven sets of measures were used in the study: 1.
well as wide variations of pain intensity without significant
background characteristics; 2. Otological questionnaires; 3.
changes of the tympanic membranes. Clinically SOM can be
Otological examination; 4. impedance audiometry; 5.
associated with restlessness or sluggishness. This insidious
Brainstem Electrical Response Audiometry; 6. Results of
aspect of SOM often makes precise diagnosis difficult.
surgery (tympanotomy, antrotomy); 7. Results of Otological
Additionally antibiotics used to treat infants presenting
examination and impedance audiometry at 3 and 6 months
with gastrointestinal and pulmonary problems can mask
intervals after diagnosis were documented. (5, 6, 7)
associated SOM making diagnosis even more challenging.
Therefore potentially lethal middle ear infections may go V. BACKGROUND CHARACTERISTICS.
undetected clinically in pediatric populations (1, 2, 3, 4). Various background characteristics were recorded for the
purpose of identifying risk factors associated with SOM.
II. OBJECTIVES
These included data regarding the following: social-
This article describes our experience in diagnostics of
economic status of parents, their age and history of any
silent otitis media in infants of the first year of life.
chronic illnesses. Specifically questions were asked
regarding family history of ENT - related diseases;

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additionally data was obtained regarding pregnancy, Statistical analysis (Stjudent-criterium, Fisher-statistics
condition of birth, gestation age, weight and Apgar scores at and discriminate analysis) was made.
birth; a history was taken regarding nutrition and
VI. RESULTS
development of infant during first months before the onset of
Some predisposing factors to SOM.
ear disease; history of respiratory tract infection, intestinal
Life histories were analyzed in all 3 groups of patients.
disorders; antibiotic therapy; some information of child
Risk factors for SOM development include:
behavior and other (52 points).
hypotrophy (p < 0,0001, F = 46,3) inflammatory diseases
Otoscopy
during first months of life (p < 0,0001, F = 40,2)antibiotic
These were designed to obtain Otoscopical profile for
therapy (p < 0,0001, F = 35,8)pregnancy complications (p <
each child. The ―Carl Storz‖ set was used.
0,0001, F = 18,3)low birth weight (p < 0,0001, F = 9,3)
The items covered in each of the examinations included
Otoscopy
40 points (color, contour, luster, translucence, light reflex,
Healthy infants (400 ears) were examined to assess
landmarks and others).
normal tympanic membrane in infants during the first year
Impedance Audiometry.
of life. 104 ears (52 %) had translucency reducing, 64 ears
An Impedance meter set was used for impedance
(32 %) had color changes. The pars tensa was dull and
audiometry. Tympanograms were evaluated according to
opaque in 27 % and appeared red in 16 % of ears which were
classification by Jerger, (1970) in modification by М. Tos
otherwise normal. The pars flaccida was thick in 27 % of
(5)
ears examined. The light reflex was irregular or absent in 49
C2 C1 % of ears. The majority cases of tympanic membrane
A abnormalities were found in infants younger than 6 months
С А
of life. Tympanic membrane changes were observed more
often in group of infants, suffering from SOM. Therefore we
registered translucency reducing, thickness in majority of
В cases (98,1 %), light reflex was absent in 95,1 % of ears.
Sensitivity of otoscopy in determination of SOM was 98,1
%, but specificity was 48,0 %. We found some important for
SOM-diagnostics symptoms. But our opinion is that
Fig.1. Tympanogram types. Schema.Type A: pressure +50 - -99 mm,Type diagnosis of SOM cannot be established on otomicroscopical
C1: pressure -100 - -199 mm H2O Type C2: pressure <-200 mm H2O,Type findings alone because similar signs can be present in
B: no peak of compliance
healthy infant‘s ears. This explains the limitation of
otoscopy in this age group.
Impedance audiometry 400 ears of healthy infants were
Gа tested. Type A was registered in all cases. Middle ear
pressure was in level of + 50 to - 80 mm H2O. Compliance
was registered in the range of 0,21 to 0,5 sm3. Absolute
C gradient was in level of 0,06 to 0,2 sm3, relative gradient
W was in level of 0,25 to 0,2.Infant with suspected silent
inflammation of the middle ear were investigated repeatedly.

Fig.2. Schema of compliance characteristics calculation. Gr=C/GaW –

width C – compliance Ga – absolute gradient Gr – relative gradient

Compliance and absolute gradient as well as relative Type A

gradient were calculated according to Brooks (1968).(3, 5).
The presence or absence of an acoustic reflex was tested
ipsi laterally at 1000 Hz and 95, 100, 105, 110 dB SPL,
using automatic impedance audiometry (5).Brainstem
Electrical Response Audiometry.
The ―Audiostar‖ (―Madsen Electronics‖) was used.
Recordings were obtained under commonly used conditions.
Briefly, ABRs were recorded from cup electrodes applied at
C, A1 and A2 (international 10 - 20 system). Clicks 0,1 ms
in duration were presented through TDH - 39 earphone at 7
intensity levels in 10 dB steps (70 - 10dB) until ABR
threshold was established. Peak Latencies (I, III, V) and
ABR threshold were registered; Function Latency-Intensity
(V) was made.(6).
All of these children received medical treatment, 12 % of Fig.3. The gradual reducing of compliance indexes in cases of normal
children underwent surgery – Myringotomy or Myringotomy middle ear preassure.
and Antrotomy.(7) Type A was registered in majority of cases (66,2 %), type
All patients were followed for at least 1 year. B - in 30,8 %, type C - in 3 %. Compliance (for types A and
C) was in level of 0,1 to 0,3 sm3, in majority of cases (84 %)

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less than 0,21 sm3. Absolute gradient was less than 0,06 pathology. Threshold evaluation was usually minimal.
sm3, relative gradient - less than 0,25. Persistent wave PL I prolongation in serial recordings was
The gradual reducing of compliance indexes and normal the striking ABR findings among infants with abnormal
middle ear pressure was found in repeated investigations in tympanometry. As PL I prolongation was more pronounced
SOM-group. than that of wave V, the I - V inter-peak latency was often
Normal middle ear status, absence of any inflammatory shorter than expected for age. Latency - Intensity function
changes correlated with type A of tympanogram. Beginning slope was not grossly altered in these cases.
of pathological process in middle ear cavity provokes
Algorithm of SOM - diagnostics
development of edema of mucosa, proliferation of
SOM - diagnostics is based on a few steps. The first step
granulation tissue without any effusion, what influenced on
is the SOM prognosis in infants of the first year of life.
compliance and its characteristics – absolute and relative
Pediatrics in ICU estimates the history data of every child
gradient. Gradually decreasing compliance in the conditions
(particular attention is given on the most significant risk
of open auditory tube does not change the type of
factors for SOM - development) and forms the risk group of
tympanogram – it remains type A. (presented on Fig.3). But
SOM. The second step is the otoscopy examination of the
the height and roundness of the tympanogram are gradually
infants of the risk group. Otology specialist chooses the
changed till type B, which correlated with big amount of
patients with minimal otoscopic changes and forms the
granulations, edema and effusion.
group of infants with suspicion of SOM. The third step is the
Type B was registered in majority of infants of OOM-
audiometric investigations - impedance audiometry and
group. Type C was found in 17,7 % and type A with
ABR. If impedance audiometry changes are observed the
reducing of compliance indexes - in 15,2 % of ears. The
BERA is registered. Impedance audiometry data are used for
gradual reducing of middle ear pressure was more
information of middle ear pathology presence and it
characteristic for ears with obvious otitis media.
character. BERA data give us possibility to estimate the
This results were compared with cytological and histology
profound of middle ear pathology and degree and character
examination of surgical findings.
of hearing impairment.
High correlation of type A with reducing compliance
indexes and proliferation were found. Effusion was VIII. CONCLUSION
correlated with type B. We were able to compare the diagnosis and
We propose that pathogenesis of otitis media in infants prognostic values of otomicroscopy, pneumatic otoscopy,
develop in two ways. (Fig.2) impedance audiometry, and pure tone audiometry. We
Fig 2. Two ways of development of otitis media by present an algorithm of the management of SOM in infants
correlative analysis. on the basis of our analysis. This algorithm was also
The first way is classical with the basis of dysfunction of verified in patients from the control group. We were able to
the Auditory Tube and vacuum development in middle ear. correctly-diagnose this disease and prognosticate its course
The second is the development of otitis media in in over 97% of cases.
conditions with open auditory tube. Findings of the The application of elaborated diagnostic algorithm
impedance audiometry and surgery confirm this hypothesis. of SOM significantly improves the results of treatment.
REFERENCES:
1 2 [1] Marchant C.D., Mc Millan P.M., Shurin P.A. :
A
C1 Objective diagnosis of otitis media in early infancy by
tympanometry and ipsilateral acoustic reflex thresholds
C2
- J. of pediatrics, 1986, v. 109, N 4, pp. 590 - 595.
[2] Paparella M.M., Shea D., Meyerhoff W.L., Goycoolea
B M.V.: Silent otitis media: clinical applications.
Laryngoscope 96: 978, 2009
[3] Paparella M.M., Schachern P.A., Cureoglu S : Chronic
Silent Otitis media – Journal of ORL, V. 64, N 2, 2002
p. 65-72
[4] Bluestone, Charles D.: Studies in Otitis Media:
Fig 2. Two ways of development of otitis media. Laryngoscope Volume 114(11, PART 3) SUPP. NO,
105, November 2004, pp 1-26
VII. ABR [5] Абабий И.И., Дьякова С.А.: Диагностика
Auditory Brainstem Response Indexes were investigated латентных воспалительных заболеваний среднего
in healthy infants group. Hearing threshold level and peak уха у детей первого года жизни при помощи
latency (PL) of wave I were the most constant. Other indexes импедансометрии. - Журнал ушных, носовых и
(PL III, PL V) showed dependence from age, maturity and горловых болезней. 1994, N 5, с. 4 - 7.
pathology of neurological system. [6] Абабий И.И., Дьякова С.А. Антохий И.Н., Манюк
We looked at the influence of silent ear inflammation on М.К.: Показатели коротколатентных слуховых
ABR and found that hearing threshold level depends on вызванных потенциалов у детей грудного возраста с
presence and degree of pathological processes. We воспалением среднего уха. - Вестник
compared the peak latencies in healthy infants and infants оториноларингологии. 1995, N 4, с. 28 - 31.
with silent otitis media. The difference of PL I was the most [7] Ababii, S.Diacova, M.Maniuc, A.Chiaburu, S.Parii. :
statistically reliable. The evidence is already mentioned are Variantele otitelor medii acute la copii - Arta Medica.
the most sensitive and reliable indicators of middle ear Chişinău, 2008, Nr 4 (31), p. 20 - 22.

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Installation for Local Hyperthermia in Crossed

Laser Fluxes
Iurie NICA*, Serghei ZAVRAJNÎI, Andrei GRITZCO, Iurie TIRON, Dumitru ESHANU, Vladimir
MUSTEATZA, Andrei STALBE
Institute of Electronical Engeneering and Nanotechnologies „Dumitru Ghiţu”, Chişinău, MD – 2028
*
e-mail: [email protected]
Abstract – As is well known, on heating up the tumor over 43 – 440C the tumor cells dies, whereas healthy tissues
cells remain alive up to 500C. We propose local overheating malignant morbid growth, with infrared radiation from
a laser system, focused on a specific area, forming this way a powerful, dispersed in the space, source of energy. To
achieve the therapeutic dose in the body at depth of 10-12 cm is necessary to be used lasers with the radiation
between wavelength range of 700nm - 850nm, for which there are seen windows of transparency in biological tissues,
and the total power of 5 - 15 W.
We have developed a installation, including: a block of laser diodes with individual collimating optics, directed in a
common point; multi-channel thermometer of the irradiated area; two-axis table for accurate positioning of the
irradiated sample with temperature sensors fixed on it relative to the common point of crossing lasers fluxes;
computer, integrating all elements of the installation in one experimental - measuring station.
The experimental results confirm the ability of the radiation with a wavelength of 808 nm to penetrate the biological
tissue to a depth of up to 90 mm and deeper. The effect evaluation of addition energy in the common point of the
lasers beams demonstrate that to achieve the desired temperature of the tissue up to 43-440C to a depth of 9 cm is
sufficient 5 ÷ 6 lasers with power emission 4W to wavelength of 808nm. In order to avoid the burning of the surface
tissues of the body is necessary to ensure the power flow density not higher than 200mW/cm2, which requires
collimators or they're systems that provide a uniform flare by each laser corresponding to the area (20cm 2, in case of
4-watt lasers).

Keywords – local hypertermia; diode laser; crossed rays; near infrared region.

heated biological tissue located in the immediate vicinity of

the radial head of the optical guide. The volume of the
I. INTRODUCTION
heated area can be increased by using a flux with a higher
The problem of combating cancer diseases is one of the
irradiance [1], but this may cause unpredictable
most acute problems of the contemporary medicine, which
consequences, for example: the tissue temperature reaches or
must be solved worldwide. In combating cancer tumors are
exceeds critical value at which begins the vaporization of the
used several strategies: surgical interventions,
intracellular liquid, which could trigger dangerous unknown
chemotherapeutic and radiological procedures, and more
processes such as boiling or carbonization of the tissue [2]
recent - local or general hyperthermia and photodynamic
The photodynamic therapy method, which speculates the
therapy; which are used individually or in various
property of the malignant tumors to concentrate the
combinations. From invasiveness point of view of the human
photosensitive materials in the pathogenic cells, can be
body the most sparing
achieved in two ways. The most widespread - photo
procedure is hyperthermia which benefits from a specific
chemotherapy uses photo sensitizers, which molecules got
property of the cells (proteins) affected by the cancer namely
stimulated when absorbing of photons initiating such effects
- the death at 43-45 C, temperature that does not affect the
as: destruction of the mitochondrion; substantial changes in
adjacent healthy cells. The hyperthermia of the malignant
oxygen metabolism by generating of singlet oxygen ( 1O2),
malformations could be achieved through the different
which is extremely cytotoxic, and a large quantity of free
methods: hot water jets, electromagnetic fields, infrared rays,
radicals [3-5].
etc.
The second way - photo thermotherapy, involves photo
Hyperthermia procedures can be made relatively simple if
sensitizers that emit a large amount of heat in the process of
the malformations are located on the surface of the body or
photons absorption. Usually these are nano-dimensional
organs to which we have direct access. The situation is more
structures, such as: metallic powder, nanotubes, nanorods or
complicated when the tumor tissue is located deeper.
nanoshells with dielectric core and metallic shell [6]. The
Currently in medical practice are investigated and
main disadvantage of this method consists in the formation
implemented several variants of local hyperthermia using
of free radicals and chemical components, the role of which,
non invasive or minimum invasive methods for heating the
currently, is not researched enough.
tumors located in depth of the biological tissue. During
laser-induced interstitial thermotherapy (LITT) (or II. THE HYPERTHERMIA INSTALLATION: THE
interstitial laser photocoagulation) the light is delivered FUNCTIONAL BLOCKS
through flexible fibers inserted into the center of the tumor. Classical hyperthermia is based on fact that to
Laser light at the tip of the fiber raises the temperature of the temperatures of 42-450C cell's DNA suffers irreversible
tumor cells and damages or destroys them. Disadvantage of pathologic modifications and cells dies, while healthy cells
this method is the possibility of treating only small volumes are recovering to remove excessive temperatures.
of the pathological tissue (1-2 cm areas diameter). The cause Speculating this property of tumors, in the laboratory
consists in modifications of the optical properties of the "Medical Equipment‖ of the Institute of Electronics

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Engineering and Nanotechnologies "D. Ghiţu" has been or decreases (by disconnecting the laser diode) the optical
developed a device designed for monitored heating into power until the temperature will reach the required value.
malignant tumors located in depth of the tissue. The device This method represents the discreet method of temperature
consists from several sources (laser diodes) which radiates control in the region. Another method is based on continuous
into infrared region of the spectrum (808 nm). Radiation monitoring and correction of the thermal field with an
with this wavelength penetrates into the tissue up to a depth accuracy of ± 0.10 С.
of 70-120 mm for about 10 W/cm2 irradiance [7]. But these
irradiations may cause substantial photothermal damages of
the superficial tissues for irradiation time longer than 50ms.
Therefore, the main problem consists into irradiating the
malignant tumors, without affecting the tissues between the
surface and the tumor. The problem is solved by transporting
the energy through the different channels to the tumor,
placing the tumor in place of the intersection of the several
laser beams.
The main elements of the installation are (Figure 1):
• Set of laser diodes, equipped with optical beam forming
equipment and orienting it into a common point;
• Module for measuring the temperature, equipped with a
set of thermal sensors able to convert the temperature into
electric signal and electric signal into binary code for
computer data processing. In its version of the installation,
as thermo sensitive components are used thermocouples
CrNi / Ni FeCu; Fig. 1. Block diagram of the installation for study of local hyperthermia
• The tilting table (X / Y positioning) serves for accurate Each laser diode is individually monitored by the system.
positioning of the region which must be heated in the flows The data which define the thermal regimes are transmitted
crossing point. Positioning is carried out by two stepper through the RS232 serial interface to the executive modules,
motors driven by PC. which converts the data into the optical power, producing
• PC - which function is to ensure the connection between themselves the required temperature inside the irradiated
all modules of the installation, thereby creating an integral sample. The format of the data package contains the address
experimental system. of the module which the PC addresses to, and data about the
As a source of coherent optical radiation are used devices required optical power. Creating and maintaining the
ATC C4000-500 MFA-808-3-F200, which main elements working regime of the each laser diode is carried out based
are diode diodes with 808nm wavelength, which have a on comparing the data received from the computer and data
linear dependence between optical power and the electric obtained by the monitoring loop of the optical power. In the
current intensity which flows through the laser diode structure of the monitoring loop of the optical power is a
(maximal optical power 4W). photodiode, irradiated by a part of the electromagnetic flux
Temperature measurement of the irradiation region can be produced by the laser diode. The signal level produced by
accomplished by using thermocouples. The electromotor the photodiode is directly proportional with the intensity of
power created by thermocouples is applied to the positive the radiation. The optical power control module processes
terminal of the operational amplifier (CMOS). Dependence the received data from the PC and monitoring loop after a
between the value of the output signal of the amplifier input specific algorithm, applying after that, an electrical signal
signal value is linear in range of (0-50)0C. The maximum adjusted to the sub-modules, whose function is to create the
possible values of the amplifier output signal is optical power corresponding to the signal.
corresponding to his power supply. The analogue signal
received from the operational amplifier output is transmitted III. THE REALIZATION OF THE LOCAL
to the analog-to-digital converter input - (ADC). Each HYPERTHERMIA IN BIOLOGICAL TISSUE
converter input has a thermocouple. The data obtained from 3.1 Experiments purposes
ADC are sent to the computer to be processed and displayed 1. Confirmation of the depth penetration of the biological
as an image of the thermal field. tissues by the laser radiation with wavelength of 808 nm.
The computer, through the RS232 serial interface controls 2. Monitoring and estimating the energy composition effect
the commands transmission to position and irradiate the of the coherent infrared radiation beams which intersects in
object, followed by collection, storage and processing the depth of the biological tissue.
data obtained as a result of 2D and 3D images of created 3. Analyzing the possibilities of determining the constants
thermal fields. Based on submitted orders (the temperature that describe the thermal and optical characteristics of the
registered in the given point) to the control module of the biological tissues for thermal processes prognosis of the
optical power of the laser diodes and received data irradiated tissues.
describing the temperature distribution into the sample, the 3.2 Experiments Organization
computer manages the irradiation process. If the current An isotropic sample of biological tissue (egg white) fills
temperature in studied area does not correspond to the the bottom of a glass cylinder with very thin walls. The
expectations (the difference is more than (0.2-0.3) 0C), the cylinder has a diameter of 100 mm. In the sample are
microcontroller, based on comparing the amount of data implanted the thermocouples forming a cross with
containing information about the necessary temperature and perpendicular arms. The thermo sensitive peaks are in a
amount of data containing the actual temperature, increases horizontal plane parallel to the bottom of the cylinder. The

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thermocouples are located on the arms of the cross at a presented in the charts. On charts, the recorded size variation
distance of 20 mm from each other. The central from initial value to saturation value occurs in 3.75 sec,
thermocouple is located at the intersection point of the arms which exceeds . at about 150 times the interval of radiation
that are on the longitudinal axis of the cylinder. (Figure 2) increase. The same behavior occurs and in case of radiation
decrease. So, the thermocouple does not register the
influence of the electromagnetic field (Foucault currents).

Figure 2. Fluxes emitted by the lasers are mutually perpendicular. The

thermocouples are situated on the beams axis
Fig. 4. Time dependence of the signals recorded by the thermocouples
In the experience has been used two lasers (laser diodes)
Thermal inertia of the thermocouples, when measured
with the same optical power in infrared emission (808nm)
separately (2.5 ms /° C .... 8.4 ms ° C /°) is much lower than
which beams propagates along those two rows of
the temporal variations shown on charts. So, the assumptions
thermocouples intersecting in the position of the central
that are registered charts demonstrating the direct heating or
thermocouple T2. The optical power emission of the W opt
cooling into thermocouples are not founded. Remains the
laser diodes was 250 mW. The glass cylinder walls absorbs
conclusion that are registered temperature variations in the
about 0.05% of the irradiance, so absorption can be
biological sample where are implanted thermocouples.
neglected. The temperature registration regime of is shown
Environmental temperature T with internal sources, which
in the description of the temperature monitoring module with
energy absorbing regions along the fluxes of radiation,
8 channels.
described in the equation:
The lasers operated in such regimes as: intervals of
absence of the radiation; irradiation of both lasers
(1)
simultaneously; irradiation of one laser or another (Figure
3). For highlighting of as many nuances (details) of the
Where c - is the specific heat capacity of the environment,
process, the lasers operating intervals were quite long (30'').
 - density,  - thermal conductivity, D - absorption,
W0 - The optical the power of the flow at entry into the
environment, S - cross sectional area of the radiating flux,
r - the module of the vectorial radius of the investigated
region.
Equation (1) describes the time intervals I, II, V, VI for
thermocouples T0, T1, T3 or II, III, VI, VII for
thermocouples T4, T5, T6 and T7.
Same equation applies for thermocouple T2 for the time
Fig. 3. The temporal charts of the alternance regimes of the laser operation intervals I, III, V and VII.For time intervals II and VI its
value must be equal to the sum of the optical power of both
3.3 Experiments Results
optical lasers.
For non-irradiated areas or for times intervals when lasers
In the Figure 4 is represented graphs of the time dependency
of the recorded signals by thermocouples in described don‘t work, so when W0 = 0, the equation is:
working lasers regimes.
The synphasic variations of the signals values registered (2)
together with the operating regimes of the lasers This relates for the time intervals III, IV, VII, VIII for
demonstrates the recorded influence on the sample. Is thermocouples T0, T1, T3 or I, IV, V, VIII for
observed synphasic variations on all thermocouples, thermocouples T4, T5, T6 and T7. The temperature in the
including those situated deeply in the biological sample (90 region T2 is described by this equation for time intervals IV
mm). This confirms the ability of deep penetration into and VIII.
biological tissue by the 808 nm infrared radiation. Is observed quick warming intervals when the temperature
The signal recorded by the central thermocouple (T2) gradient in the observed region dV is not high and heat
illustrates composition of the infrared fluxes in the region of dissipation β*  2T*dV cannot match the energy
their intersection. accumulation which comes from released energy absorption
When switching the lasers, the radiation increases and
decreases abruptly . . . and manifests itself in the worst case,
during 25 ms, which is much faster than the variations In cases when warming the irradiated regions of the
biological sample is faster than warming non-irradiated

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regions, increases the temperature gradient in the irradiated

regions and therefore, increases the heat evacuation from
these regions. In this case we observe a pronounced decrease
in growth speed of the temperature.
The decrease of the temperature that occurs when
"extincting" the lasers demonstrates the redistribution
process of the heat for thermal balance in the sample volume
and is described very well by expression (2). Each following
state of thermal balance is installed to a higher temperature
than from which has started the previous warming, which
demonstrates the accumulation process of the heat in
biological sample.
For time intervals corresponding to the functioning of
both lasers (II and VI) the curves shows a small growth
(compared with the temperature growth caused by the
irradiation of "its own" laser) caused by the penetration of Fig. 6. The temperature variations ΔT in one cycle of irradiation of the
biological sample with 808 nm infrared radiation. Top - the values along the
the photons by the spreading mechanisms and the heat laser beam 1, bottom- the values along the laser beam 2.
diffusion of an amount of energy . . . coming from nearby
radiated regions. The curves erosion is caused by the
dispersion . of the recorded data and determined by the
resolution capacity of the entire channel . of the temperature
recording ~ ± 0.05 ° C.
The different values of the initial temperatures in Figure
5.5 is caused by the distinction of the biological sample
temperatures (6.5 ° C) and environment (27° C), which
causes the heat transmission through the cylinder glass walls a b
Fig. 7: The distribution of the temperature variations ΔT in the biological
and biological sample stratification by the temperature sample in selected moments: a) along 1 laser beam, b) along 2 laser beam.
(Figure 5).
Moment t1:
Figure 7 а) Figure 7 b)
Exponential The temperature
distribution of the variation exclusively
temperature variations in T2 region which is
ΔT towards T0, T1, T2, common for both
T3 according with (1) lasers fluxes. For
points T4, T5, T6, T7
Fig. 5. The temperature field formed in the biological sample from the heat substantial variations
exchange with the environment. On the left- indications for thermocouples
T0, T1, T2 and T3 on the right - the indications for thermocouples T4, T5, of the temperature are
for, T6 and T7. not registered because
laser 2 doesn't work.
IV. PROCESSING AND ANALYZING THE Figure 7 b)
EXPERIMENTS RESULTS The temperature
The temperature variations ΔT = T- To (To - biologic variation exclusively
environment temperature before "switching ON" the lasers, in T2 region which is
T - biologic environment temperature at the time of common for both
measure.) at points where are situated the thermocouples, lasers fluxes. For
recorded in the process of biological environment radiation points T4, T5, T6, T7
with radiation wavelength 808 nm are shown in Figure 6. substantial variations
For analyzing of the biologic environment reaction to of the temperature are
applied irradiation, we will explore the field distribution of not registered because
temperature variations ΔT = T- To for a few characteristic laser 2 doesn't work.
temporal moments. We will choose the following items: Moment t2:
t1 - 1 laser works in steady state, laser 2 does not work;
t2 - both lasers works steady, at the next moment 1 laser
will be "off"; Figure 7a) Figure 7b)
t3 - 2 laser works in steady state and relaxation processes Continues the Same as 7 a)
caused by "off state" of the 1 laser has ended. exponential growth of
the temperature
according to (1) in the
center of (T2) we
observe a significant
warming since W0
factor which describing
energy absorbing is the

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sum of the optical

radiation which
penetrates into the The analysis of the composition effect of the coherent
environment from both infrared radiation beams energy intersecting in the depth of
lasers the biological sample suggests the need of substantial
increasing of the lasers number energy characteristics
equivalent to those used (250 mW) and of collimators
We mention, that until "switching ON" the laser 2, (Øbeam = 7.14 mm) for heating with ΔT ~ 7 ’ 100C at the
in the point T1 were much more warmth than in the depths of 90 mm.
T2. Therefore the heating process in T2 is slower When using more powerful laser diodes (4 W) can be
compared with heating in T1. In case b) for enough 5 ’ 6 pieces, but then to obtain the irradiation of
thermocouples T5 and T2 the process is reversed. 200mW/cm2 (supportable for the surface tissues) collimators
Which differences are explained on charts a) and b) or systems are required to ensure the uniform irradiation of
in the moment T2. the surfaces with areas of about 20 cm2.
A solution would be to use the impulsive radiation regime
Moment t3: (50-200 ns with the frequency () equal to 1-50000 Hz) with
Figure 7a) Figure 7 b) more powerful lasers.
Cooling process takes Is shown the Any approach is possible because in the development of
place in accordance temperature the installation have been used the block-module concept
with (2) apart from breakdown on the which is very flexible and allows any reconfiguration of the
center (T2) where direction T4, T5, T2, installation.
occurs the T6, Т7 (according with ACKNOLEDGMENTS
accumulation of the temperature variation The work was supported by the Suprem Council for
heat from laser 2. in the center. See the Science and Technological Development of the Academy of
Decreasing the comments Figure 7а). Science of Republic of Moldova (Project 06.420.007A)
temperature in the For a longer regime
center (T2) compared duration of irradiating REFERENCES
with its value at time t2 the sample, the [1] M. Prudhomme, J. Tang, S. Rouy, G. Delacretaz, R.
explained through . the exponential curve will Salathe, G. Godlewski, Diode laser and interstitial
flow at reduction due to keep the trend, hyperthermia against colonic cancer. Effect of power
"off state" of the laser according to (1). settings on necrosis size, Proc. SPIE, 2327, 1994, pp.
1. Now in this region 283-286.
comes less radiation, [2] D. Wyman, W. Whelan, B. Wilson, Interstitial laser
and therefore is photocoagulation: Nd:YAG 1064 nm optical fibre source
accumulated less heat. compared to point heat source, Lasers Surg. Med., 12,
For thermodynamic 1992, pp.659-664;
balance is necessary a D. Wyman, W. Whelan, Basic optothermal diffusion
lower rate of theory for interstitial laser photocoagulation, Med. Phys.,
evacuation of the 21, 1994, pp.1651-1656.
surplus warmth, thus a [3] М.Л. Гельфонд. Фотодинамическая терапия в
lower temperature онкологии. Практическая Онкология, Т.8., №4,
gradient. 2007.
[4] B.W. Henderson, T.J. Dougherty, How does
photodynamic therapy work? Photochem. Photobiol.
Vol.55, 1992, pp.145-157.
V. CONCLUSIONS [5] G.Jori, E.Reddi, The role of lipoproteins in the delivery
Was confirmed the depth penetration of the biological of tumour-targeting photo-sensitizers, Int. J. Biochem.
tissue at the laser radiation wavelength of 808 nm. Vol.25, 1993, pp.1369-1375.
Variations of the temperature were registered by all [6] Y.Feng, et al. Optimal Design of Laser Surgery for
thermocouples implanted in the biological sample, including Cancer Treatment Through Nanoshell – Mediated
those most distant, located at 90 mm from the beam entry Hyperthermia Therapy, Nanotech , Vol.1, 2005, pp.39 –
location in the sample. 42.
The signal registered by the central thermocouple T2 [7] Х.П. Берлиен, Г.Й. Мюллер, Прикладная лазерная
demonstrates the composition effect of the coherent infrared медицина, М: Интерэксперт, 1997.
radiation beams energy intersecting in the depth of the
biological tissue.

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The Role of Microscopic Techniques in

Performing Tympanoplasty in Children
I. ABABII, L. DANILOV, M. MANIUC, P. Ababii, S. DIACOVA
SMPhU ―N. Testemitanu‖ Department of ORL
Abstract
Introduction
Tympanoplasty is a delicate microsurgery, surgery repairing an anatomical lesion of the middle ear, caused
by suppuration of chronic otitis.
Objectives
The main direction of the study is to determine the efficacy of tympanoplasty under microscopic control
preoperatively, during surgery and postoperatively.ListenRead phonetically
Materials and methods
In the clinic of pediatric otorhinolaryngology, 220 tympanoplasties were performed in children aged 8 to 18
years in the period 1995 – 2010. For examining the affected ear was used the surgical microscope "Opton".
During surgery it was used the retroauricular access, given the narrow ear canal and need to perform control
antrotomy in children. The temporal fascia, previously taken above the operated ear, was used as a graft. The
fibrous ring of the tympanum perforation edge was removed and the skin of the posterior wall of the
external auditory canal with the tympanum ring and the posterior part of the tympanum were taken off.
During operation, after a detailed microscopic examination of middle ear, it was planned the type of
tympanoplasty. As support for the fascial graft was used the gelfoam applied in the middle ear. It was used
the surgical technique ―Underlay‖ or „Overlay‖.
Results
Positive results after tympanoplasty using surgical microscope, characterized by integral neo tympanum, lack
of exacerbations of the inflammatory process of the middle ear, were obtained in 83% of operated children,
including 45% cases with the improvement of hearing.
Conclusion
Microscopic control of the affected ear before, during and after surgery improves clearly the quality of
microsurgical intervention, reduces the number of ear complications, improves hearing in children and
reduces their invalidity.

perforation of the tympanic membrane. This assumes that

I. INTRODUCTION
the middle ear space, its mucosa, and the ossicular chain are
Otorhinolaryngology is continuously developing from one
free of active infection. There is no direct inspection of the
decade to another, as a result of technical progress
middle ar during this procedure. Tympanoplasty implies
(microscopes, optical endoscopes, laser) and microsurgical
reconstruction of the tympanic membrane but also deals with
instruments, by constant improvement of means of
pathology within the middle ear cleft, such as chronic
investigation and treatment.
infection, cholesteatoma, or an ossicular chain problem.
Classical Otology has changed substantially in recent
Before deciding to undertake a tympanoplasty, a
decades by finding and describing new otic diseases, by the
rigorous testing should be carried out to detect and eliminate
appearance of new operative techniques aimed at a
any existing problems (adenoids, nasal septum deviation,
functional and reconstructive surgery of the middle ear [3].
pharyngitis, rhino-sinusitis etc.); general testing will detect
Hearing is crucial for child‘s development. It assures one
the general diseases of the patient [1, 6].
of the main needs - verbal communication.
Indications for tympanoplasty:
Tympanic membrane is one of the elements of the
-permeable auditory tube (controlled by artificial
transformer, impedance adapter and reducing loss of sound
eardrum tolerance test, by tubal blowing or even
energy system of the myringo-ossicular system, contributing
impedancemetry);
through its surface to the hydraulic transformation (myringo-
-disabling traumatic or post-otitic "dry" perforations;
platinary) and serves to protect the cavum tympani region [2;
- appropriate vascular bed - for nutrition of the graft.
4].
Contraindications to tympanoplasty are divided into two
Myringoplasty has two main goals: sound protection of
major groups:
the round window and restoring the surface and the tension
1. Absolute contraindications (unconditioned):
of the tympanic membrane using a graft.
a) complete hearing loss;
Tympanoplasty is a delicate microsurgery, surgery
b) mixed hearing loss with the prevailing of the perception
repairing an anatomical lesion of the middle ear, caused by
type;
suppuration of chronic otitis. This functional surgery aims to
c) completely blocked auditory tube, if tube permeability
achieve an improvement in hearing. Tympanoplasty requires
can not be restored;
a spirit of analysis, being not a standard operation [5].
2. Conditioned contraindications:
Myringoplasty and tympanoplasty are descriptive terms
a) intracranial complications;
defining surgical procedures that address pathology of the
b) reheated chronic suppurative otitis media;
tympanic membrane and middle ear. Myringoplasty is an
operative procedure used in the reconstruction of a

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

c) eczema and dermatitis of the ear canal and auricular need to perform the control antrotomy. As a graft the
region; temporal fascia taken above the operated ear or tragus
d) extended decay of the tympanic box walls; perichondrium were used.
e) reduced permeability of auditory tube; For convenience during surgery, a dual instrument table
f) various nasal conditions, nasopharyngitis, and various was elaborated. On the inferior part is placed the patient's
general diseases such as tuberculosis in the active stage, head, on superior one - the microsurgical instruments
syphilis, infectious contagious diseases, etc. [3]. needed. Another device developed by us, is the one for
Conditions necessary for sound transmission after mounting ear spectaculum, which consists of a fixing
tympanoplasty: mechanism to the surgical table, a telescopic arm and an ear
1. Permeable auditory tube (controlled by artificial speculation mounting mechanism. This device practically
eardrum tolerance test, by tubal blowing or even assures the surgeon‘s bimanual work.
impedancemetria), for ventilation and drainage; At the beginning of surgery, firstly the ear canal is cleaned
2. Closing the perforation of the eardrum or the space with by careful aspiration. The fibrous ring of the eardrum
neotympanum; perforation edge is removed and the skin of the posterior
3. Restoring the sound transmission path from the neo- wall of the external auditory canal with eardrums ring is
tympani to perilymph (columelar effect); taken off. When the front edge of the perforation or at least
4. The two windows should be free on both sides of the the tympanic ring was present, it was used the Underlay
membranous labyrinth. technique - fascia placed under the flap.
The rate of success of pediatric tympanoplasty is likely Graft over the remains of the eardrum (the technique of
not a matter of age, but a matter of patient selection. Careful "Overlay") was applied when the anterior fibrous ring or
attention to factors such as technique, eustachian-tube perforation anterior edge was missing. As support for the
function, and site and size of the perforation will likely fascial graft was used the gelfoam applied in the middle ear.
increase the rate of an intact tympanic membrane with The gelfoam sponges soaked with Sol. Hydrocortizoni were
improvement in hearing. No one variable determines applied on fascia followed by tampons soaked with
outcome. Clearly, some factors studied are age-related, but antibiotic ointment. After 8 - 10 days, all the tampons are
age in itself should not be an indication or contraindication removed from the ear canal and antibiotic ointment is
to treatment. The overall success rate of tympanoplasty, with applied locally.
or without mastoidectomy, in the treatment of chronic
III. CONCLUSION
pediatric otitis media, was high and did not depend on
Positive results after tympanoplasty using surgical
patient age, the status of the contralateral ear, the inclusion
microscope, characterized by integral neo-tympanum, lack
or absence of surgical mastoidectomy, or the method of
of exacerbations of the inflammatory process of the inner ear
mastoidectomy (when this procedure was employed).
were obtained in 83% of children operated on, 45% of cases
Tympanoplasty may be expected to improve hearing in cases
being with improvement of hearing. Microscopic control of
of chronic otitis media accompanied by perforation, but not
affected ear before, during and after surgery, improves
in cases of cholesteatoma.
clearly the quality of microsurgical intervention, reduces the
II. OBJECTIVES number of ear complications, improves hearing in children
The main direction of the study is to determine the and reduces their invalidity
efficacy of tympanoplasty under microscopic control
REFERENCES
preoperatively, during surgery and postoperatively.
[1] Ataman Traian. Cofochirurgia, 1993
Materials and methods
[2] Black j., Hickey S. An analysis of results of
In the clinic of pediatric otorhinolaryngology, 220
myringoplasty in children International Journal of
tympanoplasties were performed in children aged 8 to 18
pediatric Otorhinolar. 31(1995) 95-100
years in the period 1995 – 2010. Surgeries were performed
[3] Ciuchi V. Patologia inflamatorie cronică a urechii
under general anesthesia and the control of the microscope
medii. Sechelele postotitice. Bucureşti, 2004.
"Opton".
[4] Isaacson G. Tympanoplasty in children Otolaryngologic
Preoperatively, the patient is examined in the dressing
clinics of north america.Volume 27.Number 1994 p.
room, using a microscope. The ear canal and eardrums of the
593-604.
child is examined, place of perforation of the affected ear is
[5] Perkins R. Tympanic membrane reconstruction using
evaluated, pathological eliminations are excluded and the
formaldehyde-formed autogenous temporalis fascia:
final diagnosis is established, chronic epitympanitis or
Twenty years‘ experience. Otolaringol Head Neck Surg
mesotympanitis in remission. During surgery
1996; 114: 366-79.
(tympanoplasty) surgical microscope is used for more
Potsic P. Tympanoplasty for the Anterior – Superior
detailed examination of the middle ear, the mobility of
Perforation in Children. TheAmerican Journal of
osicular chain is evaluated (hammer, anvil, stirrup) and if
Otology 17;115 – 118, 1996.
possible, mobility of the oval window. Following these
examinations, the type of tympanoplasty is planned during
surgery.
Detailed microscopic examination of the neotympanum is
also carried out after surgery, after removing the tampons of
the ear canal. Postoperative complications are excluded, the
vascularization of the neotympanum is evaluated.
During the surgery the retroauricular way was used,
taking into account the narrow auditory canal in children and

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Biomedical Physiotherapeutic Complex

Valerian DOROGAN, Vitalie SECRIERU, Tatiana VIERU, Stanislav VIERU, Andrei DOROGAN,
Eugeniu MUNTEANU, Ştefan Balica
Technical University of Moldova
[email protected]
Abstract – The paper describes the biomedical physiotherapeutic complex elaborated in Laboratory of
Micro-Optoelectronics of the Technical University of Moldova. The elaborated complex includes the
implementation of a large range of realizations of microelectronics and modern nanotechnologies and of
medicine research. A concept of realizing a physiotherapeutic complex is described in the paper.

Index Terms – aero ionization, laser therapy, trans-coetaneous electrical nerve stimulator, millimeter
waves, module structure.

software, which permits to guide the output ports and their

I. INTRODUCTION
functionality control. The netbook usage permits to
The authors had been involved in the elaboration and
graphically visualize the selected parameters for therapy.

Laser Therapy Checking

USB of optical
Interface Ultraviolet emition
Tehrapy
NETBOOK
Biomedical
physio- Therapy with Checking of
therapeutycal millimeter millimeter waves
Battery system waves emiter

TENS
Therapy
Charging system
Aeroionisation
Therapy

Fig. 1. Block scheme of the physiotherapeutic complex.

implementation of physiotherapeutic complex, because The supply is made from the network and from an
Republic of Moldova has lack of medical and autonomous supply system, which assures the system‘s
physiotherapeutic devices in regional and ambulatory mobility and excludes the electrical power network
centers. The paper presents the obtained results. jamming. The system permits to use 5 independent ports
(peripheral modules) designated for laser therapy in IR,
II. BIOMEDICAL PHYSIOTHERAPEUTIC DEVICE
ultraviolet therapy, millimetric waves therapy, therapy
CONCEPT
through trans-coetaneous electrostimulation of nerves and
A new physiotherapeutic complex system was elaborated
therapy with ionized air.
during study and experimental elaboration in the field of
modern technologies. It assures a complex physiotherapeutic III. OPERATING MODE OF THE
treatment using the methods: trans-coetaneous PHYSIOTHERAPEUTYCAL SYSTEM
electrostimulation of nerves (TENS), laser radiation therapy The execution program of the physiotherapeutic complex
in the visible and IR range, ultraviolet radiation therapy, has a model alike an operating system. The structure of
therapy using ionized air. program functioning of the physiotherapeutic complex is
The therapeutic complex system is consisted of an represented in figure 2.
electronic block (Main Module) based on an advanced The linkage between peripheral modules is made by the
microcontroller, which assures the functionality of all program core, which controls the functioning state of these
elements, working regime setup, patients and operating modules. The interaction with the PC (user) is assured at the
regimes‘ information storage. The system is connected to the same time.
netbook through a USB interface, equipped with specialized

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PC
BOOTLOADER UART

ANALOGIC COMMAND-line
INPUTS interpreter

FORMAT FORMATTING
Analog data ENGINE DATA

DIGITAL
DIGITAL OUTPUTS
INPUTS

OUTPUT
CALCULATION
CHARACTERISTI
PARAMETERS CS

SERIAL OUTPUT

Fig..2. Operating scheme of the firmware

moment the most popular idea is to equip any kind of device

IV. COMMUNICATION OF COMMAND-LINE WITH
with the possibility of firmware update. This is why the
THE SYSTEM
device possesses an ―update port‖, or uses one of the general
The data obtained from PC through the asynchronous bus
use ports. The update procedure is different from the general
is interpreted through a command-line. The used command-
communication one of the selected port. The program
line has the following advantages:
frequency that is responsible for update is named bootloader
 usage commodity; and is run in a special way. The physiotherapeutic complex
 increased flexibility; is also equipped with a bootloader making the update and
 extended data operating possibilities; device modernization possible at a maximum range. The
 autonomous functioning. update is performed from PC through the communication
The command-line will search the word, which will interface of the device (USB) using a special program.
correspond to a command from the PC part, at the beginning The execution of bootloader is made immediately after the
of the received data sequence, for example ―PTC_TEMP‖. complex turns on. If the linkage between bootloader and PC
In this case, the core will determine the execution of is stabilized in 2 seconds, the bootloader starts up the update
temperature read function, will prepare the answer for PC regime of the basic program. The firmware updates in
and will order the transmission of data. After existent data sequences, each sequence being verified using a sum control.
transmission towards calling stack, the results about the After finishing the update the program control turns into the
current temperature inside the physiotherapeutic complex execution sequence of the complex. If the linkage was not
will be transmitted towards. setup after 2 seconds, the basic program will be executed.
The command-line represents a standby module, which
has lots of received data operating possibilities. One of the VI. INTERACTION OF MODULES OF THE
possibilities is the determination of command parameters. PHYSIOTHERAPEUTIC COMPLEX
For example the PC sent the command ‖TENS_D 100‖. The The operation with the physiotherapeutic complex
respective command has to setup the time duration for the modules is made using the following components:
TENS module to 100 μs. The command-line will determine  Digital inputs;
the parameters of the income command, which has the value  Analog inputs;
100 in our case.  Digital outputs;
Although, the command-line usage imposes some  Analog outputs;
impediments during operation caused by the following The digital inputs are used to visualize some states for the
shortcomings: respective module. The state of the button placed on the
 the closed structure does not permit the operation optic head can serve as example for the laser module. The
with all data inside the command-line system; button is used for an easier interaction of the user with
 high execution time and big program volume; complex during the procedures.
 high volume of the used operating memory. The analog inputs of the main module are used for
monitoring the output circuits‘ state of the complex. The
V. MAIN MODULE analog signal converted into digital one demands a special
It has to be mentioned that not only peripheral modules formatting, because different modules have different output
can be modernized, but, also, the main module. At the parameters. The read analog signal is represented in a special

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

form, the final representation in voltage would be for the laser‘s work current. The potentiometer will form the
TENS module. The core will determine the module stop for reference voltage, which corresponds to the laser‘s current
protecting against an eventual output shortcut if the output source. characteristics.
voltage value would be lower on ¾ than the setup voltage
VIII. PC APPLICATION
value.
A PC application was created for communicating with the
The digital outputs possess 2 functions: signal creation
physiotherapeutic system.
and module connection. Initially, the module is turned on in
The main requirements for the application are reflected by
standby state. After that the output signal is generated and
the USE-CASE diagram (figure 4) and the program
the module turns form standby state into functioning regime.
functionalities by the classes‘ diagram.. A driver for RS232
In order to simplify the module stop it is necessary that the
device was installed, for controlling the module from USB
PC would indicate the stop command of the output signal.
port, and will contain a dll file with a set of API commands,
Digital potentiometers of 8 bits are used to form the
which will be used by the PC to execute the commands.
analog outputs. The guidance of a digital potentiometer is
The program controls a medical device though the USB
made using the synchronous bus TWI. Two digital
port, which has a graphical interface with access for
potentiometers are coupled in serial mode in order to
modifying and deleting patients‘ data into a database,
increase the precision up to 9 bits. The nonlinearity of the
represented in Access data file. This way the doctor will be
output signal has also increased, but remained in acceptable
able to visualize and control the technical regimes for each
limits.
person, configure the TeraLaser or other device. The
VII. OPERATION EXAMPLE FOR THE LASER program provides a display control of the module‘s response
THERAPY MODULE. to the queries applied through USB port.
Power Setup IX. CONCLUSIONS
A prototype of a complex system for physiotherapy was
elaborated as a result of the activity in the frame of a project,
Valid Error which will contain different modules like: main module,
NO
diapasone? Message communication module with the PC, Teralaser module, air-
ion-therapy module, and trans-coetaneous electrostimulated
YES therapy module of the nervous terminations (TENS).
Principles that vise the Visual Studio medium, C#
Data Prepare
language were engaged for PC connection and guidance. The
connection of one peripheral device through the USB port
was realized using this language (RS232 driver). Different
libraries were also used such as ADO.NET for registering,
Wiper value Watt-Amper modifying and deletion of patients‘ data in the Access type
calculation Characteristic
files. The commands‘ transmission towards the periphery
and response receiving was realized in the program. The
program guides the peripheral equipment using a set of
Setting of
wiper
commands, such as ―help/r/n‖, ―TENSVOLTAGE 40
mW/r/n‖ ect. Each module has its own properties and table
in database. Any king of database registration vises the
Setup Error properties selected by the doctor.
NO
approval? Message
REFERENCES
YES
[1] http://ftdichip.com/Drivers/CDM/CDM20602.zip -
communication driver
Succes [2] http://ftdichip.com/Documents/ProgramGuides/D2XX_
Message Programmer%27s_Guide(FT_000071).pdf – description
Fig. 3. Block scheme of laser‘s power setup. of FT2XX APIs.
Conforming to the functioning specifics of the quantum [3] http://www.codeproject.com/KB/cs/serialcommunicatio
therapy module it is necessary to setup the laser output n.aspx - comunicarea prin porturi USB, Autor Tapan
power by making the PC query the execution of power Dantre
setup. [4] AVR109: Self Programming
http://www.atmel.com/dyn/resources/prod_documents/doc1644.pdf
The block scheme of laser emission power setup is
[5] D. Knuth, The Art of Programming. Addison-Wesley,
presented in figure 3. The core will verify if the if the power
1973
corresponds to the 5-50 mW diapason. Further, data
[6] Using the TWI module as I2C master on tinyAVR and
preparation and the calculus of potentiometer values will be
megaAVR devices
done, which will correspond to the laser watt-ampere
http://www.atmel.com/dyn/resources/prod_documents/doc2564.pdf.
characteristic. The watt-ampere characteristic of the laser is
positioned in a data array from the address space of the
internal EEPROM of the microcontroller. The calculus of
the potentiometer value is coming after calculating the

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International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

uc Use Case Model

Introduction of patient in
DB

Crating of patient
list
Doctorl
Selecting of
Frequency type

Modification of
Patient personal
«include» data

Setting of frequency
diapasone
«include»
Laser
Delete from list
Configuration
of patients
«include»
Frequency setup

«include»
«include»

«include» «include»

Setup of time
intervals
Power setup

Pots setup
Time setup

Fig. 4 USE-CASE diagram of the PC application

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

The Change of Peripheral Excitability Caused

by Millimeter Waves
Aurel SAULEA, prof., Dr. hab., Victoria CHIHAI, lector-assistant
Department of Physiology and Biophysics, State Medical and Pharmaceutical University „Nicolae
Testemitanu” of the Republic of Moldova

Abstract – We conducted a double blinded prospective trial to evaluate the change peripheral excitability
effect of millimeter waves (MW) under experimental conditions. Sixty healthy volunteers were exposed to
active medical MW generator and to a disabled sham generator. Characteristics of continuous wave
electromagnetic output from the active generator were: wavelength 5,6 mm incident power density 10
mW/cm2 and duration of exposure 15 min and 30 min. MW produced a significant (p<0,0001) decreasing of
peripheral sensibility in group with duration of exposure 30 min and non-significant decreasing of peripheral
sensibility in group with duration of exposure 15 min. decreasing of peripheral sensibility (sensitivity) was
appreciated by increasing of cronaxia – one of parameter of peripheral sensibility.
With on average 200% of the 30 volunteers 11 (36,6%) reacted to the active MW generator with an decreased
peripheral sensitivity by individual reactions varied from 300% to 345% comparison with their own
preexposure levels.
MW therapy con be used as a supplementary or alternative treatment for decrease peripheral sensitivity for
example peripheral pain.

and after exposition to MW generator we have recorded

I. INTRODUCTION
value of cronaxie.
Electromagnetic millimeter waves (MW) are one of
Volunteers from second group was exposed to an active
components of environment. Technical progress change
sham MW generator during 30 min, before and after
wavelength, frequencies on incident power levels of
exposition we have recorded cronaxie. In this way we a
millimeter waves. At present electromagnetic millimeter
formed a baseline reading of cronaxie for each group of
waves with incident power levels < 25 mW/cm have been
exposition. The medical MW generator ―КВЧ универсал‖
used for medical purposes in several Eastern European
used in this study emitted a continuants electromagnetic
chantries for more them a decade [1].
signal with frequency of 8 Hz (corresponding
Our analysis of literature reveled the more material
wavelength 5,6 mm) and incident power density of 10
accumulated the present about biological effect and radiant
mW/cm2 . the hand skin between thumb and index finger
energy of electromagnetic millimeter waves [2].
(corresponding to biological active point G4) was exposed
The first biological structures which feel MW action are
to the generator MW, the patient was sifting in an chair.
peripheral skin structures: receptors, capillaries, organically
The waveguide of the generator was located at the skin
and non-organically water solutions [3].
surface. The order of exposure of volunteers to an active
This is a very important feature of MW which con be
and sham generator was varied randomly.
used for study any peripheral effects and changes of any
Cronaxie was recorded by system ―Neoropuls‖ by active
peripheral parameters.
electrode located in the point G4: method begin by
Very few publications [2] contained clinical results with
recording of rebases - minimal sensitive threshold and after
the use of MW obtained in a double-blinded manner. What
then time action of double rebases will be cronaxie.
because we effectuated a double- blinded study in healthy
Two identical devices were used for exposure to
human volunteers for investigating changes of peripheral
electromagnetic MW and sham exposure. The output of the
sensitivity in MW action. Sensitivity modification was
sham generator was disconnected, but all of the external
studding by increasing or decreasing of cronaxie – one of
features of both generators were the same.
parameters of peripheral sensitivity.
The generators were marked 1 and 2 and the responses of
The results of our study are described below.
the volunteers were analyzed separately.
II. METHODS Comparison of baseline readings with the results of true
Sixty volunteers participated in the study. The volunteers and sham exposures was performed by using Mann-
were students of University of Medicine and Pharmacy Whitney U test. The level of significance was set at
from Chisinau (R.Moldova). All students were informed (P<0,001) for gust for one test.
about the physical and biological properties of MW and all
III. RESULTS AND DISCUSSION
of then gave their consent to participate in the study. The
Possible adverse effects were monitored by observing the
criteria for volunteers were: heating adults 18/20 yr old,
volunteers and by asking them questions about any
none was a chronic pain sufferer or was taking any
reactions in time of exposition. No adverse effects of
medication. Volunteers were divided in 2 groups by 30 in
exposure to MW were noticed.
each group.
The response of volunteers exposed to MW 15 min
Volunteers from ferst group were exposed to an active
peripheral excitability increase and cronaxie decrease by
and a sham MW generator with duration 15 min. Before
4,2% (Fig.1).

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

The response of the same volunteers exposed to sham Our results, obtained under double-blinded conditions,
generator 15 min peripheral excitability decrease cronaxie show that a 30 min exposure to the MW produce in
increase by 14,3%. creasing of cronaxie one of the parameters of peripheral
The response of volunteers exposed to MW generator 30 excitability. MW has three levels of interaction in human
min peripheral excitability decrease cronaxie increase by body: primary sensors of MW in the organism;
21,2% (p<0,0001). The response of the same volunteers pathwaystransmitting the signal to the regulating center;
exposed to sham generator 30 min peripheral excitability biological and chemical substrates implementing the
decrease - by cronaxie increase by 19,9% (fig.2). response to the stimulus. Some clinical results indicate that
Our results indicate that MW produce decreasing of the central nervous system participates in response to MW
peripheral excitability in healthy volunteers . This is stimuli; for example, electroencephalogram changes were
significant increasing (p< 0, 0001) of cronaxie in time of registered in healthy volunteers [6] and children with
exposition to 30 min. cerebral paralysis [7] as results of their exposure to MW.
Exposition to 15 min or to shame generator not produce Also the ability of neurons of organisms to react to low-
significant decreasing of peripheral excitability (in creasing power MW signals [5,6]. Thus nerve ending possibly
of cronaxie). participate in the primary reception of MW. Our results
open any explication of this possibly mechanism. But, in
summary, mechanisms of MW remain to be elucidated
more.
REFERENCES
[1] Rradzievsky A., Rojavin M., Cown A., Ziskin M.
Suppression of pain sensation caused by millimeter
waves: a double-blinded, cross-over, prospective
human volunteer study. Anesth Analg.1999, 88:836-
40.
[2] Rojavin M., Ziskin M. Medical application of
millimeter waves. Q J Med 1998; 91:57-66.
[3] Korpan N., Saradeth T. Clinical effects of continuous
microwaves for postoperative septic wound treatment:
a double-blinded controlled trial. Am J Surg 1995;
170:271-6
Fig.1. Changes of cronaxia in MW after 15 minutes.
[4] Walsh N., Schoenfeld I., Ramamurthy S., Hoffman J.
Normative model for cold pressor test. Am J Phys Med
Rehabil 1989;68:6-1.
[5] Alekseev S., Ziskin M., Kochetkova N., Bolshakov M.
Millimeter waves thermally alter the firing rate of the
Lymnaea pacemaker neuron. Bioelectromagnetics
1997;18:89-98.
[6] Akoev G., Avelev V., ASemenjkov P. Reception of
low-intensity millimeter waves electromagnetic
radiation by the electro receptors in skates.
Neuroscience 1995; 66:15-17
[7] Antonova L., Zhukovskii V., Kovalenko V., Semenova
K. The clinico-electrophysiological assessment of the
efficacy of microwaves resonance therapy in the
rehabilitative treatment of patients with cerebral palsy
Fig. 2 Changes of cronaxia in MW after 30 minutes.. in the firm of spastic diplegia. Vopr Kurortol Fizioter
Lech Fiz kult 1995; 4:13-7.
[8] Saulea A., Chihai V. The millimeter waves in medicine
and biology. The XIII international symposium,
Russia, Moscow, 2003; 100-102.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

The Implementation of Modern Digital

Technology in X-ray Medical Diagnoses in
Republic of Moldova – a Stringent Necessity.
Andrei ROSCA
Technical University of Moldova.
e-mail: [email protected].

Abstract – The study includes the analyses of state of technical X-ray diagnostic equipment from public medico-
sanitary institution of Ministry of Health of Republic of Moldova (IMSP MS RM) at 01.01.11.
The traditional RD apparatuses’ were morally and physically outrun at 96,6% (in raional MSPI- 93,5%),
inclusive the dental one -92,0% (in raional MSPI-97,2%), X-Ray exam -100%, mobile – 84,1% etc.
The exploitation of the traditional RD apparatuses’ with high degree of physical and moral wear essentially
diminished the quality of profile investigation, creates premises for diagnostic error perpetrating, increase the
collective ionsating irradiation of population etc.
In recent years it starts the subvention of MSPI HM RM with digital RD dispositive, a process, which very hard
unfold because of grave socio-economic crises in Republic of Moldova (since 01.01.11 only 30 apparatuses are
pure digital). Despite these obstacles the subvention of MSPI HM RM with digital equipment represent a
stringent necessity and a time request.

Key word– traditional X-ray exam, digital X-ray exam, and moral wear, the digital dispositive subvention.

from the total population of Republic of Moldova.

I. INTRODUCTION
The utilization of traditional X-ray diagnostic dispositive TABLE 1. THE TECHNICAL STATE OF TRADITIONAL FIXED X-
(RD) at present time in Republic of Moldova represent a RAY DIAGNOSTIC DISPOSITIVE IN MSPI HM RM AT 01.01.2011
outrun procedure which decrease considerable the X-ray Type of Total of Inclusive The rate of
exam quality, increase the ionsating irradiation doze of institution dispositive morally and morally and
population etc. This using is essentially disturbing by physical physical
absence of the exchange pieces, which are not produced outrun (abs) outrun
any more, the patients exam by second hand dispositive, dispositive
supplied by humanitarian aid is very difficult because of (%)
lack of necessary documentation (using manual the scheme Republican 148 126 85,1
of dispositive, the certificate of corresponding to European Municipal
standard requests etc.). (Chisinau, 114 101 88,5
In the same time, thanks to modern technological Balti)
progress, appears a new digital technology, which present a Raional 358 335 93,5
considerable support in assurance of qualitative assistance Total 620 562 90,6
with medical RD improves the diagnostic quality decreases
the ionsating irradiation, perfectly meet the European In the same time the rate of X-ray exam dispositive,
standards etc. using till present for population screening in the purpose of
Material and methods. It was analyzed the information early revealing (opportune) of persons with suspicion to
included in official annual statistic form (f.30-san), 2010, evolutionary lung tuberculoses, malignant neoplasm‘s and
using the documentary statistic and comparative analyzing other pathologies of thoracic cave is 100%.
methods. And in dental practice X-ray is often used. The
II. RESULTS AND DISCUSSION. performing of dental X-ray by dental traditional RD
Because of deep socio-economic crises existing actually dispositive (5D1, 5D2) needs the expecting of same
in Republic of Moldova, the rate of fixed traditional X-ray radioprotection rules: using of dental apron or lead rubber
exam dispositive morally and physically outrun in MSPI collar and glasses (preferably) from lead glass because of
HM RM at 01.01.2011 were by 90,6% data included in the impossibility of collimation of ionsating irradiation fascicle
table nr.1. etc. During 2006-2010 years in MSPI HM RM was
The table 1 data show us that the rate of morally and performed since 100897 dental X-ray exams in 2006 till
physical outrun dispositive in republican institution is 146149 in 2009 (in 2010 - 130838). In the same time the
85,1%, but in municipal institution – 88,5, because of absorbed doses of ionsating irradiation by performing jf one
substitution of lesser number of traditional dispositive with traditional dental X-ray exam is 0,7 milligrey (1 Gy = 1
analogy-digital, and pure digital. The highest rate morally J/kg=100rad), when for the same radiophotography,
and physical outrun dispositive were found in raional performed by Visiograph accumulate an absorbed doses
MSPI, which considerable decrease the assistance quality only 0,05 mGy or 12 times lesser (in same cases even
of RD, granted to rural population, which constitute 60% more), substituting with success the traditional dental
radiophotography, being a modern dental radiodiagnostic

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

method. In this context the high degree of physical and As it is shown by table 3 data in MSPI HM RM exists 44
moral outrun of traditional dental RD dispositive into MSPI dispositive of digital RD, inclusive 9 tomography
HM RM constitute at 01.01.2011 – 92,0% (in regional computers and 30 mobile dispositive and just 2 visiographs
institutions-97,2%, because of using of RD MT dispositive, for dental necessity the technical state of which is very
which does not use the modern digital technologies good. This circumstance permits radioprotection
(Visiograph). optimization, irradiation security assurance, improvement
In MSPI HM RM are also used the mobile X-ray of medical X-ray exam quality.
dispositive, for investigation of patients with trauma,
III. CONCLUSION.
surgery, neurosurgery etc. gravely, which can not move to
1.At actual time 90,6% from total traditional RD
radiodiagnostic lab‘s. The technical state of this category of
dispositive from MSPI HM RM is morally and physical
dispositive in included in table 2.
outrun, inclusive radiophotography dispositive – 100%,
TABLE 2. THE TECHNICAL STATE OF MOBILE DISPOSITIVE OF dental X-ray exam 92,0% (in regional MSPI- 97,2%),
TRADITIONAL X-RAY EXAM FROM MSPI HM RM AT 01.01.2011. mobile – 84,1%( in regional MSPI-88,3%).
Type of Total of Inclusive The rate of 2.The use of morally and physical outrun dispositive
MSPI dispositive morally morally and decrease essentially quality of medical care, contributed, in
(abs.) and physical great measure of increasing of collective ionsating
physical outrun irradiation of population of republic.
outrun dispositive 3.The created situation at the moment in Republic of
(abs) (%) Moldova input the substitution of all traditional RD
Republican 57 48 84,2 dispositive with those digital, which will improve the
Municipal radiodiagnostic quality, decrease the near by 8 times the
(Chisinau, 30 22 73,3 collective irradiation of population, to warn the revealing
Balti) of cancer induced by medical ionsating irradiation etc.
Raional 77 68 88,3 REFERENCES
Total 164 138 84,1 [1] Dânga V., Roşca A., Prepeliţă S., Tverdohleb O.,
Bahnarel V., Stanchevici V. The efficiency,
From the data from table 2 the majority of mobile qualitassurance and radioprotection during
dispositives are morally and physical outrun, need prophylactic X-ray exam from m. Chisinau in 1996-
substitution with those digital, the absorbed dose of 2007 time period. Bulletin of the Academy of Sciences
irradiation, being 6-8 lesser than in case of using traditional of Moldova. Medical Sciences. Chisinau, 2007,
dispositive of RD TM. N.5(14), p 29-32.
Recent time the Ministry of Health of RM start the [2] Practice quideline for digital radiography. In Practice
subvention of MSPI with new technology, included digital Guidelines and Tehnical Standards. Reston, Va:
one. American College of Radiology: 2007: 23-57.
The technical state of digital RD, inclusive computer [3] Rosca A. - The medical imagining and radiotherapy
tomography, considered by us digital in MSPI HM RM at activities in Republic of Moldova in the new economic
01.01.2011 is included in table 3. condition and masseurs directed to its improvement.
the actual medical imagining and radiotherapy
TABLE 3. THE TECHNICAL STATE OF DIGITAL RD DISPOSITIVE, problems. Materials of the first congress of
INCLUSIVE COMPUTER TOMOGRAPHY IN MSPI HM RM AT
01.01.2011 Radiotherapist and Radiologists of Republic of
Moldova. 5-6 October 2000, Chisinau p11-16.
Inclusive
Total digital
dispositive Computer
digital
tomography
Type of Inclusive Inclusive
morally morally
M SPI Statio- visio-
total and % total and mobile
physical physical
-nary -graph
outrun outrun
Republican 22 2 - 8 2 13 - 1
M unicipal
(Chisinau, 15 - - 1 - 14 - -
Balti)
Raional 7 - - - - 3 3 -
Total 44 2 5,1 9 2 30 3 2

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Sensors of Ultraviolet Radiation for Medical

Equipment
Authors: I. ABABII, E. ARAMA
State University of Medicine and Farmacy „Nicolae Testimiţanu” from R. Moldova
Departament of otorinolaringology and
departament of Human Physiology and Biophzsics.
Abstract. – The results of elaboration, construction and implementation of ultraviolet radiation detector with
high sensibility are presented, which is used as portable device for measuring the intensity and dose.
Photodetectors possess high stability at radiation and are promising for multiple practical applications,
including for the construction of x-ray detector and of transducer to register electrons flux density. The
optimal parameters give the possibility, to use the detectors in medicine, biology, ecology and agriculture.

Keywords – UV radiation, doze, UVimeter, photorecervers, wavelength, photosensitivity.

crystalline in vivo [2].

I. INTRODUCTION
The UV radiation in the optimal doses stimulates the
The ultraviolet UV radiation acts effectively upon the vital
development of young organisms and stops the apparition of
activity of living organisms and plants. This fact leads to
the rachitic and the anemia, but the radiation that has a
their wide application in biology, medicine, agriculture.
maximum of about λ=300 nm at certain dose provokes the
According to the opinion [1] the radiation UV is divided in
cancer. The effect of this type of radiation on the plants also
three regions: UV A, UV B and UV C. Ultraviolet A (λ=320
depends on the dose.
’ 400 nm) belongs to the solar light which reaches the Earth
With the context of that mentioned, the necessity of exact
surface produces a weak erythematic effect; UV B (λ=280 ’
appreciation of UV radiation dose by the UVimeter is
320 nm) has the action on the skin, causing a more
evidently, the element of registration of radiation is the
pronounced erythematic effect followed by pigmentation;
radiation UV photoreceiver. The great interest to the UV
UV C (λ=220 ’ 280 nm) has more dangerous action on the
radiation receptors was increased considerably last years.
living matter.
This interest is thoroughly justified on the fact that the above
A great majority of biological vegetable and animal media
mentioned spectral range in comparison with other spectral
absorb the UV radiation with the wavelength shorter than
subranges, especially those of visible light, is insufficiently
230 nm. The proteins absorb radiations with the wavelength
provided with the detectors of small dimensions.
of λ=275 nm; nucleic acids and fatties are also absorbing of
UV. It is sufficient to mention, that the human eye is II. EXPLANATION AND COMPARISON OF
exposed during its life to the radiation of UV that belongs to CHARACTERISTICS AND PARAMETERS
the solar radiation spectrum. The main function of ocular Some models of detectors are proposed recently for the
anterior pole (cornea and crystalline) is that of focusing this UV domain. The elaboration of portative apparatus is
radiation on the retina, being in the same time as an efficient necessary for the extended application of UVimeter in the
filter for the UV A and UV B and protecting the retina of above mentioned ranges. For this elaboration, the application
their dangerous action. The radiation of the wavelength of semiconductor structures as the photoreceivers is
λ=295 nm is absorbed completely by cornea. The crystalline necessary, because they posses all necessary qualities: are of
absorbs radiations UV A and UV B (295 ’ 400 nm) which small dimensions, resistant, and self supplying, posses the
crosses the cornea and can have photo traumatic effects on guaranteed protections [4]. For example, the authors of the
the structural crystalline proteins. The prolonged exposition paper [5] propose detectors with barrier on the surface of the
(big dose of UV radiation on the crystalline) leads to the epitaxial films n-n+-GaP . The measurement device of UV
cumulative photochemical deterioration and leads to the radiation UVR-21 is made on their base. The simplicity of
actinic ophtalmia, cataract, destroys the retina and leading to production is mentioned in the paper as the quality of
the blinding. The mechanism, by which the UV A and UV B advantage and their exploitation. The researchers from the
radiation produces cataract, is not so clear; the processes of Ukraine SPhI of AS suggest photodiodes made on the base
biochemical nature and biological one can take place in the of halogenides of Cd for the commercialization, which can
photochemical moment and the formation of cataract [2]. be applied for the registration of UV in different subranges
There are numerous epidemiological and laboratory studies, of wavelengths [6]. We suggest different detectors for this
which demonstrate that the photons of UV radiation that spectral range on the base of layered multisulfides [7,8]. The
touches the eye (especially UV B) are strong cataract technology of preparation of layered monocrystals is simply,
dangerous for the human crystalline. This fact generated a but the method of appreciation of characteristics is already
great interest for the mechanism of the action of UV B elaborated, being described in the papers [9,10,11]. For the
radiation on the crystalline proteins, and also on the ADN of bacterial subrange the photoresistors of the oxide and of
the epithelial cells from the crystalline. There are studies in cadmium aluminum sulfide are elaborated (CdAl2S(O2))
the specialization literature, which shows that the UV [12].
radiation determines the changes in the structure of An analogical UVimeter with those mentioned was
crystalline proteins and can modify the interactions of them, elaborated, built and implemented by the coworkers of State
responsible for the maintenance of transparency of the University of Medicine and Pharmacy ―Nicolae

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Testemitanu‖ at the Othorinolaryngology and the department

of Human Physiology and biophysics, in collaboration with
the Applied Physics Institute of Moldavian AS [7, 13-15].
One of the basic properties of semiconductor material used
for the elaboration of UV radiation detectors is the large
band gap (Eg≥3.0 eV) necessary for the exclusion or
reducing to the minimum the sensitivity at visible and
infrared radiation. This request is satisfied successfully by
the compounds Zn3In2S6 (a), Zn3 GaIn6S6 (b), and Zn3 AlIn2S6
(c) that belong to the group of halogenides with the
crystalline structure as the form of layers and have the
energy bang gap equal to 3.05, 3.25 and 3.37 eV respectively
[10, 14]. The photoreceivers are elaborated and built with the
spectral characteristic as the rectangle shape (Π), on the base
of layered monocrystals, which have the high sensitivity in
the limits of photons with the energy higher than the energy
band gap hν>Eg. This property is characteristic for the
named transition due to of small speed of recombination on
the surface of these semiconductors. The process of
elaboration and building of photoreceivers is described in the
papers [13-16]. The above mentioned monocrystals were
used in order to build the photoreceivers. The monocrystals
present the mounts with the surface area S ≥ 100 mm2,
which are cleaved easily up to the thicknesses of 10’500
μm.
The photodiodes with the surface barrier (SBS) – Shottky Fig. 1 The spectral dependence of photosignal of Shottky diodes on the base
diodes were elaborated as the photosensitive structures of the compounds Zn3InAlS6 (a), Zn3InGaS6 (b) and Zn3In2S6 (c) with
which have the following principle advantages: the rectifying contact
- high photosensitivity into a high spectral range of The maximum of the open circuit voltage (VOC) of the
wavelengths; structure makes 400 – 600 meV and the rectification
- the electrical current supply device is not coefficient is 102 - 104. The maximum of VOC spectrum is at
necessary, because the photocurrent is generated on the 3.5, 3.7 and 3.2 eV for the SBS made of the compounds a, b
base of radiation that is received; and c, respectively.
- The Lux – amperical characteristic is linear into a The filters УФС – 2 and ЖС – 3 with the thickness of 0.1
large interval of received flux; cm are used in the real receivers for the limitation of spectral
- Simple technology of fabrication. sensitivity and exclusion of nondesired band. The typical
The detailed study of SBS was performed with different spectral characteristics are presented in the fig.2, but the
contacts on the base of layered monocrystals ZnIn2S4 [9,10]. main parameters of detectors are presented in the table 1.
The analysis of obtained results allowed the formulation of TABLE 1. MAIN PARAMETERS OF DETECTORS
their performed characteristics.
The film of Pt with the thickness of 10-15 nm was used as Current sensitivity, A∙cm2/W 4∙10-4-3∙10-3
the rectification contact with the uniform transparence in Upper L – IPC line limit, W/cm2 10-4-10-2
whole range of near UV. The layer of ITO serves as ohm Base resistance, Ω 105-3∙106
contact (mixture of SnO2 and In2O3). Both contacts were Photosignal duration, s 10-3
deposited on the crystallographic planes by the method of
thermal vaporization into a vacuum (0001) situated on both The research of the process of endurance of photodiodes
surfaces with the thickness of 10-20 nm. The coplanar exposed by UV radiation with high intensity (102W/m2)
contacts were deposited in the case of the detector on the and long (3.6∙105 s and more) proved that the structures with
base of the compound CdAl2S(O2) . the contacts of gold or platinum do not indicate any omens
The normalized spectral distribution of the photosignal of of endurance. The application of these metals is preferable,
SBS made on the basis of multisulfides a, b and c is because they influence little the cost of photoreceiver and for
presented in fig.1 (T = 300 K), which has large distribution one device only 2 mg of Au or Pt are consummated, the
and more pronounced removing in the range of short duration of functioning of photoreceiver is enough long. The
wavelengths in comparison with the photoconduction photoreceivers are applied for the measurement of absolute
spectra. This is explained by the leakage of charge carriers in values of the UV fluxes radiation and work 4-5 years. The
the contact region of the respective structure. UVimeters and dosimeters are elaborated for UV radiation
The value of forbidden band gap Eg of the compounds a, on their base. Both high stability and the simple system of
b and c increases in the named order, but the maximum of registration of the signal provides for these devices the
spectral distribution of the signal is removed in the direction considerable advantages with respect to those built on the
of short waves of spectrum. In this case the SBS can be built, base of other compounds [15].
whose photosensitivity spectrum covers the entire near UV It is evident that the UVimeters used for the measurement
region, but with decreased relative sensitivity in the visible of smaller intensities will work long term. In order to
spectral range (λ=380400 nm). increase the functioning term, the neutral homogenous filter
for the near UV was used, which attenuate the intensity of

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about 10, 100 times. The filter represents a layer of Ni action of radiation of radioactive nature, the structures Pt-
with the respectively thickness deposited on the support of Zn3In2S6-In were studied at the action of electronic flux with
quartz by the method of vaporization into a vacuum. the energy about 40 keV.
The compounds with the stoechiometrical vacancies, from
which belong also those studied, have the high level of
stability.

Fig. 2. Spectral characteristics of photosignals of diodes: (1)Pt-Zn3In2S6

without filter; (2) with filter; (3) Pt-Zn3Ga(Al)InS6 with ЖС-3 filter.

The elaborated photoreceivers on the base of Shottky

diodes Me-Zn3In2S6 have sensitivity in the fields of
wavelengths 220’400 nm. In order to reach some high
performance of sensitivity in the field of spectral bands with Fig.3 The typical spectra of the photoconduction of ceramic CdAl2O4 (1) and
CdAl2S4
the erythematic effect A, B and A+B, the cheap optical
filters were used on the base of vitreous compounds. In order As the depth of penetrating of electrons by
to register the radiation from the range A+B, the more semitransparent electrode of Pt in the monocrystals does not
convenient is the filter UFS - 2 with the thickness d=1 mm, exceed some μm, the influence of ionization belongs to the
but for the registration of the field A the system composed of lacked portion of the diode, but the space of the
filters UFS - 1 (d=1 mm) and SS-13 (d=2 mm) was used or semiconductor with the thickness of about 10-20 μm is not
the system composed by filters UFS – 1 (d=1 mm) and FS - affected practically to the influence of radiation. So that, in
1 (d=2 mm). For the registration of the field B the filter UFS order to lead the influence, those parameters were chosen
- 1 was chosen (d=1 mm) in the combination with GS - 3 that determine the region of barrier: the spectral distribution
(d=2 mm). Thus, for all three domains of erythematic of Voc, sensitivity, direct portion of volt-amperic
radiation the filter UFS-2 must be used, it was installed in characteristic at small voltages and indirect current. These
the interior of the transducer, but for the filter SS - 13 (FS - parameters were measured for a set of diodes, before and
1) and GS - 3 the possibility of dynamical installation was after irradiation with the doses 6∙10 16, 1017, 6∙1017, 1018
foreseen. For the commodities of the users the special el/cm2. For first two doses the characteristics of diodes
construction [14] was elaborated that in front of transducer coincide with those initial. The change of the parameters of
the obturator disc with three windows is installed (without diodes are observed beginning with the dose 6∙1017 el/cm2
filter and with filter GS-3 or SS-13 (FS-1)). Rotating the and is manifested by the changing of photosensitivity and
obturator disc, the fixing of one from those three windows in maximum of Voc, the direct and indirect approximated
front of transducer takes place for the registration of increasing four times, the removing of the maximum
radiation dose or the intensity in one of the above mentioned position of photosignal to small energies of about 0.6 at the
domains. It is evidently, that the standardization of electronic dose 1018 el/cm2.
block was performed separately for each of those spectral The combination of high values of photosensitivity and of
domains (A, B, and C). The used crystals as is stated in the stability creates the perspective that the multicomponent
paper [17] have the high stability and, so that the elaborated halogenides compounds can be used as the detectors for
photoreceivers on their base will resist to the action of Roentgen radiation. The detectors of Roentgen radiation
physical factors. were built experimentally on the base of the compounds a, b,
The spectra of elaborated photoresistors on the base of and c with the resistance at darkness 109 Ohm and high
ceramic CdAl2O4 and monocrystals CdAl2S4 are presented in sensitivity in the range of quanta 1-10 keV. The factors of
the fig. 3 [12]. They cover the spectral range 220’320 nm amplification, measured in the range of energies 2-7 keV
with high sensitivity at the wavelength of about 250 nm. The exceed the value of 104 el/quantum. The time resolution does
diodes have the high stability of functioning into a medium not exceed 10-9 s. These parameters allow the
with a high degree of humidity, maintaining the absolute recommendation of named detectors for the diagnosis of
sensitivity of 10-5 A∙cm2/W. Thus, we can look forward, laser plasma. We mention that on the base of above
that the devices will resist to considerable fluxes of ionized described detectors, using the experimental possibilities of
radiation. In order to study the stability of photodiodes at the the Institute of Applied Physics of AS of RM, the portative

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UVimeters were built and elaborated for the Republican [5] A. Malic, Y. Vygranenco, B. Shabashkevich et al.//Int.
Hospital of Children ―Emilian Coţaga‖ where they were Semicond. Conf., Sinaia, Romania, vol. 1, 2001, pp.
approved successfully. In conclusion we mention, that using 185-188.
the layered crystals of Zn3In2S6, Zn3GaInS6 and Zn3AlInS6 , [6] V.N. Komashchenko, K.V. Kolezhuk, E.A. Venger et al.
the detectors of UV radiation with high sensitivity were built Pis’ma v ZhTF, vol. 28, 19, pp. 32-36, 2002.
and implemented in medicine at the portative devices for the [7] I. Ababii, E. Arama. UV Dosimeter for Medical
measurement of intensity and radiation dose (practically all Aplicatio. Analele Ştiinţifice ale USM, seria "Ştiinţe
near UV). For example, we show the photographs of one fizico-matematice", 2002, pp. 45-49.
devices built on the base of our elaborated diodes. (Fig. 4). [8] I. Ababii, E. Aramă. Dozimetru pentru recepţionarea
ultravioletului în Medicină. Analele Ştiinţifice ale
USMF, 2002, vol.1, pp. 164-171.
[9] Е.Д. Арама, Н.С. Грушко, В.Ф. Житарь, С.И.
Радауцан. Электрические и фотоэлектрические
характеристики диодов Ni-ZnIn2S4. ДАН СССР,
1976, т. 227, N6, c. 1329-1383.
[10] Е.Д. Арама, Н.С. Грушко, В.Ф. Житарь,
С.И.Радауцан. Влияние базы на параметры диодов
изготовленных из высокоомного ZnIn2S4.. Письма в
ЖТФ, 1997, 2, вып. 6, c. 254-258.
[11] S.Radautsan, V.Raylyan, I.Tsiulyanu, V.Zhitar,
M.Marcus, N.Moldovyan. New Zn3InGaS6 phase and its
main properties. Progr. Cryst. Growth and Charact.
Caracas, 1985, pp. 397-399.
[12] Н.А. Молдовян. Выращивание и исследование
фотопроводимости ZnAl2S4 и CdAl2S4 .Изв. АН РФ,
Fig. 4. The measurement device with the digit display of UV radiationwith сер. Неорганические Материалы, 1993, т. 27, №9,
the intensity in limits of values 10-4’2∙10 mW/m2 the spectral domains, nm: С.1969-1971.
280’400, 320’400, 320’360; the dose - 0’1.6∙105 J/m2.
[13] V.F. Zhitar, N.A. Moldovyan, E.D. Arama, S.
The current supplying – 220 V. Radautsan. Short-wavelength radiation detection on the
These photoreceivers with high stability at the irradiation layered sulphides.. XV Annual Semiconductor
and in accordance with it, they can found multiple practical conference, Sinaia, Romania, ICCE, 1992, pp. 267-270.
applications, also for the creation of Roentgen radiation [14] E.Aramă. Recepţionarea ultravioletului cu detectori pe
detectors on the base of the named semiconductor sulfizi stratificaţi. Intelectus, Chişinău, , vol.4, 1999, pp.
compounds and for the registration of density of electron 72-75.
fluxes. [15] E. Arama, I. Ababii, V. Zhitar, T. Shemyakova. UV
Detectors Based on ZnxIn2S3+x and Related Compounds.
REFERENCES
Intern. semiconductor Conf., Sinaia, Romania, 2003,
[1] Nagi I. Iosif. Biofizica, Timişoara, 1990.
vol.1, pp. 147-150.
[2] I. Jeru, E. Bendelic, V. Boiştean, E. Aramă.
[16] В.Ф. Житарь, Т.В. Абрамова, Е.Д. Арама, В.К.
Particularităţi ale tratamentului medicamentos în
Якуша. Кинетика фотопроводимости и
cataracta senilă, Analele Ştiinţifice ale USMF, vol. 4.,
люминесценции ZnIn2S4.. Изв. РАН, сер. неорган.
2003, pp. 289-293.
Материалы, 1991, т.27, N11, c. 2245-2247.
[3] A. Stănilă, Cristalinul, Sibiu, 2001
[17] Н.А. Молдовян, Д.С. Ременко. Фотосопротивление
[4] E. Arama, ,Archives of the Balkan Medical Union,
ультрафиолетового диапазона. Авт. свид. СССР
2002, p. 164.
N1050.

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Influence of Face Mask on Breathing During

Hyperventilation Test
Tudor BESLEAGA1, Pascale CALABRESE2, Victor VOVC1, Pierre BACONNIER2, Ion
MOLDOVANU1, Andre EBERHARD2
1
State University of Medicine and Pharmacy “N. Testemitanu”, Chisinau, R. Moldova
2
Lab. PRETA-TIMC, University Joseph Fourier, Grenoble, France

Abstract- The aim of present study was to evaluate the changes of breathing pattern related to the influence of
the face mask during voluntary hyperventilation. We compared respiratory variables in recordings with and
without mask in different periods of hyperventilation test. Our finding – the mask increases some variables
at rest (inspiratory time) and during recovery period after voluntary hyperventilation: (inspiratory time,
tidal volume and pulmonary ventilation). The mask decreases respiratory variability at rest and during
recovery periods. These effects can be provided by behavioural influence and the additional dead space of
apparatus.

without facial mask, the FETCO2 was collected by nose clip

I. INTRODUCTION
(protocols THV and THV20). Before the recording without
Respiratory inductance plethysmography (RIP) is a non-
mask we recorded the 2 minutes period of quiet respiration
invasive method for measurements of rib cage and abdomen
simultaneously with flowmeter and RIP to calculate
respiratory movements. These rib cage and abdominal cross
individual adjusted filter. Analysis: All signals were
sectional area changes allow calculating respiratory volumes.
digitized at a rate of 100 Hz. The 15 most regular
Respiratory airflow is recorded by pneumotachograph, but
consecutive breaths of the airflow signal formed the
the using of mouthpiece or a facial musk can change
reference part [1]. A least squares method was used over
breathing pattern by behavioural influences and by
this part of signal to obtain a RIP volume signal (VRIP) by
additional apparatus dead space.
combination of rib cage (RCRIP) and abdominal
Calabrese et al. [1] compared pneumotachographic
(ABDRIP) signals compared to the integrated flow signal
airflow (PNT) and RIP derivative signal of quiet respiration,
(VPNT):
during voluntary hyperventilation and recovery periods, RIP
VRIPk= τ RCRIPk + α ABDRIPk (1)
derivative signals were filtered by an adjusted filter based on
Where τ =2 was imposed [3]. The derivative of VRIP
each subject pneumotachographic airflow signal (PNT).
(FRIP) was then calculated by using centred divided
Authors concluded that the adjusted filter calculated from
differences:
quiet respiration can be used in different conditions: quiet
FRIPk = (VRIPk+1 - VRIPk-1) / 2Δt (2)
respiration, hyperventilation and recovery after
A transfer function was calculated over the reference
hyperventilation to obtain adequate derivative RIP signal.
part between RIP derivative and airflow signal to take out
Change of interactions between automatic and
an adjusted filter. Then the adjusted filter calculated on the
behavioural regulatory mechanisms of respiration occurs
reference part of signals was applied on the entire recording.
during voluntary hyperventilation. The aim of our research
We calculated adjusted filter from rest period in recordings
was to determine the influence of the mask on breathing
with mask (THVm and THV20m) and from two minutes
pattern in healthy subjects in different periods of
recording period with PNT and PIR preceding recordings
hyperventilation test.
without mask (THV and THV20). The derivative signals PIR
II. MATERIALS AND METHODS were used to calculate respiratory variables for all periods of
We studied six healthy volunteers between 25 and 39 test.
years of age, five of whom were men. All subjects provided Recovery periods are divides in three intervals: first three
informed consent and the study was approved by the minutes- REC3m and REC20_3m, 4th -6th minutes- REC6m
relevant ethics committee (CHU Grenoble). Breathing was and REC20_6m, last three minutes- REC9m and
recorded with a flowmetter Fleish head n°1 and differential REC20_9m. Respiratory variables: mean duration of
transducer (163PC01D36, Micro Switch) mounted on the respiratory cycle (Tt), inspiratory and expiratory times (Ti
face mask (dead space of apparatus was 60 ml) and with RIP and Te), tidal volume (Vt), mean inspiratory flow (Vt/Ti),
(Visuresp, RBI). End tidal CO2 fraction (FETCO2) was Ti/Tt ratio, minute pulmonary ventilation (Ve), tidal CO 2
measured using infrared CO2 analyser (Engstrom Elisa/Elisa fraction (FETCO2) and their variation coefficients were
MC). Subjects were recorded in semi-supine position at rest calculated.
– 3 min (REST), during voluntary hyperventilation at each
III. RESULTS
subject spontaneous respiratory frequency and recovery – 9
The values of respiratory variables (medians, quartiles,
minutes (protocol THVm); and successively at rest – 3
superior and inferior values) calculated for periods of
minutes (REST20), during voluntary hyperventilation at 20
performed tests (THV, THVm and THV20, THV20m), also
breaths/min - 3 minutes and recovery period (REC20) - 9
the significant differences determined with test Wilcoxon are
minutes (protocol THV20m). Subjects were encouraged to
represented on the figure n°1.
increase tidal volume in order to decrease FETCO2 by 1%
below the rest levels. These two protocols were repeated

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Fig. 1. Respiratory variables of hyperventilation tests recorded with and without mask (THV, THVm and THV20,THV20m)

Fig. 2. Variation coefficients of respiratory variables determined in periods of tests recorded with and without mask (THV, THVm and THV20, THV20m)

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The mask increases inspiratory times at rest (REST) and V. CONCLUSIONS

during second interval (REC6m) of test THV. During test The application of the respiratory inductance
THV20 the mask increases Ti at rest (REST20), tidal volume plethysmography provides more native breathing pattern by
Vt during the last 3min (REC20_9m) and minute ventilation excluding influences of the facial mask. It can be useful in
Ve during REC20_6m interval of recovery period. the study of breathing pattern in voluntary hyperventilation,
The variation coefficients (medians) of respiratory and its application is suitable in the study of breathing in
variables of tests (THV, THVm and THV20, THV20m), and anxious patients.
significant differences determined by Wilcoxon test are
represented on the figure n°2. The mask decreases variation REFERENCES:
coefficients of Tt and Te during REC3m interval and Tt, Te, [1] P. Calabrese, T. Besleaga, A. Eberhard, V. Vovc, P.
Vt/Ti and Ve during last 3min of recovery period (REC9m) Baconnier. Respiratory inductance plethysmographie is
of THV. The mask decreases variation coefficients Tt of the suitable for voluntary hyperventilation test. Conf Proc
second rest period (REST20) Ti/Tt during first three minutes IEEE Eng Med Biol Soc. 2007:1055-7.
of recovery (REC20_3m) and Tt, Ti, Vt and Ti/Tt during [2] A. Eberhard, P. Calabrese, P. Baconnier, G. Benchetrit,
interval REC20_6m ―Comparison between the respiratory inductance
plethysmography signal derivative and the airflow
IV. DISCUSSIONS
signal―, Adv. Exp. Med. Biol., 499, pp. 489–494, 2001.
Precedent studies describe influence of the face mask on
[3] R.B. Banzett, S.T. Mahan, D.M. Garner, A. Brughera
the respiratory variables [4], [5]: increase of the tidal
and S.H. Loring, ―A simple and reliable method to
volumes and ventilation, decrease of the respiratory rate. We
calibrate respiratory magnetometers and respitrace―, J.
found more differences between breathing with and without
Appl. Physiol., Vol. 79, pp. 2169–2176, 1995.
mask during recovery periods after voluntary
[4] J. Askanazi, P.A. Silverberg, R.J. Foster, A.I. Hyman, J.
hyperventilation tests. The changes between automat-
Milic-Emili, J.M. Kinney (1980). Effects of respiratory
metabolic and behavioural regulatory mechanism make these
apparatus on breathing pattern. J. Appl. Physiol. 48, pp.
period more sensitive to behavioural influences produced by
577–580, 1980.
the facial mask. The decrease of respiratory variability in the
[5] R. Gilbert, J.H. Auchincloss , J. Brodsky, W. Boden.
records with mask can be also explained by these
Changes in tidal volume, frequency, and ventilation
behavioural influences. The absence of differences during
induced by their measurement. Journal of Applied
voluntary hyperventilation periods can be explained by
physiology. vol. 33 no. 2, pp. 252-254, 1972.
domination of voluntary control of breathing.
The small dead space of the face mask and
pneumotachograph had minimal effect on the breathing
pattern, but it cannot be completely excluded.

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Heart Rate Variability: the Involvement of

Breathing Pattern (chest breathing, abdominal
breathing) and Anxiety.
Andrei GANENCO1, Victr VOVC1, Ion MOLDOVANU2, Svetlana LOZOVANU1
1
State University of Medicine and Pharmacy “Nicolae Testemițanu”
2
Institute of Neurology and Neurosurgery
Abstract- The relationship of heart rate variability to thoracic and abdominal components of breathing
pattern, as well as to slow paced respiration, was studied in healthy volunteers with different level of anxiety.
Subjects with high anxiety showed lower levels of heart rate variability, slow respiration increased the low
frequency component of HRV in both groups, chest and abdominal respiration reduced HRV.

Keywords- heart rate variability, breathing pattern, paced respiration

applied to calculate spectral power of RR intervals and

I. INTRODUCTION.
following values of HRV were calculated: power spectral
It‘s well known that heart rate variability (HRV) is a basic
density (PSD), absolute and normalized high-frequency (HF)
homeostatic parameter and some changes in this parameter,
spectral power, absolute and normalized low-frequency (LF)
especially its decreasing, can be a marker of possible sudden
spectral power (normalized LF and represent the relative
death at patients with heart diseases [1]. Also, it‘s known
value of each power component in proportion to the total
that abdominal respiration has a positive effect on the
power minus the VLF component) and LF/HF ratio.
organism, and pranayama (respiration used in yoga system)
Statistical analyses: t-Tests were used to assess the
is considered as physiologic one with great catabolic effect.
statistical significance of differences for HR power and its
There are even some methods of breathing training for
components in different conditions. Values are means ± SE
increasing HRV.
unless otherwise stated.
Otherwise, it‘s known that elevated anxiety of one person
associates with autonomic disorders and psycho-autonomic III. RESULTS.
syndrome, described in last century by germane authors [2] Subjects with high anxiety had lower values of PSD, as
and developed ulterior by F. Vein and his school. This shown in fig.1, and this difference was described in all 4
syndrome is considered as basic concept in present science tests under different conditions of breathing, as mentioned
of autonomic disorders. before. However, inside the group with low anxiety, the PSD
Interaction between thoracic and abdominal components didn‘t show any important difference between periods of
of the respiratory pattern also exhibits some interest [3]. recording. The opposite effect is seen in the group with high
Experimental studies on healthy people and patients which anxiety, PSD being decreased during abdominal and chest
show the involvement of respiratory pattern and its variants respiration, and increased during 6 per minute paced
(abdominal respiration, chest respiration, hyperventilation) breathing.
are very few.
The purpose of this study is to analyze heart rate
variability at different forms of breathing pattern and in
relation to anxiety level in healthy volunteers.
¤
II. METHODS. ¤
¤ *
The subjects were selected by screening with State-Trait ¤ * *
Anxiety Inventory (STAI) Spielberger. 12 subjects (6 males,
6 females, mean age 20.59±0.43) formed the group with low
anxiety (15-30 points), and 13 subjects (6 males, 7 females,
mean age 20.49±0.38) formed the group with high anxiety
(more than 45 points). ECG and pneumotachogram were
recorded using MP35 unit from BIOPAC Systems. The
recordings were performed in following conditions:
Fig. 1. Spectral power density in subjects with low (in the left) and high (in
spontaneous breathing (3 min), spontaneous breathing with
the right) anxiety during spontaneous, abdominal, thoracic and metronome-
limited thoracic movements (by belts) i.e. ―abdominal‖ guided breathing (* - p<0.05 for the comparison inside the group, ¤ - p<0.05
respiration (3 minutes), spontaneous breathing with limited for the comparison between the groups).
abdominal movements (by belts) i.e. ―chest‖ respiration (3 The main reason for low values of PSD in high anxiety
minutes) and paced breathing (guided by metronome) with group will be probably shorter RR interval (847±13 ms in
breathe rate 6 per minute (3 min). Simultaneously, end-tidal low anxiety group, 670±11 in high anxiety group), since the
fraction CO2 was continuously measured by the capnograph increased heart rate leads to smaller fluctuations in RR
MEC-2000 in order to maintain it at constant values. interval. Also, PSD had decreased during both abdominal
From ECG, heart period was calculated as interval and chest respiration, although heart rate didn‘t change.
between two successive R waves, fast Fourier transform LF was slightly elevated in subjects with high anxiety

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(41.74±2.3 vs. 18.06±1.28, fig. 2). During abdominal and LF/HF ratio followed the same changes as LF, was the
chest respiration, the values of LF didn‘t differ neither same during thoracic and abdominal breathing, and
within the group nor between the groups. During paced markedly increased during slow breathing in both groups
respiration, LF had increased in both groups, and this (fig. 4). No differences were found in LF/HF ratio between
situation reflects not an increased sympathetic discharge, but the groups.
an increased possibility for the same sympathetic neural
outflow to modulate the heart rate. *
*
¤
*
*

Fig. 4. LF/HF ratio in subjects with low (in the left) and high (in the right)
anxiety during spontaneous, abdominal, thoracic and metronome-guided
Fig. 2. LF in subjects with low (in the left) and high (in the right) anxiety breathing (* - p<0.05 for the comparison inside the group, ¤ - p<0.05 for the
during spontaneous, abdominal, thoracic and metronome-guided breathing comparison between the groups).
(* - p<0.05 for the comparison inside the group, ¤ - p<0.05 for the
comparison between the groups). IV. CONCLUSIONS.
1. The subjects with anxiety present lower values of
HF wasn‘t significantly different between spontaneous power spectral density, due to reduced mean RR interval
breathing and chest /abdominal breathing, but decreased 2. Slow rate respiration (6/min) increases the LF
significantly in paced respiration in both groups (fig. 3). In component of HRV, since LF component in this case is
low frequency respiration (< 9 breaths/min), respiratory modulated by both sympathetic and vagal activity.
frequency and low frequency overlap, and the RR variability
is modulated by both parasympathetic and sympathetic
nervous system, and both will increase the LF component of REFERENCES.
the HRV, leaving HF at low levels. [1] Task Force of the European Society of Cardiology and
theNorth American Society of Pacing and
Electrophysiology, Heart rate variability: standards of
measurement, physiological interpretation and clinical
use, Circulation, vol. 93, 1996, pp. 1043–1065
[2] W. Fhiele, Psycho-vegetative syndrome, Ment. Welt.,
vol. 1, 1966, pp. 9-13
* * [3] V. I. Minyaev, V. G. Davydov, The role of the thoracic
and abdominal components of the respiratory system
during hyperventilation combined with chemoreceptor
stimulation of various intensities, Human Physiology,
vol. 26, n. 4, 2000, pp. 451-455.

Fig. 3. HF in subjects with low (in the left) and high (in the right) anxiety
during spontaneous, abdominal, thoracic and metronome-guided breathing
(* - p<0.05 for the comparison inside the group, ¤ - p<0.05 for the
comparison between the groups).

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Optical Power Control Module

Andrei GRITZCO, Sergey ZAVRAJNYI, Andrei STALBE, Iurie NICA
Institute of Electronical Engeneering and Nanotechnologies „Dumitru Ghiţu”,Chişinău, MD – 2028
*
E-mail: [email protected]
Abstract – This article describes the optical power control module, of laser diodes, which is included in the
therapy installation using local hyperthermia. The function of this module is to produce and maintain, during
the entire duration of the therapy procedure, the stable optical power, which has an enormous significance in
efficiency of therapy using local hyperthermia.
Also the module obligations are: monitoring the laser diodes performance, which also plays an important
role in proper functioning of the entire system. This module can serve up to four laser diodes simultaneously,
is equipped with RS232 serial interface, necessary to control module via computer. For this purpose, was
prepared a computer program that allows the operator to install optical power level for each of the four laser
diodes and to monitor laser diodes efficiency.
The main element of this module is the microcontroller ATmega16, equipped with a periphery,
corresponding the requirements of given module

collect information about the temperature in the tumor

I. INTRODUCTION
region).
The principle of local hyperthermia is to create inside the
- optical power control module of the laser diodes.
human body at a certain depth of temperature (accurate),
- cooling system (its function is to evacuate the excess heat
necessary to destroy tumor tissue (~ 43.5 ° C).Temperature
produced from laser diode operation)
excess or insufficiency may even harder aggravate the
- power supply module (electric power for all sub modules
situation.
of installation)
In this project, the primary concept, was to develop the
Each of these sub modules meet the vital functions for the
device would allow the therapy of cancer, infectious diseases
normal functioning of the entire device.
with high energy infrared radiation, which practical has no
harmful effects on humans when compared with traditional II. THE DESCRIPTION OF THE OPTICAL POWER
therapy with roentgen rays (after which the patient passes a CONTROL MODULE OF THE LASER DIODES
rehabilitation period). Another advantage is that the device
does not need a specialized room (concrete walls, special The main function of this module is to create and maintain
clothing, dosimeters) and can be easily moved from one a certain level (set by the operator via computer) of the
place to another (it is quite mobile). Also construction of the optical power for laser diodes. The precision of the installed
device was designed so, that each module in case of damage level has a huge significance in terms of efficiency of the
to be changed in a short period of time and without great therapy using local hyperthermia, so the module is equipped
expense. with an optical power monitoring loop, which continuously
The installation is equipped with a set of high optical checking the actual optical power with the necessary optical
power laser diodes (full power ~ 4W), based on power (installed by operator) and in case of deviation –
heterojunctions InAlGaAs, with wavelength of emitted introduce the necessary correction.
radiation equal to 808nm. Each diode laser is also equipped Also one of the functions of the module is to monitor the
with an optical collimator to create a parallel flux, with effectiveness of the laser diodes to prevent they‘re damage.
minimal divergences. In order to avoid, due to overheating, These effects can occur in case, when the heating speed of
the damage of the intermediate tissues during the radiation the laser diode exceeds the speed of the heat surplus
penetration through the body and to focus all energy on the evacuation by the cooling system, which leads to lower
tumor, was designed a division of the needed flow in a optical power of emitted flow by the laser diode. Therefore,
smaller flows, which in the sum will have the same effect on the optical power monitoring loop (which role is to maintain
the tumor. For this, the laser diodes must be placed at certain a constant optical power), is to detect the decreasing of the
angles, chosen by the doctor, depending on tumor location optical power level, and if this occurs, to increases the
and state (depth, the distance to vital organs, the dose intensity of electric current which flows through the diode
required, etc.). laser, in order to restore the installed level of the optical
The installation is also equipped with RS232 serial power.
interface for data exchange with the computer. Through this
interface and main program, is handled the optical power of
the laser diodes, monitoring the heat fields (temperature
distribution in the tumor area), monitoring the efficiency of
the laser diodes (laser diodes operates in the normal mode or
begins to degrade). The program also records all thermal
field variations in a file for future analysis.
Fig.1 Laser diode thermal loop
Installation for therapy using local hyperthermia can be
divided into the following sub modules: The increase of the electric current intensity, therefore,
- thermal field monitoring module (the basic functions is to leads to further warming of the laser diodes (in case when

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cooling system fails to evacuate the exceeded heat) and expensive. Another method - use a large number of laser
respectively decreases the efficiency of the laser diode. A diodes, which have the same thermal effect on the tumor, but
such situation can be characterized as a "thermal loop". which will operate at a lower level of optical power, which
It is very important to avoid the entering of the laser diode would allow a longer period of operation of laser diodes.
in the "thermal loop" for several reasons: first of all to ensure
an effective therapy, and secondly - to avoid the damage of As shown in Fig.2, the module can be divided into three
the laser diodes (rather expensive). Therefore the monitoring functional blocks: digital block, analog block and photo
function of the laser diode efficiency (went in the thermal sensor.
loop or is functioning in normal mode) has a great Digital block provides the connection between computer
significance in the normal functioning of the entire and optical power control module, via the RS232 serial
installation for therapy using local hyperthermia. interface. Data frame transmitted to the control module
TD ~ A  Po  t (1) contains the information about the optical power, laser diode
where: address, however data transmitted to the computer (collected
• TD - laser diode temperature, during time interval Δt from the analog block) contains the information about the
• A - parameter that depends by the nature of the laser diode electric currents flowing through the laser diode (required
• Po - optical power of emitted flux of laser diode for monitoring effectiveness of the laser diode). The
• Δt - time interval, during which the laser diode emits software running on the computer analyzes the received data
radiation with optical power Po and operates according to the obtained results. Data received
As shown in relation (1), since the optical power level, at by the digital block (from the computer) are processed and
which operate the laser diode, is higher, then the work time sent to the analog block, through the 3-wire interface, which
should be less, to keep the diode at a temperature at which will be converted into an analog signal that will control the
the cooling system can serve it. Solving this problem can be: laser diode optical power.
equipping every laser diode with a powerful cooling system,
able to serve any heating level, but such a system is quite

Fig.2. Scheme - Block of laser diode optical power control module

Fig.3 Optical power monitoring loop and laser diode efficiency monitoring loop

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Functions of analog block are based on creating and basic element of the optical power monitoring module.
maintaining the optical power level introduced by the Photo sensor main function is to monitor the optical power
operator. Optical power level is transmitted via 3-wire of the laser diode (together with op-amp). The photodiode,
interface by the digital block to the digital-analog converter which is a part of the photo sensor, is connected in a
(DAC, component present in the analog block). DAC photoconductive mode, which reduces it parasitic capacity
converts the digital signal into an analog signal that is and increases the optical sensitivity, which, in this case, is
applied to non-inverting input of the operational amplifier very important. The R4 resistor also regulates the photo
(OA). OA, together with the power transistor T1, controls sensor sensitivity. The signal produced by the photodiode
the current flowing through the laser diode (directly and the resistor R4 is applied to the non-inverting input of
proportional to the optical power of emitted radiation, see the operational amplifier, component present in photo
Fig.4). OA, depending on the received electric signal at the sensor. Resistors R6 and R7 regulates the signal
inverting input (from photo sensor), increases / decreases the amplification factor. Capacitor C performs the function of
intensity of the electric current flowing through the laser filtering various oscillatory signals which are produced by
diode, therefore acting on optical power of the emitted parasitic capacity of the photodiodes or other devices in the
radiation. The differential amplifier, measures the voltage same room ( network noise: ~(50 – 60)Hz ). The signal
drop on resistor R2, which is directly proportional to the produced by the photo sensor is applied to the operational
electric currents flowing through the laser diode. This amplifier inverting input.
voltage is applied to the ADC input (component present in
the digital block).
So analog block, together with photo senor forms two
monitoring loops: optical power monitoring loop and laser
diode efficiency monitoring loop.
Optical power monitoring loop, continuously check the
laser diode optical power level through an operational
amplifier and photo sensor. Part of this loop are the power
transistor T1, which operates as the current supply for the
diode laser and laser diode itself, which according to the
electric current intensity flowing through it, produces a
coherent stream of infrared radiation with an optical power
well known. Dependence between the emitted radiation
optical power and the electric currents flowing through the Fig.5 Photosensor‘s scheme – block
diode laser is linear and direct proportional.

Fig.4 Dependence of the laser diode optical power of the electric current

The laser diode efficiency monitoring loop, as previously

mentioned, is intended to prevent the entry of the laser diode
into "thermal loop", which can damage it. The loop
continuously monitors the electric currents, flowing through Fig. 6 Monitoring laser diode efficiency
the laser diode. Measured by the differential amplifier, the
voltage drop on the resistor R2, is directly proportional to To achieve communication between the computer and
the electric currents flowing through the laser diode and optical power control module, was developed a protocol that
respectively with its optical power. The signal obtained at provides, together with RS232 standard, data transmission
the differential amplifier output is applied to the ADC input without distortions and losses. One function of the software
(component present in the digital block). The binary data, running on computer (except for data transmission and
obtained after analog to digital conversion, are transmitted reception) is to process the received data, regarding the laser
via RS232 serial interface to the computer, where they are diodes efficiency, with the following graphical display of the
processed and displayed by the optical power control module dependence between the laser diode optical power and
software. If the software detects a situation when the laser efficiency
diode has entered into "thermal loop" – stops local
hyperthermia therapy procedure.
In Fig.5 is presented the photo sensor block – scheme, a

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III. CONCLUSIONS REFERENCES

Within the installation for therapy using local [1] А.Ю.Кузьмин, Интерфейс RS232. Связь между
hyperthermia, was developed, optical power laser diodes компьютером и микроконтроллером, Москва, Радио
control module, able to monitor up to four laser diodes at the и Связь, 2004.
same time. Module operation was tested within the [2] J.G.Graeme, Photodiode Amplifiers: op amp solutions,
installation, obtaining accurate results in maintaining the Library of Congress Cataloging-in-Publication Data,
level of optical power, responsiveness (for switching power 1995
transistors rather than ~ 25us) and high sensitivity. As [3] P.Horowitz, W.Hill, The art of Electronics, Cambridge
mentioned previously, to avoid laser diodes entering into the University Press, 1980
"thermal loop" is proposed to provide them with more
powerful cooling system and also increasing the number of
laser diodes, which would increase the overall safety of the
installation for therapy using local hyperthermia.

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Photon Irradiation Device for Antimicrobial

Therapy
Iurie NICA1*, Leonid POGORELSCHI1, Eugen MAXIMOV1, Valeriu CEBOTARI1, Constantin
IAVORSCHI1,2, Vitalie BOLOGA2, Vladimir NAHABA3, Emilia ŢÎMBALARI3
Institute of Electronical Engeneering and Nanotechnologies „Dumitru Ghiţu‖, Chişinău, MD – 2028
Institute of Phthisiopneumology „Chiril Draganiuc‖, Chişinău, MD – 2025
3 State Medical and Pharmaceutical University "Nicolae Testemiţanu", Chişinău, MD – 2004
*E-mail: [email protected]
Abstract - A device for a procedure for preoperatively preparing patients with progressive drug-resistant
fiber-cavernous tuberculosis also for treatment of other diseases, as lungs and other organs is developed. The
device performed process of treating infected cavities and contains: mercury tube, focusing system for
selection of segment of the radiation spectral band 250-500 nm, optical guide with connectors and a puncture
needle. Use the tube with high pressure mercury vapor as a radiation source allows to obtain the broadband
photon radiation for treatment more efficient and for recovery time reduce. It also provides a substantial
simplification of the device and reducing its costs. The device was used to approve the method of treatment of
infected cavities by means of endocavitary broadband irradiation. In the experiments we used cultures of
Escherichia coli and Candida albicans. Effect of annihilation of bacteria colony is almost directly
proportional to the duration of exposure and complete suppression occurs within 2 min.

Institute of Tuberculosis ASM FR, where was developed the

I. INTRODUCTION
method of photosanitation of pulmonary cavities in fiber-
One of the most difficult issues of the modern medicine is
cavernous tuberculosis cases [2,3], which is the most
the combat against the infectiuos diseases. At the same time
dangerous clinical form of this disease from epidemiological
the problem of the increasing resistence of the infected
point of view . As noted in the published studies,
microorganisms against the most up-to-date antibacterian
photosanitation of lungs cavities reduces the number of
preparations (the chemotherapy problem), is becoming more
resistant and multi-drug-resistant tuberculosis forms, helping
urgent. Because of this we propose to develop a device for
to improve the situation of tuberculosis evolution overall.
photosanitation with ultraviolet C radiation of the human
The mechanism of DNA molecules modification consists
cavites populated with colonies of unspecific or/and
in forming in them, under the action of photons, of thymine
tuberculosis microflora. Ultraviolet laser technologies used
dimmers by saturating the covalent connections between two
in the treatment of destructive forms of tuberculosis begin
neighboring bases [4].
their history with the development and utilization of
ultraviolet laser with nitrogen as the working substance
(medical installation "Almiţin" with wavelength λ = 337 nm
developed in 1995 under the management of Nobel laureate
Academician Prokhorov A.M.). This installation has been
made in small series in Russia (Samara) and has been used
successfully in Central Institute of Tuberculosis (Moscow),
clinic Chytram (Indore, India) and University Hospital Fig.1 The model of DNA modification under the influence of ultraviolet
Blumfonten (South African Republic) on treatment of more radiation
than 1500 patients. Currently, this device is no longer To note, that speed of DNA destruction is very high.
produced. In the process of supplementary investigations Recently [5] has been demonstrated that the reaction of
have noted that the maximum photosanitation effectiveness dimerization of the thymine (pyrimidine C5H6 N2O2) under
of tuberculosis caverns occurs when using ultraviolet from the action of ultraviolet radiation takes about 1 pcs (10-12
region C (240-280 nm ), with the absolute maximum
sec). Acumularea acestor modificări de structură în ADN
efficiency for λ = 254.6 nm . From these considerations has
microorganismelor cauzează micşorarea vitezei de
been developed device "Amulet" with the wavelength λ =
reproducere a microorganismelor şi, deci, anihilarea lor.
266 nm . This wavelength is achieved by multiplying the
The researches performed demonstrates that for different
frequency of neodymium laser radiation λ = 1064 nm . Mass representatives of nonspecific microflora, lethal doses are
production of the installations with 266 wavelength has not different. Liveness and lethal doses at wavelength 248 nm
been made because of high cost and low power obtained in for 5 initial strains: Pseudomonas aeruginosa, Escherichia
the flow of radiation (5mW) [1]. coli, Enterobacter aerogenes, Klebsiella pneumoniae and
The main component of the installation "Maria" is KrF Staphylococus aureus are reprezented in Pic. 2[6].
excimer laser, which generates pulsed laser radiation with We mention the varied sensitivity of different strains at
wavelength 248 nm and frequency of 100 Hz . By using ultraviolet laser emission energy. The most sensitive strain is
an optical system, radiation is admitted to the end of a sterile 2
single-use optical fiber inserted through . an cavernous Staphylococus aureus with letal dose 3 mJ / cm , and the
pulmonary micro drainage. most resistant Enterobacter aerogenes – 7 mJ / cm 2 .
Namely this installation is currently used at the Central

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more efficient treatment and reducing the period of healing

the patient. The device for treating the infected cavities,
using wide band photon irradiation method consists of: tube
of mercuric steam 1, quartz condenser 2, the shutter 3, the
spectral radiation selecting device 4, optical connector 5,
optical guide 6, optical connector 7, the distal segment of the
optical guide 8, punction needle 9, power supply unit 13,
which through the power stabilizer 10 supplies tube 1, timer-
dozer 11 (which drives the shutter 3) and measuring device
of the radiation power injected into the optical guide 12,
photoreceptor 14 assembled with the optical connector 15

Fig.2 Dependence, dose - liveliness, at bacteriostatic action of laser

radiation of wavelength 248 nm, on the nonspecific microflora

How we see from dependence of the number of colonies

that survive the radiation dose of irradiation, for wavelength
2
248 nm , the absolute lethal dose is 8-10 mJ / cm .
In particular, we mention the absence in the specialty
literature, of the genetic modifications evidences of the
human body cells under the action of ultraviolet radiation C
[7,8]. Fig. 3. Block diagram of the photosanitation device

II. DEVICE FOR PHOTOSANITATION OF THE Using the tube with the high pressure mercuric steam as a
INFECTED CAVITIES OF THE HUMAN BODY radiation source allows obtaining a wide band photon
radiation, substantially simplifying and reducing the device's
The proposed objective is to perform the necessary cost.
investigations and developing a photosanitation device with III. IRRADIATION PROCEDURE AND RESULTS
ultraviolet radiation C of the human body cavities populated The device for treating the infected cavities with wide
by non-specific microflora colonies and / or tuberculosis. band photon irradiation method was made and used to
These investigations and the development of antimicrobial approve the method of infected cavities treatment through
irradiation devices are necessary because of the permanent wide band endocavitary irradiation method.
growth of the pathogenic flora resistance to antibiotics [9]. The experiments were performed in laboratory of medical
From all the information, that we possess, is not apparent diagnostic and laboratory of microbiology at the Institute of
the necessary of coherence ultraviolet radiation in order to Phthisiopneumology, virology and immunology at the
destroy the bacteria. Basically, as a radiation source could be Faculty for training doctors at Medical University "Nicolae
LEDs. We have developed and manufactured an irradiation Testemitanu" researching the in vitro the influence of the
module with LED T9F25C (Optodevice Co. Seoul., Ltd.) wide band radiation on the different bacterial strains. The
[10]. But currently the produced LEDs by (Seoul Optodevice radiation parameters have had the following values: optical
Co.., Ltd., Photon Systems, Inc. and others) which are power at wavelength 254 nm - 1mW, and in range 280-500
radiating in region C have an insufficient optical power nm - 15mW. In the experiments were used cultures
emission. Escherichia coli and Candida albicans.
From what is known, mercuric lamps have a very strong Were performed 10 inseminations and from obtained
sterilization action, the character of their radiation not being cultures were prepared suspensions following standard
coherent. Important is, firstly, the wavelength of the photon technologies. In Petri dishes with agar - blood have been
(i.e. energy), intensity and duration of irradiation. dropped 0.1 ml of suspension with a concentration 106
From these reasons, the device of fotosanare with microorganism in 1cm3 of solution. Petri dishes thus
ultraviolet radiation C of the human body cavities populated prepared were exposed to 10, 20, 30, 40 s and 1, 2, 3, 4, 5
by non-specific microflora colonies and / or tuberculosis, as min. Were irradiated sectors with 1cm3 areas, leaving the
a source of radiation serves the discharge in arc in the non-irradiated sectors for comparison between the exposed
mercuric tube at high pressure. This way, we eliminate the sectors. Petri dishes were incubated 24 hours in thermostat at
most expensive element from structure of the irradiation the temperature of 370C. The calculations were performed by
device - the laser / LED. The use as a source of the radiation an optical microscope with x100 zoom. The results are
the mercury tube at high pressure, allows more efficient presented graphically in figure. 2.
treatment method by increasing the band used in the process How is apparent from the presented results, the effect of
and achieve a device that generates the wavelength band
microorganisms annihilation depends approximately directly
250-500 nm with the possibility to select spectral segment of
the radiation. proportional to duration of exposure until, basically, total
The wide band radiation in addition to the pronounced deletion within 2 min. Not irradiated sectors are covered by a
bacteriostatic effect, exercise a stimulating action on dense layer of colonies of microorganisms.
microcirculatory processes in irradiated area, resulting at

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[2] V.G.Dobkin, M. A. Bagirov, D. R. Faizullin, G. P.

Kuzmin. Endocavitary ultraviolet laser irradiation in the
preoperative preparation of patients with progressive
fibrocavernous tuberculosis. Проблемы туберкулеза и
болезней легких, №2, 2006, стр. 25 – 28.
[3] О.В.Ловачева, И.Ю.Шумская, Н.Ф. Сидорова,
Г.В.Евгущенко, А.В. Никитин, Использование
эндобронхиального лазерного ультрафиолетового
излучения в комплексном лечении туберкулеза
бронхов. Проблемы туберкулеза и болезней легких
,№12, 2006, стр. 20 – 24.
[4] T. Douki, A. Reynaud-Angelin, J. Cadet, E.Sage,
Bipyrimidine photoproducts rather than oxidative
lesions are the main type of DNA damage involved in
Fig. 4 The dependence of liveness of the Candida albicans colonies and the genotoxic effect of solar UVA radiation,
Escherichia coli Biochemistry, 42 (30), 2000, pp.9221 –9226.
[5] Wolfgang J. Schreier, Tobias E. Schrader, Florian O.
Koller, Peter Gilch, Carlos E. Crespo- Hernández, Vijay
N. Swaminathan, Thomas Carell, Wolfgang Zinth, and
Bern Kohler. Thymine Dimerization in DNA Is an
Ultrafast Photoreaction Science 315, 2, 2007, pp.625-
629.
[6] http://genestho.ru/article2.shtml Лечение
деструктивных форм туберкулеза с помощью
эндокавитарного воздействия лазерным
Fig. 5 The irradiation results of Staphylococcus aureus bacterial colonies ультрафиолетовым излучением
grown on agar - blood (irradiation time = 15,45,60s and 2,3,5 min) [7] М.Г.Винокуров, Н.Н.Николаева, Н.И.Косякова, В.А.
Печатников , Действие ультрафиолета С на
These results are above those obtained through the лимфоциты и нейтрофилы периферической крови
monochromatic irradiation using laser device [1,2]. человека, Медицинская иммунология, N 3-4, 1999,с.
In conclusion, the method and device proposed, allow 10-18.
quick removal of the pathogenic microorganisms [8] И.Н.Рямзина, В.А. Черешнев, Влияние
populations from the wounds and infected cavities, rising - аутовенозного ультрафиолетового облучения крови
thus, the speed and efficacy of treatment. отдельно и с ацетилсалициловой кислотой на
This work is performed within the 09.808.05.05A project состояние гемостаза больных перенесших инфаркт
financed by the Supreme Council for Science and миокарда, Российский кардиологический журнал
Technology of the Academy of Sciences of Moldova №5 , 2003, c.72-75.
REFERENCES [9] Tim Maisch. Anti-microbial photodynamic therapy:
[1] http://www.aetechnologies.ru/dev/14-details.htm useful in the future? Lasers Medical Sciences 22, 2007,
Создание лазерного комплекса для лечения pp.83–91.
туберкулеза [10] [10] Nica Iu., Vieru S., Vieru T., Banari E. Modul de
iradiere cu lungimea de undă 255 nm cu fibră optică.
Salonul IV de Inventică şi Tehnologii Noi, Simferopol,
Ukraina, 25 – 27 septembrie 2008

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Temperature Monitoring System

Serghei ZAVRAJNYI, Iurie TIRON, Andrei GRIŢCO, Andrei STALBE, Iurie NICA
Institute of Electronics Engineering and Nanotechnologies "Dumitru Ghiţu"
Chisinau, MD 2028R.. Moldova, e-mail: [email protected]
Abstract – The multichannel temperature probe for studying the behavior of thermal fields is described in this
article. As temperature sensors used Chromel - Alumel thermocouples. Thermoelectric each thermocouple
(from 11mV to 13mV) increased its own amplifier to output voltage from 0 to 5 V corresponds to a temperature
ranging from 0 to 50oC. The optimal solution for this case was the use of two-stage amplifier based on low-noise
operational amplifiers. Data converting, data collection and data transfer to PC is based on ATMEGA16
microprocessor company Atmel. Signals from the amplifier module used for the analog inputs of
microprocessor. The microprocessor receives the amplified analog signals from each thermocouple, converts
them and transmits the data according to the protocol USART to the PC. USART pins are connected to the
MAX232 and ADM 485 transceivers. The system operates in accordance with the software application that is
based on data received from the COM port allows it to control the temperature of the object at certain points, as
well as using mathematical interpolation procedure to determine the temperature at other points of a
predetermined extended region. Multichannel temperature probe allows us to observe thermal fields in the
temperature range 0 ° C … 50 ° C up to 0.1 ° C.

- Temperature transducers
I. INTRODUCTION
- The data acquisition and transmission system
Bellow is described one variant of multi-channel
- Temperature monitoring software
measuring device of physical values, intended for use in
The system has 8 channels of temperature monitoring.
various complexes of equipment for scientific research
or control different processes. It is able to communicate with
2.1 Temperature transducers
the devices within same complex, through RS232 and
Temperature transducers are thermocouples of cromel-
RS485 standards. Setting up for measure the physical values
alumel type, which have coefficient of thermal sensitivity of
is performed by replacing the sensors and the corresponding
40 µV/°C.
correction function, stored in the microcontroller memory of
Thermocouples conductors are protected by a Teflon
the multichannel meter. In this article, the device is
hose.
considered as multi-channel temperature measuring
instrument for studying the behavior of thermal fields in the
amount of physical bodies, part of the research method of
local hyperthermia of malignant neoplasms.
As it is known that, one of the possible ways to combat
the cancer can serve the destruction of malignant tumors
cells with local overheating. Possibility of exercising of this
method is associated with the fact that, during the heating of
the body over 43 - 44 °C, is observed the destruction of
tumor cells while healthy are more stable to heat tissue
preserve the viability up to 50 °C.
Thus, it is strictly necessary to respect the two major
limitations: on the one hand, overheating should not exceed
the boundaries of viability of normal cells, on the other - the
temperature of the tissues should exceed 43 Ñ, because
insufficient heating only stimulates the growth of the tumors.
As can be seen, acceptable treatment range of temperatures
is narrow, about 5 °C. This imposes certain requirements on
temperature measurement accuracy - better than 0.1 °C. To
prevent localisation of the disease affected tissues in a region
with temperatures below 44 °C, is necessary to monitor the
heat dissipation and dynamics of its distribution, based on
simultaneous measurements of temperature in several
specific locations in the overheated region. Under these
requirements has been designed the described multi-channel
temperature meter.
II. TEMPERATURE MONITORING SYSTEM
The temperature monitoring system is intended to Fig. 1 Principial scheme of a signal amplification module from
monitor the temperature values in control points and thermocouple
construction of the temperature field. The system consists of
the following functional levels:

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The hose is covered with a mesh shield. The screen, in scheme of a two channel thermocouple signal amplifier
addition to the useful signal protective function from noise, module is shown in Figure 1.
serve as mechanical support, offering increased mechanical
strength conductors. The own low consumption of 2.2 The data acquisition and transmission system
operational amplifiers, 150µA, allows realization of an The data acquisition and data transmission system to PC
amplifier system which is powered from an independent is realized based on ATMEGA16 microprocessor, from
source such as a galvanic cell. Cold jonction of the ATMEL company. The signals from the amplifier modules
thermocouple are inside of the isothermal block with a are applied to the analog inputs of the microprocessor. The
compensaty diode. microprocessor reads the values achieved on each analog
In order to achieve amplification of the thermocouple pin, converts them and transmits digital data via USART
signal, in the temperature range of 0 ° C - 50 ° C, the output module to the computer. The device consists of four modules
voltage 0mV - 5000mV, is necessary to increase the of 2 amplifier channel each. USART pins are connected to
amplification factor up to 10V. Optimal solution for this case the MAX232 and ADM485 transceivers via 74HC4016
was serial adding of a another amplification stage based on digital keys. This type of connection offers selectable data
operational amplifier. Because integrated circuit have four transmission serial interface. With 74HC4016 keys can be
operational amplifiers, reasonable solution is to make two choose the RS232 or RS485 interface. Principial scheme of
parallel analogue channels on a single PCB board. data acquisition and data transmission module is shown in
Developed module has its own voltage stabilizer to avoid the Figure 2.
influence of supply and the digital circuits noise. Principial

Fig. 2. Principial scheme of the data acquisition and transmission module

2.3 The data exchange packet format field in the second byte is reserved.
Package for data exchange between PC and data The program consists in initialization section of the
acquisition system is composed of two bytes. In the first peripheral equipment involved in data collection process
(ADC and USART unit) and data transmission section.
Block - diagram of the microprocessor program shown in
appendix A.
2.4 Temperature Monitoring System.
The system represents a software application, which,
based on data obtained from the COM port, allows
Fig. 3. Data exchange packet format. monitoring the temperature of the studied objects at the
procedure determines the temperature on a previously
byte, the two most significant bits contain the peripheral defined domain. The domains on which is determined the
system address that is addressed computer. Three the least temperature field can have multiple configurations: Irregular,
significant bits indicate the channel number on which the Linear, Rectangle, Sector, Radial, and Cross
temperature is to be read. The remaining three bits and bit

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The program consists from functions for processing the measure with the distance to the calculated point at a
events from the main window of graphic elements, another certain power. Power exponent determines the smoothing
large group of functions are mathematical and graphical degree of the surface.
processing functions. We will focus, more detailed, on the
Also known as Shepard method (1968). Mathematical
last ones, giving them a greater interest.
relationships of this method are:
- Bicubic interpolation. Represents an extension of one-
dimensional cubic interpolation used for interpolation of
two variables function, which values are known from a
regular grid of points. The interpolated surface is
smoother compared to bilinear interpolation algorithms
or "Nearest-Neighbor interpolation" Mathematical
relations for the interpolation method are presented
below

where fi(xi ,yi ) is the function value in the control point, hi –

(1)
the distance between the calculated point and the control
point, wi – weight value for that control point.
The algorithm presented above is used to construct a
surface on a field where the control points are placed
(2) irregularly. Power parameter p takes the value of 2.8, chosen
(3) experimentally, providing a convenient smoothing of the
(4) surface.
(5) - Point representation in Cartesian and cylindrical
(6) coordinates. Depending on the type of the domain on
which is defined the temperatures field, is more
(7)
convenient to process data in Cartesian or cylindrical
- Ponderable interpolation. Represents an interpolation
coordinates. The interpolation occurs in Cartesian
method which allows the construction of a surface based coordinates for irregular, linear and rectangular areas
on control points which are positioned irregular. In type. For sectoral, Cross and radial areas type the
determining the function value in a particular point, each interpolation is carried out in cylindrical coordinates. The
control point contributes in a inversely proportional built field is visualized only in Cartesian coordinates

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Allows you to visualize the temperature field interpolated temperature 50 ° C corresponds white color. At the bottom
on the basis control points in real-time control. The observed side of the picture are presented the control tools of the
surface will have the height of the Z coordinate, and the three-dimensional image: rotation around the axes x, y, z,
point value will be proportional to the temperature at that vertical and horizontal image displacement, separated
point. On the right side of the image is displayed the colors scaling on x-y, and z. Using the checkbox "Solid Surface"
ramp fieacare correlated with the the temperature for each we choose the type of the viewed surface of temperatures
color. Temperature of 0 ° C corresponds the black color, field: as a continuous surface form or in a grid form

Fig. 5.„Temperature Field‖

Fig. 5.„Temperature Field‖

In the Figure 6 are represented graphs of the time multi-channel measuring instrument of physical
dependency of the recorded signals by thermocouples in magnitudes designed for use in various sets of equipment
one experiment on the heating of the inner regions of a for scientific researches or control of different processes. It
biological sample by the 808 nm infrared radiation. is able to communicate with the hardware complex, in
which is included, in the regime of serial code in a standard
RS232 and RS485. This allows increasing the measurement
channels by simply connecting to the installation of
multiple measuring modules. Setting up the measurement
of any physical value can be made by replacing the sensors
and the corresponding tabulation of the correction function,
stored in the controller memory of multichannel meter that
will monitor several physical values.
IV. ACKNOLEDGMENTS
The work was supported by the Suprem Council for
Science and Technological Development of the Academy
of Science of Republic of Moldova (Project 06.420.007A)
Fig. 6 Time dependence of the signals recorded by the thermocouples
REFERENCES
Blurring curves determines the resolution of [1] Х.П. Берлиен, Г.Й. Мюллер. Прикладная лазерная
temperature meter, ~ ± 0,05 ° C, which is satisfactory when медицина. 1997. М: Интерэксперт.
it is necessary to control the temperature with an accuracy [2] В.А. Григорьев и В.М. Зорин. Тепло- и
of 0.1 °C. массообмен. Теплотехнический эксперимент.
III. CONCLUSIONS Справочник. 1982.
The above-described multi-channel temperature meter, [3] D.Wyman and W. Whelan Basic optothermal diffusion
which allows to observe the thermal fields within the theory for interstitial laser photocoagulation Med. Phys.
temperature range of 0 ° C... 50 ° C through the 1994, 21, 1651-1656.
simultaneous measurement of temperature at several points [4] М.Л. Гельфонд. Фотодинамическая терапия в
on the studied area with a precision 0.1 ° C, is a options for онкологии. Практическая Онкология. 2007. Т.8.
№4
.

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Device for Testing of Biological Material

BELIC O.1, ARAMĂ E.2, ŞTEFANEŢ M. 1, IAVORSCHI A.3, PÎRŢAC V.3, BABUCI A. 1
Human Anatomy Department of State Medical and Pharmaceutical University ”Nicolae Testemiţanu”
Department of Biophysics, Informatics and human Physiology of State Medical and Pharmaceutical
University ”Nicolae Testemiţanu”
Department of Microelectronics and Semiconductor Devices. Technical University of Moldova.

I. INTRODUCTION
The conjunctive formations which stand at the basis of the
ligamentous apparatus of different organs and systems,
consists of dynamic structures which react promptly at
multiple factors of both the internal and external
environment. The structure of these ligaments and their
biomechanical properties are a reflection of the morph-
functional of the viscera in different periods of life, normally
and pathologic.
Considering the fact that the information concerning the
interest problem is not sufficiently described in the specialty
literature, we decided to make an analysis of the biographic
data about the biomechanical properties of conjunctive tissue
with similar structure with the ligamentous apparatus of the Fig.1. Device for testing of biological material
spleen.
The device is made of modules. The main one is the
Peritoneal coats, collected from bovines are characterized
microprocessor. His functions are:
by a high elasticity [1]. The average tearing force which goes
- directing the stepper motor;
to a square mm in cross section of the peritoneal slides is
- tensile force measurement;
equivalent to 6-7 kg. Their presence varies from 12-20%
- measurement of data and displaying it on the menu
against the initial length of the studied probes.
screen;
The extension degree and the tearing force of the aortic
- measurement of data and storing it in the memory.
wall diminishes with aging by 2-2,5 times [2]. The most
Sensor used for measuring tensile force is a tens-metric
extensible are the ascending and abdominal portions, less
resistive transducer in the shape of a balanced bridge strain
extensible - stick and descending thoracic portion of the
gauge Wheatstone. The exiting signal from the bridge varies
aorta.
proportionally with the tensile force. This signal has low-
Our data [3] states that the greatest force applied at the
voltage values – 20…30 mV, this is why it must be
extension (longitudinally determined), which can be
amplified with the help of an instrumentation amplifier. The
supported by the ligament‘s slide of uterus from the lot with
amplified signal is applied at the entrance of the module
the age from 41-48 years, is equal with 20,48±3,65 N. The
Converter Analog Digital from the structure of
necessary effort for the tearing of the implied ligamentus
microprocessor for subsequent digital processing.
diminishes with the age, reaching 7,21±1,7 N (after 67
Stepper motor is a synchronous motor type with apparent
years).
poles on both armatures. At the apparition of the command
Thus, according to the results obtained (4), and the error
signal on one of the stator poles, the rotor will move until his
values peak loads, caused by enlargement of the coronary
poles will be aligned in front of the opposite stator poles.
ligament of liver samples in all age groups of males (I (17-
This type of rotor rotation is basically from pole to pole.
35ani) -14.97 ± 1.3 N) (II (36-60 years) -16.83 ± 4.1 N), (III
Motor command is done electronically and displacements
(> 60 years) -15.68 ± 1.3 N), average values take precedence
are obtained for the well-known motor, which allows us to
over those indices for women taken (I (35ani 16) -12.93 ±
make strains of the ligaments for a specific length. The
1.7 N), (II (36-55ani) -12.90 ± 0.7 N), (III (> 55ani) -13.72 ±
microprocessor operates the motor coils using the drivers -
0.9 N), statistically significant differences have not been
controlled circuits for the excitation coils.
determined (p> 0.05).
The display device is designed to display the device menu,
II. STRUCTURAL SCHEME AND THE DESCRIPTION of the measured data and the device status.
OF THE DEVICE Command buttons are necessary for the navigation in the
The device has a color screen for displaying the data. The device menu, in manual movement of the mobile arm and to
internal memory allows saving the results for almost 80 start the measurements automatically.
measures, the connection with the computer allows The memory is necessary for the storage of data. During
transferring data, for their visualization as a diagram with the the measurements, values are saved at every step of tensile
help of some special software. strength selected by the user. Connecting the device to the
The external look of the device can be seen on Figure 1. computer you can copy data from the device database, can
process them using specialized program, view and print the
dependence of tensile force on length stretch.
The internal structure of the device is shown in Figure 2.

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 "Extension arm" - as the button is pressed to move the

mobile arm to the right;
 "Withdraw arm - the left button is pressed to move the
mobile arm to the left;
 "Automatic Mode" - the investigation takes place.
 In the middle of the page is displayed with case, force
(in Newtons) and length (in millimeters).
Fig.2.
1 – carcass of the device;
2 – the platform of the device;
3 – a step motor;
4 – threaded rod;
5 – movable arm;
6 – nut;
7 – metal mounting bracket;
8 – rod;
9 – stoper;
10 – strain gauge;
11 – immovable arm;
12 – determining sample clips;
The device for testing of biological material contains a
carcass (1), mounted on a platform (2), on which is placed a
step motor (3), the shaft of which is connected to a threaded
rod (4), on which is mounted by a nut (6) a movable arm (5). Fig.4. Home menu page
One end of the movable arm (5) is freely mounted on a rod III. INFORMATIONAL SYSTEM FOR PERSONAL
(8). On the platfrm (2) is fixed a strain gauge (10), connected COMPUTER
to a immovable arm (11). At the ends of the movable (5) and At the initial stage was in question that BelForce
immovable (11) arms are mounted two clamps (12) for information system to perform the following functions: data
fixations of biological material. acquisition from the device BelForce, backup personal
In automatic mode investigations over the biological computer in the local directory, the saved data editing
material, the step motor will make a movement of the (removing erroneous data and the immaterial), graphic
moving arm with the step selected by the user, after which it visualization of data in the form f (F) = Δl, where F - tensile
will perform tensile force measurement. Measured force force (N) Δl - stretching the sample (mm), removal of data
value will be displayed on the screen and stored in the from memory device, print the results.
internal memory device, and futher can then be transmitted
to the computer. At the same time seeking the maximum
force, which will break the force investigating the biological
material. During the detection of maximum force, the stretch
length value is also saved.
Investigation process is interrupted when you press
"Stop" or trigger switches to limit arm movement (Stoper).
After stopping the investigation process, the screen will
display the value of breaking force and length.
The menu allows the device to view the force and length
during the investigation, breaking force and length after
finishing the investigation, allows to set the step size and
record number in memory.
Navigating the menu is done with three buttons that are
placed underneath the display. Near each of these buttons are
displayed on-screen icon that signifie one button
functionality. In Figure 5 are icons that can appear for each Fig.5. Graphical user interface
button.
The program structure is simple and allows fast access to
all functions of the program, obtaining such an easily
accessible graphical user interface. The exception is the
graphics printing results, where the user can configure the
Fig.3. Icons used to represent function buttons
printer, sheet size and other options that are specific to
Home menu page is shown in Figure 4. different types of printers. It was created a graphical user
In the top of the page, the first display device status. interface shown in Figure 5.
Depending on the operation of the device will be displayed: In the process of making GUI Standard components were
 "Hold order" - does not perform any operation and the used programming environment Borland C++ Builder. For
investigation has not yet occurred; instrument panel component was used Toolbar1 TtoolBar
 "The results of measurement" - the investigation has class. Were added to the required number of command
ended and displays the results; buttons using New Button. Component was used in class
ImageList1 TImageList and icons have been added for each

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command button ImageList1 Add ... . After adding all the GUI components and their
Then the connection was made between the component configuration is going to be written a program code that will
and Toolbar1 ImageList1 ImageList1 Images using the perform all the functions and operations by default.
property, so it can display icons in buttons ImageList1
IV. CONCLUSION
surface. The buttons 32x32 pixel size is set to display icons
The developed device allows the accurate determination
normally.
of the strength and elongation of the sample of biological
To achieve the panel information component was used
material until the fracture.
Label1, Label2 Tlabel class has been configured to display
color and text size. Two components were added and REFERENCES
ImageList3 ImageList2 the necessary images were [1] Кузнецов Н.Н. Брюшина крупного рогатого скота и
introduced. препараты из нее как новый пластический материал
List of directories of records (tree form) was created with для медицинской практики. Дисс. на соискание уч.
the component class TreeView1 TTreeView, ImageList4 ст. д.м.н. Кишинев, 1958.
component was added and the icons were loaded for each [2] Фрунташ Н.М. Биоморфоз аорты человека.
directory and file in the list. Two buttons were added to the Кишинев, 1982, 176.
component control class TButton Button1 and button2. The [3] Belic O., Ştefaneţ M. Proprietăţi biomecanice ale
buttons can erase a file / directory, or all files / directories ligamentelor uterului. Curierul medical, 2006, nr2, 55-
simultaneously. 59.
To create a state panel was used component StatusBar1 [4] Catereniuc I. Morfologia aparatului neurovascular extra-
TStatusBar class that allows displaying textual information. şi intraorganic al complexului hepatoligamentar.
For graphical visualization of the status process has been Autoreferat al tezei de doctor habilitat în medicină.
used in class TProcessBar ProcessBar1 component. Chişinău, 2007.

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Advanced Potential of the Photolpetismograph

PPG-2 in the Non-invasive Vascular Diagnosis
A.SLOBOZEANU1, I.ZATUŞEVSKI2, A.CREŢU3, V. ŞONTEA4
1
Republican Clinical Hospital
2
State Medical and Pharmaceutical University ‖Nicolae Testemiţanu‖
3
Republican Center of Medical Diagnosis
4
Technical University of Moldova
Abstract – Advanced sensor device for shape analysis of the tissue-reflected mean single period
photoplethysmography (PPG) signals have been designed and clinically tested. The PPG signal shape reveals
individual features of the patient's cardiovascular state. Clinical studies of several patient groups (e.g.
diabetes mellitus, atherosclerosis obliterans, Reynaud’s syndrome) made it possible to specify components of
the PPG signal that are sensitive to the corresponding organic or functional pathologies. Comparison of the
right and left arm finger PPG signal shapes, for instance, appears to be an efficient tool for early screening of
unilateral atherosclerosis obliterans.
Index Terms – Photoplethysmography, optical bio-sensing, diabetes, atherosclerosis, Reynaud’s syndrome.

and slight fluctuations of the signal amplitude are possible.

I. INTRODUCTION
Many doctors prefer visual information (images or
Photopletismography (PPG) is a noninvasive method
diagnostic curve). To provide doctors with such visuals, the
which involves the graphic recording of the changes in the
Technical University of Moldova, Department of
volume of a body segment, closely related to the changes in
Microelectronics and Semiconductor Devices proposed a
the blood flow during the systolic-diastolic excursion.
photopletismograph (PPG-2). It provides the ability to detect
Photopletismography is a technique developed by Blazek
and acquire a signal sequence of 60 individual patients and
and Wienert in 1981 [1]. This technique, based on different
can specify the exact forms of the signal for further clinical
physical principles, has been applied in the clinical
analysis. The available internal memory allows the device to
evaluation and measurement of arterial and venous blood
input the data of up to 4000 patients into the database. This
flow.
data can be later transferred to a PC for further analysis.
The photopletismographic sensor consists of an infrared
The small size of the device and the fact that it is battery
light diode and a photodiode-strand. Emitted light penetrates
powered permits the use of the device for self-monitoring of
the upper layers of the dermis in the case where a part of it is
vascular status at home or during physical exercise, provided
absorbed and another part is reflected and captured by the
that the temperature requirements (22-25C) are satisfied and
photodiodes. Reflected light intensity, and therefore the
that the patient is in a calm state of mind.
electric signal produced by the photodiode will correspond
Below we wanted to demonstrate the capabilities of PPG-
to the volume of blood in the measured zone.
2 in the noninvasive diagnosis of cardiovascular diseases and
Photopletismography is used as a complementary functional
in the analysis of the wave-shaped pulsating blood flow.
method due to its capacity to highlight the early state of
stiffness or muscle spasm of arterioles and capillaries.
Comparing the signals from the right and left arms seems to
be an effective tool for an early detection of unilateral
obstructive atherosclerosis. Photopletismo-graphy
examination is easy to implement, however, it often involves
multiple nuisances which can lead to diagnostic errors.
Advances in microelectronics and computer technology
have opened new possibilities. PPG spectrum analysis
provides valuable information on the cardiac function, Fig.1. PPG signal form diagnosed at a healthy person
respiration, vascular and nervous system condition [2, 8].
PPG is easy and safe to use for express-diagnosis and early II. MATERIALS AND METHODS
detection of various cardiovascular diseases. For the purpose of this study we selected a group of
PPG waveform detected at the periphery may differ practically healthy persons, which gives us the normal
significantly from the one detected in the main arteries, and parameters of elasticity of the vascular system. Such
will depend on the strength of the vascular system. If the characteristics have been used in quantitative and qualitative
resistance is abnormal, which is often caused by assessment of signal parameters PPG assessed in clinical
atherosclerosis, diabetes or other vascular diseases, which trials with this device.
reset the narrowed vessels, blood flow velocity in the large Photopletismographic interpretation is based on the
arteries to small capillaries decreases dramatically. evaluation of certain quantitative and qualitative parameters
Hypertension leads to a complete loss of dicrotic peak when [9,13]. The quantitative parameters include: amplitude curve,
it reaches the periphery. Secondary peaks of PPG signals speed, time to the wave peak, and total dicrotic notch. The
could not be detected on the fingers of patients with qualitative parameters include: total wave morphology and
hypertension [12]. its components.
We should note that PPG signals are not strictly repeated

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Some signals measured initially at a group of persons are diagnostic criterion for assessing blood vessel occlusion
presented in Fig. 2. The signals were taken from the same (Fig. 5 b).
body part (tip of a thumb). Those monitored were practically
healthy. The following legend was used: male - A, G and O,
age 24-26 years, J - a man of 49 years, M - a woman of 56
years. Figure 2 shows clear differences in PPG signals
recorded from five healthy individuals. Dicrotic notch is
more pronounced in younger patients [13), which could be
interpreted as a good sign of vascular elasticity, compared
with older patients.
a

Fig.2. Different types of signals PPG recorded at a group of practically b

healthy patients. Fig.5. a - comparison of PPG signals from the fingers on both hands, in the
case of the subclavian artery occlusion, b - the angle ratio (slope) by signal
Our studies in 5 patients with diabetes mellitus have fully S left / S right
confirmed our hypothesis. All PPG signals recorded at the Reynaud‘s syndrome (RS) is a paroxysmal disorder of the
finger tips of these patients were bell shaped, with no peripheral circulation, located usually in the upper limbs,
secondary peak in the catacrota (Fig. 3). characterized by intermittent appearance of a bilateral and
symmetrical spasm of digital arteries, occurring when the
patient experiences cold or emotions, with the normal state
in other conditions. It is a rare disease, which is found
typically in young women (less than 40 years). The etiology
is unknown. PPG can provide additional information about
this disease [14, 15].
PPG monitoring was used to monitor vascular changes
during a physical exercise of a patient (L., 22 years) with
RS. PPG signal was recorded before and after the exercise.
Remarkable changes can serve as evidence of the nutrition of
Fig.3. PPG signals in 5 patients with diabetes the arm "trained" with improved blood. The results are
shown in Fig.6.
.The clinical trial in patients with atherosclerosis revealed
similar types of PPG signals. At a dose of nitroglycerin,
reflecting the pharmacological dilation of blood vessels a
secondary peak formation was observed. It is a sure
indication of an increased blood flow. The changes obtained
were shown in Figure 4.

a b
Fig.6. PPG signals taken from the fingers of both hands
before and after the tests in patients with Reynaud‘s
syndrome
a b
Fig.4. A – demonstrates the changes in patients with asymptomatic mild
III. REVIEW.
atherosclerotic changes, which have received a dose of nitroglycerin, B –
the time of the nitroglycerin-caused effect development characterized by The results presented and the analysis of the functional
T2/T1 signal and forming the secondary peak in the catacrota signal. It is a characteristics of the device confirmed the potential of PPG-
clear indication of an increased blood flow. 2 sensor, used in vascular diagnostic methodological
Thus we can see a clear time delay and broadening of the procedure and during the exercise test in the pre-clinical
signal on the right arm, compared with the left arm, which phase.
shows an increased vascular resistance and a slower speed of We have also noted other aspects of PPG signals recorded at
blood flow in the right arm. Therefore the angle ratio (slope) the finger tips which can serve as criteria for diagnostic and
by signal S left / S right could serve eventually as a dynamic screening:

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 Growth of the anacrotic phase of the pulse wave heart and respiratory rates by photoplethysmography
characterizes the resistance of the blood flow in vessels; using a digital filtering technique‖, Med. Eng. Phys., 18,
 General shape of the signals PPG: a bell, with no signs 365-372, 1996.
of reduced catacrota and dicrotic notch announces [6] Larsen P. D., M. Harty, M. Thiruchelvam et al, Spectral
various abnormalities of peripheral blood vessels analysis of AC and DC components of the pulse
(caused by diabetes mellitus, atherosclerosis); photoplethysmography at rest and during indication of
 Appearance and increase / decrease of the secondary anaesthesia. Int. J. Clin. Monit. Comput, 1997, 14: 89-
peak, assessed against a drug (e.g.: nitroglycerin) may 95.
be used to monitor the time of expansion / narrowing of [7] Nitzan M., A. Babchenko, B. Khanokh et al., ―The
blood vessels; variability of the photoplethysmographic signal – a
 Changes in the shape of the signal PPG, reached after a potential method for the evaluation of the autonomic
physical exercise or a physiological effort (blood flow), nervous system‖, Physiol. Meas., 19, pp. 93-102, 1998.
reflect the progress of the physiological state of the [8] Perez-Ocon F., A. Abarca, J. Abril et al., ―Optical
observed. measurement of cardiac rhythm using a personal
computer with telediagnosis possibilities‖, J. Biomed.
IV. CONCLUSIONS Opt., 6, No. 1, pp. 90-96, 2001.
Photopletismography with reflected light proved to be an [9] Spigulis J., U. Rubins, ―Photoplethysmographic sensor
appropriate tool for testing the prediction of the therapeutic with smoothed output signals‖, Proc. SPIE. 3570, pp.
outcome (e.g.: for the patients with high blood pressure, 195-199, 1998.
diabetes, obliterating arteriosclerosis and Reynaud‘s [10] Venckus G, J. Spigulis, ―Frequency filtering effects on
syndrome, etc.) the single-period photoplethysmography signals‖, Med.
Having reviewed research that focused on the PPG-2 device Biol. Eng. Comput., 37, Suppl. 1, pp. 218-219, 1999.
performance, we conclude that it offers the possibility of [11] Spigulis J., G. Venckus, ―Single-period
rapid and reliable estimates. photoplethysmography: a potential tool for noninvasive
BIBLIOGRAPHY cardiovascular diagnostics‖, Springer Series “Optics for
[1] Hertzman A. B. Photoelectric plethysmograph of the Life Sciences” OFLS-VI, Berlin (in press).
finger and toes in man. Proc. Soc. Exp. Biol. Med. 37, [12] Spigulis J., G. Venckus, M. Ozols, ―Optical sensing for
pp. 1633-1637, 1937. early cardiovascular diagnostics‖, Proc. SPIE 3911, pp.
[2] Ugnell H. Phototplethysmographic Heart and 27-31, 2000.
Respiratory Rate Monitoring, Ph. D. Thesis No. 386, [13] Ozols M., J. Spigulis, ―Acquisition of biosignals using
Linkoping University, 1995. the PC sound card‖, Proc. Int. Conf. “Biomedical
[3] Nitzan M., H. de Boer, S. Turivnenko et al. Power Engineering” (KTU, Kaunas, LT), pp. 24-27, 2001.
spectrum analysis of spontaneous fluctuations in the [14] Wouda A. A., ―Raynaud‘s phenomenon. Photoelectric
photoplethysmographic signal. J. Bas. Clin. Physiol. plethysmography of the fingers of persons with and
Pharmacol. 1994, 5 (3-4): 269-276. without Raynaud‘s phenomenon during cooling and
[4] Bernardi L., A. Radelli, P. L. Solda et al. ―Autonomic warming up‖, Acta Med. Scand., 201, pp. 519-523,
control of skin microvessels: assessment by power 1977.
spectrum of photoplethysmographic waves. Clin. [15] Engelhart M., H. V. Nielsen, J. K. Kristensen, ―The
Sci., 90, pp. 345-355, 1996. blood supply to fingers during Raynaud‘s attack: a
[5] Nakajima K., T. Tamura, H. Miike, ―Monitoring of comparison of laser-Doppler flowmetry with other
techniques‖, Clin. Physiol., 5, pp. 447-453, 1985.

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Complex device for recording and signal

processing of cardiac activity
Victor ŞONTEA, Anatolie IAVORSCHI, Valerii PAHOMI, Valeriu PÎRŢAC, Dmitri
ANGHILOGLU, Sergiu Railean
Technical University of Moldova
[email protected]
Abstract – there are described structural scheme of the measurement system and processing of
photopletismogram, interacting units, possibilities of software and interfaces in two modes of operation: the
pc and with a special modul.there are presented characteristics and technical parameters of the system.

Index Terms – Cardiovascular system, photopletismography, device, signal .

the final cascade to achieve an optimal level of input

signal at ADC, changing infrared radiation transmitter,
I. INTRODUCTION
applying a voltage (CDA) in the cascade amplifiers to
Besides electrocardiogram, one of the methods, for
maintain signal processing slow components at the
determining the physiology index of the human body is
desired level, digital signal processing, etc;
photoplethysmography – computerized method based on
 Interaction of Color display device;
recording and signal processing of the photoplethysmogram
 Reading and decoding data from touch screen panel that
wave. [1,2]
is on display – the determination of coordinates of the
The proposed system is assigned to the investigation of
points of interaction;
cardiovascular medical technology, the operating principle
 Making a menu-user interface extensive graphical
of which is based on the method of photopletismography
display due to large size touch screen panel;
wave. Photopletismography principle is reflection of
 Interaction with the power control unit – ensuring the
radiation (infrared radiation is usually used, but may be used
transition to sleep regime, provident power to all blocks
and another band of spectrum that would allow a good
of the device in active mode operating voltage level
penetration of skin coatings and independence of the
monitoring of battery charging;
reflected signal by other factors such as skin pigmentation)
 PC Connection – connecting the computer through the
from blood cells moving through the small vessels, under the
USB interface device can operate as a computer
skin. [3,4]
peripheral mode – photoplethysmography signal can be
Photoplethismografy recording and processing allow to
collecting and send directly to your computer , or read
obtain information about the state of cardiovascular system,
from memory and transmitted to the personal computer
the segmented blood pressure, detecion of blood vessel
only necessary data.
damage through screening large caliber method.
Data Base allows dynamic allocation of memory space for
its patients and signals. It can capture more than 65
II. STRUCTURAL SCHEME OF THE DEVICE thousands patients, each patient to 240 signals. Signal
The device is designed for ECG and duration can be adjusted from 1 minute to 24 hours, and
Photoplethysmography signal acquisition, its processing, duration of all signals is 40 320 minutes (equivalent to 672
computer data transmission, determining the signal hours or 28 days)
parameter, graphical display of heart rate on LCD color Analog site of the device consists of two symmetrical
display, storage of data and signals of the patient into the channels that process signal from two photoplethysmograph
database of patients, etc. transducers and one channel of ECG processing. Figure 2
The device is composed of several modules: the digital shows the block diagram of the analog part of the device.
module, the analog module, transmitter, LCD Display, SD
Memory Card and power control module (Figure 1).

Fig.1. Structural diagram of the device for recording and processing of the
ECG and photoplethysmogram waves

The functionality of the device is based on ARM Fig.2. Block analog scheme of the device
Microprocessor, with 32-bit architecture that works at the
clock frequency of 100 MHz. Its functions are the following: The device measures both fast component and slow
 Interaction with the analog module into a digital signal component of photoplethysmography, so the signal from the
conversion, changing the operational amplifier gain of sensor is initially separated into two signals: signal of slow

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component and signal of fast component of the window, designed to introduce a new patient database, is
photoplethysmography. the keyboard, similar to the personal computer (Figure 3).
The fast component of signal is first amplified in current
then dc component is removed by using a high pass filter
(Fig.2). Because the power supply of analog part is unipolar,
signal is raised to the „virtual gnd‖ of 1,5 V.
After this signal is amplified with a fixed amplification facto
r (Ku = 10) and highfrequency noise filtered through a low
pass filter.
To get the slow component, the signal from the sensor is
amplified in current and then the rapid component of the
signal is filtered using a low pass filter with cutoff frequency
of 0,5 Hz. After this, signal is applied to the inverting input
of a differential amplifier A2 with amplification gain 10. To
the non-inverting input of this amplifier is applied a voltage
from the digital-analog converter (CDA). This voltage is
necessary to maintain the signal voltage range from 0 to 2.56
V and exclusion of the amplifier saturation regime. Fig.3. Introducing a new patient window
Electrocardiograph signal (ECG) are gathered using three The patient's page can be accessed and the device
electrodes placed on the patient‘s body - two active database. Database interface allows us to navigate through
electrode (or warm) and a neutral electrode (or cold). The the list of patients to look for a particular patient in the
signal is amplified with an instrumentation amplifier A5, database, to remove a patient and to select a particular
after which the dc component is filtered using a high-pass patient.
filter with cutoff frequency of 0,05 Hz, and noise at
frequency above 100 Hz with a low-pass filter.
The fast and slow components of signal from output of
photoplethysmograph module and ECG signal is applied to
the inputs of a multiplexer, with which the microprocessor
selects the appropriate signal to be recorded. The analog
signal from the multiplexer output is applied to the
operational amplifier A6, whose amplification factor can be
adjusted by the microprocessor. Because of using digital
potentiometers are obtained 256 steps of the amplification
gain. This allows obtaining the ADC input signal with
amplitude that can be converted in large numbers without
quantifying losses and without the need for further scaling.
After amplification the signal is filtered by the noise
induced by power grid frequency of 50 Hz.
Getting data from analog to digital converter,
microprocessor continuously monitors the signal level. If the Fig.4. Browsing through the database window
signal amplitude is too low for a period of time, will made to On the page "Display" choose the desired signals to be
increase the coefficient of amplification, if too high - to viewed. It can be selected up to two signals. For this,
zoom out. Another action on the part of the device is press the squares that stand beside the name of each signal.
changing the value of analog voltage output digital-analog Clicking on these squares, each a check mark appears in
converter to minimize the slow component signal. them, which means it has been successfully selected, and the
The microprocessor also changes intensity of infrared right square is the abbreviated name of the signal. If the
radiation, which allows the transducer to adjust the patient was already introduced in the database, you can
properties of different patients. choose it to view previously stored signals. To compare the
The display of the device is an LCD Color, with signal obtained before and that obtained in time, choose a
resolution of 320240 pixels and 65 536 colors, which signal from memory and a signal from the sensor.
allows to display the time evolution of one or two signals Page "Graphics" is provided to view selected signals for
simultaneously, but also create a user interface, extensive display. Can be viewed one or two signals simultaneously.
menu, intuitive and easy to interact. Using the graphic With "Start" button will start collecting data and displaying
display combined with touch screen panel allows us to create on the display, the "Stop" will stop collecting data, and by
a device without many buttons, operator interaction with the using the "Memo." will store data in memory. If you select a
device being made by pressing with a special pen, called the signal from memory for display on this page we can place
stylus, directly on the Touch Screen panel, placed above the directly on the screen of photoplethysmograph basic points
display. Because of this, the menu consists of pages, buttons, and to calculate photoplethysmograph few basic parameters,
keyboard - similar to a personal computer, making it easier which can give some clues about the state of the
to access the menu for personal computer users. cardiovascular system.
User menu consists of four pages: "Patient", "Display", Page "Settings" contains the device settings: setting the
"Graphics‖ and "Settings." Page "patient" is intended to time, date, backlight, view memory status and the option of
work with the database, add a new patient into the database switching off the device. A fairly large part of the energy
or choose a patient previously investigated. At the bottom of

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consumption of the device has LEDs backlight. To reduce competitive with existing ones and can be recommended
the energy consumption of the device is provided for for the production and subsequent implementation in
automatically disconnecting the lights over a certain time health care.
after you last press a touch screen panel. Length of time it
ACKNOWLEDGMENTS
can be set by choosing one of values: 20, 40, 60 seconds or
This work was supported by the Supreme Council for
disconnect backlight.
Research and Technological Development of the Academy
of Sciences of Moldova under grant no 11.817.05.20A
III. CONCLUSION
The developed device allows the time analysis of
REFERENCES
electrocardiograms and photoplethysmograms, quality
[1] Р. М. Рангайян. Анализ биомедицинских сигналов.
parameters, allows to compare the visual signals and those
Практический подход. Москва, Физматлит, 2007.
collected previously made at the moment, allow to study
[2] R. Sam, K. Darvall, D. Adam, S. Silverman, A.
heart rate variability.
Bradbury, Digital venous photoplethysmography in the
The system has the following technical parameters:
seated position is a reproducible noninvasive measure of
 Number of channels – 2 channels of simultaneous
lower limb venous function in patients with isolated
recording of slow and fast components of
superficial venous reflux. Journal of Vascular
photoplethysmography and 1 channel
Surgery, Volume 43 (2006), Issue 2, pp. 335-341
electrocardiography;
[3] Nicolae Armencea, Victor Şontea, Andrei Bragarenco,
 Frequency Band – from 0.05 to 18 Hz (FPG) and Dmitri Anghiloglu, Valeriu Pahomi Sistem de achiziţie
hhhhhhhhhhhhhhhfrom 0.05 to 100 Hz (ECG); a semnalelor biomedicale, Proceeding of the 5th
 Signal sampling frequency – 500 Hz; International Conference on Microelectronics and
 Active mode power consumption – 0.6 W; Computer Sciense‖ Chisinau 2007 V II pp 24-27.
 Minimum operating time without recharging in active [4] Nicolae Armencea, Victor Şontea, Anatol Iavorshi,
mode – 16 hours; Dmitri Anghiloglu, Anatol Creţu. Identificarea
 Dimensions – 110X65X30 mm; parametrilor cantitativi a fotopletismogramelor:
 Weight 200 g. Proceedings of The 2 nd International Conference
The measurement and data processing of Telecommunications, Electronics and Informatics‖
photopletismograph has technical characteristics Chisinau, 15-18 may 2008. V I pp 159-164.
(price, size, number of functions performed, parameters)
high, .

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New Investigation Technologies of the

Cardiovascular System and of the Vegetative
Nervous System
V.SCRIPNIC1, V.ȘONTEA2, I.ZATUȘEVSKI3, A.SAULEA4, E.ZEMȚOVSKI5 , A.IAVORSCHI2,
V.PÂRȚAC2, V.SOCOLOV4, N.ALEXEEVA5
1
Medical Center of Social Rehabilitation; 2Technical University of Moldova; 3State University of
Medicine and Pharmacy from Moldova; 4 Free International University of Moldova,
5
Medical Pediatric Academy, Sankt Petersburg, 6Chuvash State Teacher Training University.

Abstract – Protecting and enhancing the health of the population is an important task for our country. Also
financial resources targeted to medicine are insufficient to organize the effective functioning of medical
institutions. In these circumstances is particularly important to equip the medical personnel with devices that
have high possibilities of early diagnosis, which would allow family doctors to establish a correct diagnosis of
health from the patient's first visit. On the other hand this will save human and financial resources by
optimizing the treatment process and the exclusion of laboratory and instrumental investigations which
repeats the information obtained by other methods.
Key Words – photoplethysmography, cardiovascular system, vegetative nervous system,

Fundamental investigations of the heart rate in healthy

I. INTRODUCTION
volunteers and in high performance athletes, at cosmonauts,
Computerization and automation of various diagnostic
performed by scientists V. Parin and R. Baevsky (1964-
methods in recent years does not surprise anybody, and
2009), A. Dembo (1984) E. Zemţovski (1984-2003), A .
allows ease of early diagnosis and improves doctor‘s work
Korkuşko (1987-2005), later continued by V. Scripnic and
efficiency. In our opinion, such as automated methods of
A. Saulea (1983-2010) showed that one and the same values
diagnosis as cardiointervalography (allows to establish and
of RR intervals can be interpreted as a result of the
to study the nature of links that exist between the heart and
oscillations of the length intervals between ventricular
the vegetative nervous system, the assessment of sinus node
contractions of the heart, different depending of it‘s
rhythm and function, assessment of various arrhythmias)
physiological or pathological nature.
photoplethysmography (allows to obtain information about
This means that formal assessment of the value of
the status of blood vessels and some parameters of central
frequency of contraction (FCC) and its deviation ΔRR =
hemodynamics) should be materialized in a portable
RRmax-RRmin, without taking into account the sinuous
diagnostic device. And usage of this device while
structure of the heart rate and the set degree of periodic and
performing physiological maneuvers should allow
aperiodic fluctuations, can lead to erroneous conclusions and
assessment of adaptive-compensatory reactions occurring in
serious mistakes [1,4,5]. This means that without
the human body.
knowledge of the spectrum of frequencies that belongs to the
The offer comes from a group of researchers, doctors,
heart rate, spectral forces of waves, also called respiratory
engineers, programmers united in a team in the Department
waves, slow waves (LF), very slow waves (VLF), the
of Microelectronics, led by Professor Victor Şontea allows a
physician cannot assess correctly the state of the vegetative
qualitative increase of the diagnosis by specialist doctor,
system, the sympathetic and parasympathetic activity and,
family physician. The same device can be used with success
ultimately, cannot correctly assess the adaptive capacities of
by sports medicine physicians during trainings, in scientific
the investigated patient which means that one cannot choose
laboratories that are concerned with investigations of health
the correct direction of therapy [1, 2, 6]. General knowledge
of humans with special working regimen, of pupils and
about self-organization of complex systems has been
students. It is proposed to the scientific opinion an original
formulated by Ilya Prigogine and Hermann Haken, who first
device that allows rapid, noninvasive assessment of the
described the operation of complex systems with feedback.
cardiovascular system and vegetative nervous system, to the
Proceeding from the principle formulated by N. Moiseev
abilities to
(1987) and based on the analysis of mechanisms of
to adapt to physical and psycho-emotional limited efforts
development of living nature reveals that: if there is more
and, based on these data, to establish the correct diagnosis.
than one state of a system (or process), i.e. a number of
The methodology of operation of this device is based on a
coordinated states, subject to the laws of storage, energy
theoretical and clinical foundation based on investigations
accumulation and existing links in the system, then in the
of the heart rate. The device is designed to record and to
human body is achieved that state, which corresponds to
measure the pulse wave allowing diagnosis of the condition
minimum energy dissipation or minimum increase of
of the patient's blood vessels, tracking and recording in real
entropy. Living organisms are subject to this principle [1, 2,
time the pulse heart rate and thus appreciation of the
3, and 7].
sinuous structure of the heart rate. The device was tested at
Also we must remember the principle of minimal
the Department of Functional Diagnostics of the Republican
constraint of any system, which was discovered by Le
Hospital, and Republican Medico-Social Rehabilitation
Chatelie-Braun, that allows anticipation of human body‘s
Centre.

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reaction to an external trigger, by obtaining a certain effect The operating principle is based on pulse wave
(the minimum time or minimum dynamic deviation) due to propagation and reflection, which is captured by a
effective change of the feedback signal (amplitude, or phootopletismographic transducer and processed by an
power) but also the characteristics of the object are kept original microprocessor using its own program developed by
[8.9]. These principles provided by synergistic can be used the engineers of the Department of Microelectronics.
successfully during treatment. This device allows obtaining the following parameters:
For the specialist, but especially for the family doctor, Statistical parameters of heart rate:
who is forced to go to the patient‘s home, it is very FCC – Frequency of cardiac contractions;
important to establish the status of the vegetative nervous RR med, Mo (mode) - the value of the RR interval is most
system and cardiovascular system. The proposed device can often encountered in a exract of RR intervals; Amo (mode
help establish more easily the state of the nervous system amplitude) or the frequency of tracing the length of RR
functional during the hyperventilation test, a procedure that interval that coincides with the Mo value calculated from an
takes only a minute extract of RR intervals; RR min, HR max, dX, CV,%,
The hyperventilation test provides performing of deep SDNN, RMSSD, NN 50count, pNN50%
breaths with a frequency of Spectral parameters of heart rate:
6 osc/min (5sec. inspires; 5sec. exhale) in supine position. HF; LF; VLF; spectral sum Σ; LF/HF; LF%; HF%.
Also the pulsogram is recorded. The largest spread between the integral parameters has the
Thus, a maximum and stable variation of the FCC is blood pressure index (IT) by R. Baevsky. The essence of the
obtained in healthy humans. This variation of the FCC is a above-listed parameters was demonstrated by R. Baevsky
normal reaction, called respiratory sinus arrhythmia, which (1997) using his own mathematical model of adjusting the
gives rise to respiratory waves in the spectrum of frequencies activity sinus node. After R. Baevsky, Mo characterizes the
of the heart rate and is caused by vagus nerve activity activity of the humoral chanel of rhythm regulation, AMo
(increased activity of the vague during expiration and a characterizes the sympathetic activity and ΔRR – the activity
decreased during inspiration, due to excitation and inhibition of the parasympathetic channel of the nervous system.
of the vague nucleus, which transmits signals through nerve In order to study the state of vegetative control of heart
pathways to the sinus node). In pathological cases associated rate in patients and volunteers were used rhythmographic
with vegetative dysfunction, this reaction with deviations of methods, including corellative rhythmography
the gaps between heart contractions changes. (scatterography) and intervalography.The research was
The developed device allows rapid and safe recording of performed based on VRC1 device.
the respiratory deviations of heart rate, by several methods: Hemodynamic parameters:
intervalography, correlative ritmography (scatterography). It AUD - Amplitude of the Anacrote Wave;
should be noted that the respiratory method can not be used IUD - Dicrote Wave Index ;
if the pulse is followed by palpation or auscultation. TRU - Time to Wave Reflection (dicrotic notch)
This device not only allows assessment of vegetative IUC - Ascending Wave Index.
status, but also of the sympathetic and parasympathetic
activity of the vegetative nervous system during execution of
III. THE RESULTS OF INVESTIGATIONS AND
test with hyperventilation. The doctor can assess and ensure
DISCUSSIONS:
vegetative reactions in the physiological limits of the test
Investigations made in the department of functional
given, a very important thing for athletes, convalescents with
diagnosis of Republican Clinical Hospital, in the Department
sedentary lifestyle and elderly.
of Physiology and in the Republican Center of Medical-
During the test with hyperventilation an increased
Social Rehabilitation have shown that normal activation of
parasympathetic activity occurs during exhalation compared
the parasympathetic system during the test with
with normal breathing and as a result FCC decreases (RR
hyperventilation occurs by increasing the duration of RRmax
interval increases), and during inspiration cute the
interval (0, 05 sec. ≤ RRmax ≤ 0.1 sec.), while the
sympathetic prevails, FCC increases and RR intervals
sympathetic system‘s - within the ranges of decrease of
decrease. Depending on the increase and decrease in RR
RRmin interval (0.05 sec. ≤ RRmin ≤ 0.09 sec.). Increasing
intervals we can talk about the activity of sympathetic and
the value RRmax> 0.1 sec. and decreasing RRmin> 0.09 sec.
parasympathetic systems and their functional status [5, 6, 7].
confirms the prevalence of parasympathetic activity and
sympathetic avegetative system, while lowering RRmax
II. MATERIALS AND METHODS <0.05 sec. and increasing RRmin <0.05 sec. show reduction
The study of the possibilities offered by the new VRC1 of their activity.
device proposed by the team of researchers from the Investigations carried out on healthy people and on sick
Department of Bioelectronic was made in the Functional people with heart diseases has allowed us to emphasize the
Diagnosis Department of the Republican Hospital, Head of physiological and pathological responses that characterize
Department, MD, Phd, Dr. I. Zatuşevski. Investigations were the activity of sympathetic and parasympathetic systems
conducted on 186 persons of both sexes, aged 18-68 years, from the the vegetative system. Pathological reactions are
with various pathologies of the cardiovascular system and 32 due to vegetative dysfunction.
practically healthy people, between November 2010 - April Depending on the sympathetic and parasympathetic
2011. activity report nine types of reactions were highlighted, of
With the help of HCV, a last generation portable device, which 7 physiological and 2 types of pre -pathological
one can obtain biological information to diagnose function reactions. The first 3 types of physiological reactions are
of the vegetative and cardiovascular system by characterized by normal parasympathetic activity, within
plethysmographic method. physiological limits (0.05 sec. ≤ RRmax ≤ 0.1 sec.).

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In the first case sympathetic activity is decreased, in the increasing);

second – it is normal and in the third - is increased. 3) paradoxical reaction of both sympathetic and
Vegetative activity in the first case is made predominantly parasympathetic systems (RRmax - decreases and RRmin -
by the parasympathetic system, in the second – due to the increases).
both rings: sympathetic, parasympathetic and in the third - Pathological reactions of the vegetative nervous system at
mainly due to the sympathetic system. the test with hyperventilation reveals the presence of the
The fourth, fifth and sixth case are characterized by high vegetative dysfunction, and early diagnosis will allow
parasympathetic activity (increased value RRmax> 0.1 sec.). starting of appropriate treatment.
Sympathetic activity is low (RRmin is <0.05 sec.) for case During the investigation of the objective status at sick
four, in the fifth case is normal (0.05 sec. ≤ RRmin ≤ 0.09 persons and healthy volunteers we have found different
sec.), in the sixth case is high (RRmin> 0 , 09 sec.). versions of the sympathetic and parasympathetic activity,
In case four and five the vegetative activity is due which subsequently, during the statistical processing,
predominantly to the parasympathetic system, and in case allowed the split the investigated in samples according to the
six – due to both systems: sympathetic and parasympathetic. types of rhythm disturbances which allowed to optimize the
The two types (the fourth and fifth) of heart rate are cases patient‘s stay in the hospital and increase of the efficiency of
where vegetative regulation is within the physiological treatment.
limits, but in case 6 there is a form of adjustment in which a
IV. CONCLUSIONS:
pronounced sinus arrhythmia appears and extrasystoles may
The algorithms used in the device VRC1 allows
occur, supra-ventricular migration of rhythm leader and
computerised processing , facilitating the diagnosis of
replacement impulses. So, high activity of both systems: the
various cardiac rhythm disorders in patients and assessing
sympathetic and parasympathetic leads to an arrhythmogen
vegetative disturbances (predominance or inhibition of
effect, that is why this kind of adjustment may be called pre-
parasympathetic or sympathetic) and the correct choice of
pathological.
treatment
The seventh, eighth and ninth type is characterized by low
The advantages of this device ensures reduction of
parasympathetic activity (increased RRmax <0.05 sec). The
diagnostic time and significantly increase its objectivity,
seventh type is characterized by low sympathetic activity,
and also assessment of disorders in blood circulation, the
the eighth type is characterized by normal sympathetic
changes taking place in the kinetic capacities of the heart and
activity and ninth type is characterized by high sympathetic
blood vessel tonic capabilities should ensure a certain flow
activity. The seventh can be characterized as a type in which
of blood.
the human body has very low adaptive capacities of both
The results of the investigations confirm the need to apply
systems: sympathetic and parasympathetic. This type of
the hyperventilation test, that allows objectivity of various
reaction can be called pre-pathological. Types eight and nine
arrhythmias and their division into three samples: functional
are characterized by physiological reactions, more due to
, intermediate and pathological, which allows to optimize
sympathetic regulation.
treatment and follow-up treatment in the dispensary system.
Usually, in case of normal regulation, physiological,
ensuring the execution of the test, to say, with
hyperventilation, or some other tests depends on the type of BIBLIOGRAPHY:
vegetative regulation listed above. For example, in case of [1] Baevsky R. Теоретические и прикладные аспекты
vagotonic regulation (when the vague activity is оценки и прогнозирования функционального
predominant), the vegetative activity is performed due to состояния организма при действии факторов
sympathetic system and in the case of the sympathetic длительного космического полета. М. 2005.
regulation - by the parasympathetic system and if Институт медико-биологических проблем РАН.
normotonic, they are equally active -sympathetic and [2] Дембо А.Г., Земцовский Э.В. Спортивная
parasympathetic - then adjustment is performed by both кардиология // Л-д. Медицина. 1989. С.464.
systems: the sympathetic and parasympathetic. [3] Коркушко О.В., Писарук А.В., Шатило В.Б.,
So, we can establish that between sympathetic and Лишневская В.Ю., Чеботарев Н.Д., Погорецкий
parasympathetic system there is a close interconnection and Ю.Н. Анализ Вариабельности Ритма Сердца
interdependence, which provides an adaptation to a wide (возрастные Аспекты), Институт геронтологии АМН
range of changes that come from outside and inside the body Украины Kiev, 2005
and the doctor can easily determine and distinguish the [4] Земцовский Э.В. Спортивная кардиология. - СПб.:
body's physiological functioning of the pathological. In Гиппократ, 1995. - 447 с.
vegetative dysfunctions pathological reactions appear during [5] Scripnic V. Capacităţile adaptative ale organismului
hyperventilation test, and we can establish which of the odată cu înaintare în vârstă // Chişinău, Pontos. 2009.
segments of the vegetative nervous system is unable to react 167 p.
adequately and therefore do not provide cardiac adaptation [6] Scripnic V. Posibilităţile de creştere a adaptabilităţii
to changes in external environment. organismului sub acţiunea vibraţiilor rezonante induse şi
In addition to the types of physiological, pre-pathological în condiţiile hipoxiei hiobarice naturale // Chişinău,
there are also pathological. There are three types of Pontos. 2008. 136 p.
pathological reactions: [7] Scripnic V. Norma în fiziologie. Compediul lucrărilor,
1) paradoxical reaction of sympathetic system (RRmin Ediţia a VI. Arad, România, 2002, p. 248-281.
during the hyperventilation test increases instead of [8] Haken H. Synergetic Computers and Cognition,
gradually declining); Springer, Berlin, 1991.
2) paradoxical reaction of the parasympathetic system [9] Haken Н. Synergetic, An Introduction, Springer, Berlin,
(RRmax during the hyperventilation test decreases instead of 1983.

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Millimeter Wave Nonthermal Therapeutic

Device Based on Parallel-Strip Technology
SAINSUS Iurie, RAILEAN Sergiu, ROTARU Anatol,
CONEV Alexei, RUSSEV Iurie, POSTORONCA Sveatoslav, SCERBII Denis
Institute of Electronic Engineering and Nanotechnologies “D. Ghitsu”
Academy of Sciences of Moldova, Academiei str. 3/3, Chisinau, MD–2028 Republic of Moldova
Abstract - This paper describes the therapeutic device developed at the Institute of Electronic Engineering
and Nanotechnologies ―D. Ghitsu‖ (IIEN). The device is based on the parallel-strip technology. This
technology is effective for the designing, testing, and subsequent manufacturing of low intensity microwave
generators to use in medicine, veterinary medicine, microbiology, etc.
The proposed device differs from those developed and used previously by the fact that it combines a number
of known and new methods for elaboration, which prove this device with new properties.
We do not use a waveguide (metal mechanical device) in the generator-module as the basic working
environment of the active elements (generators), instead, we use a plate with parallel stripes. The plate with
parallel strips contains two substrates, but the passive elements, such as inductances and capacities, form a
composite circuit, where the active elements (transistors, diodes varicap, etc.), form an auto-oscillating system
that generates microwaves.

which can mention:

I. INTRODUCTION
- Gunn diodes, used in domestic appliances, are of
Results and analysis of multiple publications on the issue
Russian production. these items fall under the restrictions
clearly demonstrates that the applied possibilities of
there, relating to prohibiting the export of components,
UEMA in various fields of medicine, biology, food
which can be used in the military.
industry, environmental protection, industrial technology
- Poor reliability of Gann diodes. These elements are
began to be conceived according to its real value only in
used in military systems such as rockets "air-air", therefore
recent times. It was built an impressive volume of
their lifetime is small - a few hundred hours. This was
empirical results based on which they were established the
confirmed by the large number breaks of Gunn diodes,
overall limit a series of unique phenomena: the benefic
used in appliances generator model of UEMA devices.
resonant influence to all living organisms of non-ionizing
- the frequency of oscillations Gunn diodes is very
electromagnetic waves with very low non-thermal intensity
narrow and larger deviations can be made only by means of
(UEMA) (under 10 mW/cm2) in some segments of the
mechanical processes which cannot be easily handled by
extremely high frequency bands (EIF) (wavelength 4.9,
the CPU.
5.6, 7.1mm) has a universal character; UEMA radiation
That is why our first decision was to develop a
interaction with living objects has not a thermal nature, but
millimeter wave generator using techniques that allow the
wears a specific information character for all bio-medical
generation of very high frequency oscillations without
systems [1,2].
using Gann diodes.
The device described has been called "DVG-001" and
was developed within the institutional project 06.408.027A
"Devices and methods for irradiation of living matter and II. THE TOPOLOGY OF THE GENERATOR
the study of millimeter-wave-induced biophysical effects" Figure 1 shows the topology of the first variant of the
(scientific Academician Dmitry Ghitu). plate with parallel stripes, designed to manufacture a
The device contains a number of original techniques. sample layout generator in laboratory conditions.
Projects of the manufacture of non-thermal millimeter
wave generators (UEMA) have started the design of
generators that used Gann diodes. This concept was chosen
because of the use of Gann diodes in construction of analog
devices produced in Russia and Ukraine in the late XX
century [3].
Priorities Gann diodes are well known: - Simple
construction.
- Techniques that are well described in literature.
Fig.1. Topology parallel plate strip
- A very simple power scheme.
- A very small number of elements used in construction. The plate dimensions are 58.600 x 28.600 mm; the
At the same time we used millimeter wave machines, material used is 0.500 mm thick sapphire. The plate was
developed and manufactured in the Institutional and State designed to be produced in laboratory conditions by
Programs at the Institute of Engineering and Computer electroplating method.
Science "D. Ghitu" ASM [4,5], as well as devices showed Output frequency oscillations are connected to "Iesire"
produced Russian Federation, that showed a number of terminal, which is a hole in which it engages a probe,
shortcomings related to the use of Gann diodes, among which is an antenna that transmits output frequency

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oscillations in the waveguide. Waveguide is a filter because - Enlargement of the frequency band amplitude modulation
the frequency fluctuations that are lower than the critical up to 400Hz in comparison with 10Hz to 8Hz and 16Hz,
frequency will not pass through the waveguide. The - Frequencies can drift very high frequency
waveguide technology has been used in the construction of electromagnetic waves with ± 15% of center frequency to ±
millimeter wave generator with Gunn diode. 2%
The perimeter of the plate is composed of a layer of - An 8 hours lifetime on battery (in the autonomous
copper joined with the bottom surface unit (grounded). regime) and to charge the battery without removing it from
This area is connected to the common terminal "-" of the the device.
generator voltage supply and the frequency adjustment is An original program, which was inserted into the
made to the diode voltage multiplier. The points where "+" microprocessor memory, handles all processes. Language
is applied are shown on Figure 1. We can see some lines on used to indicate the working modes is Romanian.
the drawing that can be grouped by thickness into three The device was named "DVG - 001" in honor of
categories: flat, medium and narrow. Flat lines represent Academician Dmitry Vasilyevich Ghitu, under whose
the capacities, implemented by parallel stripes technology. leadership have started work.
The medium lines represent are the one with calculated Device "DVG-001" represents a case in which a supply
characteristics (impedance), and narrow lines represent and control board is installed, which is connected to two
inductances, made using parallel strips technology. separate boards (routing board and mode board) and work
with the indicator system. The casing is connected to a
device, which is coupled with very high frequency
III. GENERATOR FEATURES
generator. Supply feed can be easily removed, if is
Among the basic features UEMA generator can be
necessary to work in autonomous regime.
mentioned:
A full documentation of implementation was developed
1. Frequency band has a generator:
that allows duplicating the device to a specialized
- Not narrower than (40-45) GGZ;
production enterprise.
- Not narrower than (50-55) GGZ;
In Fig. 2 we have illustrated the exterior of the
- Not narrower than (60-65) GGZ.
appliance.
2. Maximum generator output power density, measured at a
distance of 2 cm
- not more than 10 mW / cm ² (10 x 10-3 W / cm ²)
3. Minimum power density generator output, measured at a
distance of 2 cm
- not more than 5 ηW / cm ² (5 x 10-6 W / cm ²)
4. Materials used in preparing the generator - not limited
5. Generator dimensions - we are limited, but to satisfy the
conditions to be easily held in hand
6. Weight - no more than 0.5 Kg
7. Maximum power absorption of a generator - no more
than 1.0 W
Power supply - not more than 48V (for security reasons);
Maximum current work - in accordance with the terms
"Caietul sarcinii".

IV. DESCRIEREA APARATULUI TERAPEUTIC

DVG-001
The construction of this device were used known
techniques, such as:
- Parallel stripe Technology without the use of Gunn
diodes. Fig.2 the exterior of the device ―DVG-001‖
- ATMEGA8 microprocessor as a control device,
- Use as an indicator a matrix with almost zero current As shown in the drawing, 6 buttons are placed on the
consumption, control panel, grouped into two groups and a power
- Use Li-Ion battery as a power source to the system indicator. The case is coupled to the power network with
working autonomously the supply feed 2 and generator 3 is connected to the case 1
- Use a battery charging device and, simultaneously, the through a connecting wire. For the first time a millimeter
power of the system operating mode of the industrial wave receiver is used (Fig.3), which receives the
network. oscillations of the generator unit and which is executed on
Each of these processes themselves are not new, but two mixing diodes, united into a bridge. This technique has
used simultaneously in one device, gave it a range of new allowed compensating the change of diode parameters with
properties that allow us to count this as one of the original temperature and high reliability of measurements.
device. As we can see in figure 3, the construction is a
These techniques have allowed us to receive the waveguide design, in which two diodes 8 are installed, one
following priorities in comparison with Russian equipment of which is the detection diode and the second is used as a
and ASM IIETI developed in previous years: compensation diode for the environment temperature.

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In Fig. 4 is represented the assembly design of In Fig. 5 is the image of power and control board on
millimeter wave generator, on which we can see generator which we can see a Li-Ion battery, power adapter and
board (2), a power plate, the waveguide (6), the housing microprocessor.
(10) and the wired connection (3).

Fi.g.6 The picture of the generator connected to supply and control plate
of the „DVG-001‖ device

In Fig. 6 is shown how the construction of the generator

Fig.3 Wave receiver exterior and how the generator is coupled to the control board and
power supply.

Fig.7 The indicator of the „DVG-001‖ device

V. CONCLUSION
Fig.4 construcţia generatorului The main tests that the "DVG-001" device has
undergone showed that the construction is reliable and
complies with specifications. Frequency deviation versus
time and temperature are within the required power level
and the deviation at the ends of the band of frequencies is
small.
Device "DVG-001" can be recommended for
curative procedure at medical, veterinary, microbiology
etc. And bring an extra boost in research devoted to
one implementation of millimeter non-thermal wave
radiation therapy, which practically has no adverse
effects or consequences characteristic of drug therapy.

Fig.5 The supply and control plate

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REFERENCES ПОСТОРОНКА, С. Разработка

[1] ROTARU A. „ Metamorfozele utilizarii aparatelor экспериментального комплекса для
UEMA in medicina‖. Akademos, №4, 2008, воздействия миллиметровыми волнами на
pag.57-60. живые организмы. В: III Евразийский конгресс
[2] „Microunde‖, MAGHIAR TEODOR. BONDOR по медицинской физике и инженерии
KAROLY, CĂLUGĂREANU MIRCEA, МЕДИЦИНСКАЯ ФИЗИКА - 2010, Москва,
BREBEANU DUMITRU, Editura Universităţii din 21-25 июня 2010 г. Сборник материалов, стр.
Oradea, 2003. 228-230.
[3] Падалко В.Г., Грищенко С.Г., Зубарев В.В., [5] SAINSUS, Iu.; ROTARU, A.; CONEV, A.;
Ноговицин А.В., Николаенко Ю.Е, Чмиль В.М., RUSSEV, Iu.; POSTORONCĂ, S.; BABAC V.;
Босый В.И. «Концепция развития СВЧ PIATÎGHIN, S. Generator de microunde. Brevet
полупроводниковой элементной базы в de invenţie MD 268. 2010-08-31.
Украине», Украина, Киев, Минпромполитики, [6] JOVMIR Vasile, ŢÂBÂRNĂ Gheorghi, ROTARU
НПП «САТУРН», 1999. Anatol, DARIE Valentina Metodă de tratatment
[4] САИНСУС, Ю.; РОТАРУ, А.; КОНЕВ, А.; al plăgii postoperatorii după mastectomie, Brevet
РУССЕВ, Ю.; ПЯТЫГИН, С.; БАБАК В.; . de invenţie 2009 MD Nr 3557,

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Obstructive Sleep Apnea: Biomedical Devices

for Treatment
Victor VOVC
State Medical and Pharmaceutical University “Nicolae Testemitanu”, Chisinau, Republic of Moldova
Abstract: The review of biomedical devices for Obstructive Sleep Apnea (OSA) treatment is presented.

Traction of tongue forward does not permit the obstruction

I. INTRODUCTION
of airway by the base of tongue.
Obstructive sleep apnea (OSA) - a condition
These oral appliances are indicated in the treatment of
characterized by the presence of snoring, recurrent upper
snoring and mild-moderate OSA [4].
respiratory tract collapse at the level of the pharynx and the
The treatment of OSA by a continuous positive
cessation of pulmonary ventilation during persistent
airway pressure (CPAP) The method of OSA treatment
respiratory effort, decreased blood oxygen levels, sleep
by creating a continuous positive airway pressure (CPAP)
fragmentation and excessive daytime sleepiness [1].
was proposed by Sullivan CE et al. in 1981[5]. The
The basic marker of obstructive sleep apnea is a cessation
mechanism of CPAP-therapy action is relatively simple. If
of nasal-oral flow for 10 seconds or more, with persistent
the airways a little "blow up" during sleep, it will prevent
respiratory effort, which is due to collapse of airway at the
its collapse and remove the main mechanism of the disease.
level of the pharynx. In case of incomplete airway
To create a positive pressure uses a small compressor,
obstruction appears hypopnea - respiratory event with a
which delivers a constant flow of air under a certain
partial reduction of nasal-oral flow, combined with falling
pressure in the airway through a flexible tube and nose
oxygen saturation not less than 3%.
mask. It is also advisable to use a heated humidifier, which
The prevalence of OSA is 5-7% of the total population
provides heating and humidifying the incoming air into the
older than 30 years. Severe disease affects approximately 1-
airways.
2% of this group of individuals [2]. In persons older than 60
Devices for CPAP-therapy. An important aspect of
years the frequency of OSA increases significantly and is
CPAP-therapy is its hardware. The success of treatment
about 30% of men and 20% in women. In persons older
depends on how efficiently and effectively will operate
than 65 years the incidence may reach 50% [3].
medical equipment. There are a large number of models of
The mechanism of airway obstruction is as follows.
CPAP-apparatus.
When the person falls asleep there is a gradual relaxation of
According the last review [6] treatment with positive
the muscles of the pharynx and increased mobility of its
airway pressure in European countries is undertaken with
walls. This leads to a complete collapse of airway and
CPAP (in all countries) or APAP (95.2%) devices.
cessation of pulmonary ventilation. Despite of it respiratory
The basic unit with no additional features. The
efforts continue, and even intensified in response to growing
apparatus is a compressor, which feeds into the airways
hypoxemia. Acute lack of oxygen leads to a stress response
constant given volume of air per unit time. In case of
associated with activation of the sympathoadrenal system
system integrity and constancy of its volume pressure
and the rise in blood pressure. The afferent information
created by the apparatus would remain stable. However, the
from various organs and systems reaches the brain and
breath is a dynamic process associated with the cyclical
cause a partial arousal. The brain regains control of the
increase (in inhalation) and decrease (in exhalation) of the
pharyngeal muscles and open airways. In severe cases there
system volume. Accordingly, during inhalation is an abrupt
may be up to 400-500 pauses in breathing per night.
drop in pressure in the system, and during exhalation - its
II. BIOMEDICAL DEVICES USED IN OSA rise. The amplitude of oscillations can reach 2-4 cm of
TREATMENT water column. This negatively affects the dynamics of
Oral appliances for OSA treatment. breathing, especiall.
There are two categories of oral appliances used for during exhalation against a pressure jump. In addition, if
OSA treatment: mandibular advance devices and tongue during the treatment occurs much leakage from the mask, it
retaining devices. can lead to a significant drop in pressure and reduce the
Mandibular advance devices. The main mechanism of effectiveness of treatment. Thus, this type of equipment has
action is the forward displacement of the lower jaw and a several disadvantages, which may reduce the effectiveness
corresponding increase in the anterior-posterior size of the of treatment.
pharynx. The use of some devices requires operation of Device with therapeutic pressure compensation. This
dentist, as they are fixed to the teeth with special clamps. type of devices is upgrade by introducing a pressure
There are more than simple modifications, made of special compensation function. In the apparatus is installed a
polymer-like mouthpiece for the boxer. The device is sensor that monitors in real time the pressure in the
heated in water and becomes soft, then mounted on the breathing circuit (the tube), as well as low-inertial engine.
upper jaw and lower jaw is closed being displaced forward. When the pressure drop (on inhalation), the device
The device hardening and at subsequent installation in the accelerates the engine speed and maintains proper
mouth moves the lower jaw anteriorly. therapeutic pressure. If it is a jump in pressure (at
Tongue retaining devices. These kinds of devices are expiration), the device slows the engine speed, which also
suction devices placed between upper and lower teeth. The ensures the stability of the pressure.
tongue is pulled forward by this device during sleep period. In the event of a leak from under the mask unit detects a

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drop in pressure accelerates the engine speed and case of pressure increasing as a response to central sleep
compensate for the leak. In addition, the presence of apnea may experience a paradoxical reaction in form of
pressure compensation is important, if a person happens in worsening of the central breathing disorders. Most CPAP
locations at different altitudes above sea level. In high machines are not able to differentiate obstructive and
altitude environment the air becomes more rarefied and central sleep apnea. To avoid excessive pressure in
compressor of the unit should operate at a higher rate to response to central respiratory failure, in the apparatus
maintain the proper therapeutic pressure. provides the ability to install a certain value therapeutic
Thus, this type of devices tuned to the rhythm of breath any pressure above which the device stops responding through
person and during the entire respiratory cycle is maintain increase in pressure in the development of apnea of any
constant pressure without significant discontinuities, which origin. This parameter is usually set at 10 cm of water
improves the subjective acceptability of treatment. In column. So, if sleep apnea developed when therapeutic
addition, the devices of this type provide a stable pressure was, for example, 7 cm of water column, the unit
therapeutic pressure regardless of the occurrence of leaks in will increase the pressure. If apnea developed at the
the breathing circuit or significant drops in barometric therapeutic pressure of 11 cm of water column, the
pressure. machine it will not respond. It is clear that the algorithm
Device with auto-adjusting of therapeutic pressure can not always ensure adequate treatment of pressure
and memory function (APAP). change in the patient, especially if it combined obstructive
There were elaborated devices that provide automatic and central respiratory disorders. In the some apparatus is
selection pressure in real time - the so-called Auto-CPAP used a new technology that allow, with sufficient accuracy
or APAP devices. These devices use sophisticated to differentiate obstructive and central respiratory
algorithms for automatically adjust the therapeutic disorders. It is based on the detection of cardiac oscillations
pressure, depending on the detected disordered breathing. in the respiratory circuit. The heart's contractions are
The adjustment of pressure in real time is necessary for transfer to the lung tissue, which in turn creates a small
adaptation to a change of therapeutic pressure as a function pressure spikes in the bronchi and trachea. During the
of body position and sleep stage. Deep sleep, and sleep on central sleep apnea the airways are open, and these
back needs much more pressure to open the airway oscillations of pressure may be determined by the device in
compared with the superficial sleep and sleep on side, the breathing circuit. If the unit detects cardiac oscillations,
respectively. Comparative studies have shown that in it is interpreted as a central apnea and device not increases
application of APAP devices mean therapeutic pressure the pressure. If the oscillations are not detected, it is
was 30-40% lower compared with the required fixed interpreted as obstructive sleep apnea and therapeutic
pressure treatment, which improves the acceptability of pressure increases. According to the manufacturer's method
treatment [7]. In this case the use of APAP provided for detection of cardiac oscillation has a high specificity
similar efficacy to eliminate breath disorders compared (99.7%) and sufficient sensitivity (63.2%).
with the use of CPAP devices with fixed pressure. During
III. CONCLUSIONS
the pressure auto-adjusting the algorithm of apparatus
There are different types of biomedical devices from very
monitors 5 parameters: inspiratory flow limitation, snoring,
simple to sophisticate which can provide large options for
hypopnea, apnea, and the presence or absence of cardiac
apparatus treatment of OSA.
oscillations in the phase of sleep apnea. The normal
inspiratory flow curve has a rounded peak. Inspiratory flow REFERENCES:
curve begins to change even with minimal narrowing of the [1] Guilleminault C., Miles L. Differential diagnosis of
airways that is not accompanied by snoring or sleep apnea obstructive apnea syndrome: the abnormal esophageal
/hypopnea. In this case it is noted a flattening of the reflux and laryngospasm during sleep. Sleep Res.
inspiratory flow curve. The microprocessor unit analyzes 1980;16:410.
the shape of the central part of the inspiratory flow curve in [2] Young T, Evans L, Palta M. Estimation of the
each respiratory cycle. If it is define two or more cycles clinically diagnosed proportion of sleep apnea
with inspiratory flow limitation, the device increases the syndrome in middle-aged men and women. Sleep
therapeutic pressure. The device can respond by an 1997; 20(9):705-6.
increase in pressure only on flow limitation without [3] Jennum P, Riha RL. Epidemiology of sleep
reducing the flow (lesser degree of obstruction) or on flow apnoea/hypopnoea syndrome and sleep-disordered
limitation with reduced flow (high degree of obstruction). breathing. Eur Respir J 2009;33(4):907-14.
These presets are given by medical staff and increase or [4] Ferguson KA et al. Oral appliances for snoring and
decrease the sensitivity of the apparatus, respectively. obstructive sleep apnoea: a review. Sleep
Snoring is defined by the unit as high-pressure fluctuations 2006;29(2):244-62.
in the frequency range that overlaps the curve of the [5] Sullivan CE, Issa FG, Berthon-Jones M et al.
respiratory flow. The appearance of snoring also is a signal Reversal of obstructive sleep apnea by continuous
to increase the therapeutic pressure. The progression of positive airway pressure applied through the
airway obstruction leads to significant decrease of the flow nares. Lancet 1981;1:862-865.
- hypopnea. In the case of complete cessation of breathing
[6] Fietze I, Penzel T, Alonderis A et al. Management
apparatus detects no flow - apnea. In the case of sleep
apnea is a problem of differentiation between obstructive of obstructive sleep apnea in Europe. Sleep Med
and central sleep apnea. Central apnea may be noted, 2011; 12:190-197.
firstly, during the REM-sleep in healthy individuals, and [7] Randerath WJ. APAP or CPAP: Who benefits?
secondly, in patients with Cheyne-Stokes respiration. In the Sleep Med 2007; 8(7-8):691-692.

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Mid-term Results of Tissue Engineered Valvular

Grafts for Pulmonary Valve Replacement in
Pediatric Patients and Young Adults.
S. CEBOTARI1, I. TUDORACHE1, E. CHEPTANARU2, S. BARNACIUC2, A. CAZACU2, O.
MALIGA2, O. REPIN2, L. MANIUC2, T. BREYMANN1, S. SARIKOUCH1, D. BOETHIG1, A.
GOERLER1, A. HAVERICH1, A. CIUBOTARU2
1
Department of Cardio-Thoracic, Transplantation and Vascular Surgery, Hannover Medical School,
Hannover, Germany
2
Heart Surgery Center, National Institute of Cardiology, Chisinau, Republic of Moldova

Five-year-freedom from explantation was 100% for

I. INTRODUCTION
TEPH; 93 ± 4% and 91 ± 4% for BJV and CH conduits
Graft degeneration is a major cause of reoperation in
respectively.MRI was performed in matched 17 recipients of
young patients after pulmonary valve replacement.
DPH and 20 BJV with longer follow up (>2 years). Mean
Glutaraldehyde fixed or cryopreserved grafts lack the
age of the patients was 12.7 ± 6.1 years old in DPH and 13.0
potential to growth. Here we present the mid-term results of
± 3.0 in BJV, with a follow-up time of 3.7 ± 1.0 and 2.7 ±
implantation of tissue engineered pulmonary homografts
0.9 years respectively. Despite lower implantation age and
(TEPH) compared to glutaraldehyde-fixed bovine jugular
longer observation time, the mean transvalvular gradient was
vein (BJV) and cryopreserved homografts (CH).
significantly lower in TEPH group (11mmHg) comparing to
II. METHODS AND RESULTS: BJV group (23.2 mmHg). Regurgitation fraction was 14% ±
Thirty-seven patients with TEPH in pulmonary position 3 and 4% ± 5 in TEPH and BJV group respectively. In 3
were consecutively evaluated during the follow-up (up to 5 TEPH recipients moderate regurgitation was documented
years) including medical examination, echocardiography and postoperatively and remained unchanged during the entire
MRI. These patients were matched according to age and follow-up.
pathology and compared to BJV (n=34) and CH (n=56)
III. CONCLUSION
recipients. In contrast to BJV and CH groups,
Tissue engineered fresh allograft valves showed superior
echocardiography revealed no increase of transvalvular
performance comparing to conventional homografts and
gradient, cusp thickening or graft degeneration and normal
xenografts and exhibited increased durability, graft
ventricular function in DPH group during the entire follow-
remodelling and adaptive growth.
up. Over time, TEPH valve annulus diameters converged
towards normal z values.

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Interaction of Bacteria With Nanostructured

Zinc-oxide Thin Films
Iliana A. IVANOVA1*, Orlin ANGELOV3, Liudmila KRASTEVA2, Tatiana PESHKOVA2, Karolina
PAPAZOVA2, Doriana DIMOVA-MALINOVSKA3, Ceco D. DUSHKIN2
1
Department of Microbiology, Faculty of Biology, University of Sofia St. Kliment Ohridski, 8 Dragan
Tzankov Blvd., 1164 Sofia, Bulgaria,
2
LNST, Department of General and Inorganic Chemistry, Faculty of Chemistry, University of Sofia St.
Kliment Ohridski, 1 James Bourchier Blvd., 1164 Sofia, Bulgaria;
3
Central Laboratory of Solar Energy and New Energy Sources, Bulgarian Academy of Sciences, 72
Tzarigradsko Chaussee, 1784 Sofia, Bulgaria.
*E-mail: [email protected]
Abstract – The effect of nanostructured ZnO thin films on one Gram positive and one Gram-negative
bacterium is studied. The films are prepared by different methods: (i) RF magnetron sputtering of ZnO
target in atmosphere of Ar (0.5 Pa ) or Ar (0.5 Pa )+H 2 (0.1Pa ), (ii) Sol-gel – glass substrate is dip coated in a
colloidal sol prepared from zinc acetate, dried and then fired at high temperature in order to get thin ZnO
films; (iii) Chemical deposition – seeds of ZnO are first casted on a glass substrate and then ZnO nanorods
are repeatedly grown on them via deposition from a chemical bath. The ZnO films structures are studied by
XRD, SEM and AFM. All patterns have a polycrystalline structure with preferential (002) crystallographic
orientation and c-axis perpendicular to the substrate surface. The influence of the as-prepared films on
Bacillus cereus and Pseudomonas putida is studied by two different methods - optical density measurement
and classic cultivation (rich and poor medium). Periodic cultures of bacteria are investigated in a 24-hours
experiment for sensitivity to the ZnO thin films immersed in the bacterial suspension. Our experiments prove
that ZnO films made by wet colloidal methods (sol-gel or chemical bath) are toxic to the studied bacteria. The
ZnO thin films obtained by r.f. magnetron sputtering activate the rate of cell division and increase the
percentage of live cells in comparison with the control experiment (without ZnO film). The observed
difference can be due to the release of zinc species from the colloid-made films.

Index Terms – Bacillus cereus, Pseudomonas putida, nanostructured ZnO thin film

In our study for the first time prokaryotic tests with

Pseudomonas putida ATCC11778 and Bacillus cereus
I. INTRODUCTION ATCC12633 are used to determine the influence of zinc
The effect of a new synthesized chemicals and materials oxide thin films prepared by three different methods: (i)
on environment is often determined by bioassays. They are magnetron sputtering [11], (ii) sol-gel dip coating [12] and
quantitative measure of the total toxic potential of a sample (iii) chemical deposition [13]. Three different methods are
and show possible synergistic or antagonistic effects of used to determine the quantity of total, damaged and active
contaminants and media, in which they occur. bacterial cells: optical density measurements, classic
Microorganisms and cell cultures are preferred in toxicity cultivation in a rich solid medium and fluorescent
studies of objects, because of their short test duration, low microscopy. In the latter, BacLight Bacterial Viability Kit is
cost, environmental friendliness and large amount of the used to differentiate and count live and dead cells. We
investigated organisms. Pseudomonas putida ATCC11778 examine the sensitivity and the damages of different bacteria
and Bacillus cereus ATCC12633 tests are widely used for during their exposure on the surface of nano-structured ZnO
toxicity assessment of water and new synthesized chemical thin films immersed in the bacterial suspension [14].
compounds [1,2,3]. Some investigations of ZnO
nanoparticles have shown their toxicity to bacterial cells II. MATERIAL AND METHODS
[4,5,6]. Yamamoto [7] has reported about increased toxicity II.1. Preparation of ZnO nanostructured thin films
of nanoparticles (of diameters smaller than 100 nm) on (i) Magnetron sputtering [11]. Two sets of ZnOsamples
bacteria with decreasing of the nanoparticle size. Li et al. [8] were prepared - pure ZnO and ZnO doped with hydrogen
have studied the toxicity of ZnO nanoparticles to (ZnO:H). The thin films were deposited by r.f. magnetron
Pseudomonas putida and other bacteria and found a sputtering of a ZnO ceramic target (100 mm disc) in
dependence on the concentration of the dissolved Zn ions. atmospheres of Ar (0.5 Pa) or Ar (0.5 Pa) + H2 (0.1 Pa) at
Sapsford et al. [9] has suggested that the high temperature substrate temperatures 500C and 400C, respectively, and
treatment of ZnO nanoparticles leads to lower antibacterial r.f. power of 180 W. The thickness of the deposited films is
activity. about 600 nm. The XRD spectra were collected using
Summarizing the results, ZnO nanoparticles have in DRON 3 spectrometer with CuKα radiation (λ=1.5406 Å).
general a toxic effect to various bacterial populations in the SEM pictures are obtained by JSM-840A JEOL with LaBa6
nanoparticle suspension in water. Despite the vast number of cathode.
papers on the ZnO nanoparticles, there are not enough (ii) Sol-gel dip coating [12]. The precursors are zinc
studies on the interaction between bacteria and ZnO thin acetate, 2-methoxyethanol and monoethanolamine (MEA).
films [5,10]. The film deposition was carried out on glass substrates (ISO-

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LAB-Germany). Each deposited layer was dried up in air at SEM. Golden thin film coating was made on the film before
60°C for 30 min. Total five layers were deposited. The final observation.
annealing was carried out at 500°C for 1 hour and the film
III. RESULTS AND DISCUSSION
thickness is about 1 µm. The films were investigated by
SEM pictures of the cross section of the thin films
SEM - JSM-5510 JEOL operating at accelerating voltage of
deposited by RF magnetron sputtering are presented in Fig.
10 kV. XRD spectra were recorded by apparatus Siemens
1a (ZnO) and Fig. 1b (ZnO:H). They show columnar
D500 with CuKα radiation.
structure of the films. The XRD spectra in Fig. 2 show a
(iii) Chemical bath deposition [13]. A wet chemical
polycrystalline structure of the films with preferential
method was used to obtain ZnO films in two steps:
crystallographic orientation (002) and c-axis perpendicular
deposition of seeds and growth of nanorods on them. Zinc
to the substrate surface. The estimated grain size according
acetate dissolved in ethanol was coated onto a glass substrate
to Debye-Scherrer equation is about 25 nm in the ZnO films
for four cycles. The coated substrates were then rinsed with
and about 17 nm in ZnO:H films.
water and dried at room temperature. After that they were
annealed in air at 320 °C for 20 min. The above procedure
was repeated twice before the final growth of ZnO
nanowires. The seeded substrates were then placed in
aqueous solution of zinc nitrate and methenamine and heated
up in a closed vial at 87 °C for 3 h. The samples were then
removed from the solution, rinsed with distilled water, and
placed in a new batch of precursor solution. The growth
process was repeated eight times and finally the samples
were dried in air. The film structure is studied by SEM
a b
(JSM-5510 JEOL operating at accelerating voltage of 10 kV) Fig.1. Cross section SEM pictures of the deposited thin films by magnetron
sputtering - ZnO (a) and ZnO:H (b).
and XRD (Siemens D500 with CuKα radiation).

II.2. Toxicity tests on bacteria

Two types of bacteria were used in our tests to study the
influence of nanostructured ZnO films: Pseudomonas putida
ATCC12633 (Gram-negative) [15] and Bacillus cereus
ATCC11778 (Gram-positive) [16].
To study the effect of the as-obtained ZnO thin films and
the bacterial survival of Pseudomonas putida, two types of
nutrient media were used: a rich medium ISO 10712 for
maintaining and a poor synthetic medium ISO 10712 for
testing the toxicity. The ZnO thin films were sterilised by
ethanol inflammation and put in the nutrient medium. The Fig. 2. XRD spectra of thin films ZnO (T s= 5000C) and
bacterial inoculum is prepared in solid rich medium and after ZnO:H (Ts= 4000C) prepared by magnetron sputtering.
that adapted to poor mineral medium, by three consecutive
sub cultivations (ISO 10712). The experiment was SEM picture of ZnO thin films prepared by sol-gel dip
conducted in aerated dark and light conditions by orbital coating is shown in Fig. 3a and by chemical bath deposition
bench top shaker Certomat® at 150-170 rpm, 25˚C for in Fig. 3b.
Pseudomonas putida and 30˚C for Bacillus cereus. The
suspensions were cultivated in 100-ml Erlenmeyer glass
flasks with 20-ml nutrient medium. The ratio of the
suspension volume to the surface area of the ZnO film was
10:1 and 2,5:1. The samples of bacterial cultures with ZnO
thin films and the control experiment were collected at 3, 6,
9, 12 and 24 hours. The lighting conditions were provided by
illumination with a tungsten lamp (100 W) and energy
saving lamp Ecoline Eco 32 (20WE27 warm light at 2700 K) a bb
placed at a distance of 30 cm from the suspension. Fig. 3. SEM photographs of ZnO thin films prepared by sol-gel dip coating
The number of survived cells in the suspension was (a) and chemical bath deposition (b).
determined by the most probable number method in a rich
The mean grain size of ZnO thin film prepared by sol-gel
solid ISO medium for Pseudomonas and other medium for
dip coating (Fig. 3a) is between 20-32 nm [12]. The top view
Bacillus cereus [3]. Second, the total cell number (live plus
of SEM image of ZnO thin film prepared by chemical bath
dead) is considered by spectrophotometer measurements
deposition (Fig. 3b) shows nanorods with hexagonal cross-
(λ=600 nm) of the optical density of the sample in a poor
section of typical size 100-200 nm and surface density ~1-
medium used as the control. All samples were taken in 3
3109 cm-2. The nanorod length is about 3-3.5 m [20]. The
replicas.
XRD pattern of ZnO thin films prepared by sol-gel dip
For SEM observations, the ZnO thin film was taken
coating (Fig. 4a) and chemical bath deposition (Fig.4b) show
sterile from the bacterial suspension after the experiment and
mostly (002) diffraction peak.
put in a sterile Petri dish. Then it was dried at room
temperature in a closed dish before the observation with

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Cultivation of bacteria is conducted in 6-well plastic plates

and the results of optical density are presented in Fig.7
versus the time.
1.0
control
ZnO MSD

Optical density (a.u.)

0.8 ZnO:H MSD
ZnO nanorods
0.6

0.4

0.2

a b 0.0
Fig. 4. XRD spectra of ZnO thin films prepared by sol-gel dip coating (a) 0 3 6 9 12 15 18 21 24
and chemical bath deposition (b). Time (h)

The results from the control bacterial growth in rich and a

poor medium and at dark and light conditions are presented 11
in Fig. 5. 10
1.2 9

lgCFU (ml-1)
1.0 8
7
Optical density

0.8
6 control
0.6 ZnO MSD
5
ZnO:H MSD
0.4 rich medium dark 4 nanorods
poor medium TL
0.2 poor medium ESL 3
poor medium dark 0 3 6 9 12 15 18 21 24
0.0
Time (h)
0 3 6 9 12 15 18 21 24
Time (h) b
Fig. 6. Effect of ZnO thin films prepared by different deposition methods
Fig. 5. Bacterial growth of Pseudomonas putida determined by optical on the bacterial growth of Pseudomonas putida (a) - Optical density
density at different experimental conditions. method, and Bacillus cereus (b) - CFU method, in poor nutrient medium.

There is significant difference between the quantities of The data are close to each other and there is strong
cells in the control samples grown in rich and poor medium. inhibition effect of the films on bacteria until 9-12 hours.
The thin ZnO films obtained by magnetron sputtering have a The data resemble those from Fig. 5 and especially the lag-
rather smooth surface and the cells are not damaged in a phase for the ESL light illumination in poor nutrient
contact to it. Figure 6 shows the optical density of medium. Only later (12-24 hours) there is an appreciable
Pseudomonas putida (total number of cells) versus time of exponential growth.
incubation in the presence of ZnO films. It is established that Тhе data are confirmed by the most-probable number
in all experiments the optical density of the suspensions method (CFU) in a solid medium – there are no significant
treated with nanostructured ZnO thin films, obtained by deviations from the control variant and the increasing of the
magnetron sputtering, follows clearly the trend from Fig. 5. bacterial populations is generally stable with no inhibition
It increases moreover faster than the one in the control effect of ZnO MSD thin films. The data for ZnO films
experiment and the cells division of Pseudomanas putida is obtained by sol-gel method show always inhibition effect, as
similar to that in rich medium. In the case of cultivation with proved by different methods.
ZnO:H films, also obtained by magnetron sputtering (MSD), 1.2
the optical density is very close to the control sample though control
Optical density (a.u.)

1.0 ZnO MSD

a bit lower at the initial stage (within the experimental error). ZnO:H MSD
If the bacteria are cultivated with nanorods ZnO films 0.8 ZnO sol-gel
obtained by chemical deposition method there is a strong 0.6
inhibition of the cells division till the 12th hour (Fig. 6).
0.4
These observations are proven also by the classical
cultivation method determining the live cells appeared as 0.2
colonies in solid medium. The trend is an increase of 0.0
bacterial number in the presence of nanostructured ZnO 0 3 6 9 12 15 18 21 24
obtained by MSD. Pseudomonas putida cells have not lag- Time (h)
phase and the number of the live active cells is higher than in
Fig. 7. Influence of differently deposited ZnO thin films on the growth of
the control experiment especially after the 9th hour. The Pseudomonas putida in poor nutrient medium, plastic plates and
bacterial growth in the presence of nanostructured ZnO illumination with an energy saving lamp.
nanowires is inhibited and the bacterial quantity is all time
The results for Bacillus cereus are different from those of
lower than in the control experiment.
Pseudomonas putida cells. Bacillus cereus cells sporulate at
Three experiments are conducted in light conditions with
the 6th hour to form fewer colonies on the solid rich medium
energy saving lamp and ratio 2.5:1 of bacterial suspension
– about 103 CFU per millilitre. The spores after 48 hours of
and different ZnO nanofilms (Fig.7).
cultivation in rich solid medium appeared as visual colonies.

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This is the reason to count very different number of Bacillus sensitive to the impact of ZnO nanoparticles and they are
cereus colonies from the samples of the 6 and 9th hours easily damaged (Fig. 9b) because of different cell wall
cultivation at the 24th and 48th hours of Petri dish structure (Gram-positive). This is especially true in the case
cultivation. of nanofilms with irregular surface relief (Fig. 9b) obtained
As could be seen from Fig. 6 and 7 both bacteria are more by the sol-gel methods. Our results are in accord with the
sensitive to the ZnO thin films with a ruffle structure report of Greist et al. [15], who have received similar
deposited by sol-gel dip coating or to nanorods films pictures by SEM. These results are quite encouraging as a
obtained by chemical bath deposition. The tendency is the first step in the development of ZnO based biosensor [19].
same till the 24th hour of cultivation (data are not
IV. CONCLUSIONS
presented). The results could be due to the bigger surface of
The influence of nanostructured ZnO thin films on the
ZnO ruffle thin films for interaction with bacteria or to the
cells division rate of bacteria Pseudomonas putida (Gram-
higher dissolving rate of Zn ions or nanoparticles. Our
negative) and Bacillus cereus (Gram-positive) was studied.
results are in accord with the report of Huang et al. [6]. In
The ZnO films are prepared on glass substrates by three
other papers [10, 5], ZnO seems more effective for the
different methods - RF magnetron sputtering, sol-gel and
destruction of Gram-positive than for Gram-negative
chemical bath. The structure of the films was studied by
bacteria because they have simpler cell membrane structure.
XRD, SEM and AFM. All patterns have a polycrystalline
Our experiments prove the same difference that the films
structure with preferential (002) crystallographic orientation
made by wet colloidal methods are toxic for the bacteria at
and c-axis perpendicular to the substrate surface. The
least in the first several hours.
influence of the as-prepared films on Bacillus cereus and
We do not establish any significant difference in the
Pseudomonas putida was studied by two different methods -
influence between ZnO and ZnO:H films obtained by MSD.
optical density measurements and the classic cultivation in
The reason could be the smooth surface and the similar
rich and poor medium (most-probable number method -
quantity of Zn+ and nanoparticles dissolved into the
colony forming units.ml-1 (CFU). Periodic cultures of
suspension. The presence of zinc ions at low concentration
bacteria were investigated in a 24-hours experiment for
(<0,2mM) in the poor medium increases the cell division
sensitivity to the ZnO thin films immersed in the bacterial
rate. If their concentration is higher (>0.25 mM) [6], this
suspension. The films of peculiar ruffle-like surface structure
effect is opposite, i.e. toxic. Obviously, the surface
have shown considerable inhibition effect at the first 9-12 h,
arrangement of ZnO thin films changes the toxicity of
especially for the Gram-positive bacteria. The thin films,
nanoparticles [18].
obtained by magnetron sputtering show stimulation effect on
the cells division. After the sporulation at the 6th h Gram
positive Bacillus cereus cells also acquire resistance to the
ZnO thin films. Our experiments proved that ZnO films
made by wet colloidal methods (sol-gel or chemical bath) are
toxic to the studied bacteria.
These results are quite encouraging as a first step in the
development of ZnO based biosensor.

ACKNOWLEDGEMENTS
This work has been supported financially by the National
Fig. 8. SEM pictures of Pseudomonas putida on ZnO films obtained by Scientific Fund of Bulgaria (NSFB) by project DO02-207.
magnetron sputtering - after 9 hours of cultivation. I.Ivanova and C.Dushkin are thankful also to the project
COST D43 Action of EC. C.Dushkin is thankful also to
project UNION DO02-82 of NSFB. I.Ivanova wish to thank
to R. Alexieva and Dr. A. Loukanov for helpful support.

REFERENCES
[1] J. Ahtiainen, R. Valo, M. Järvinen and A. Joutti,
Microbial Toxicity Tests and Chemical Analysis as
Monitoring Parameters at Composting of Creosote-
Contaminated Soil, Ecotoxic. Environm, Safety, vol. 53,
no. 2, 2002, pp. 307-322.
[2] Y.Zhou, J. Yao, Martin M.F. Choi, Y. Chen, H. Chen,
R. Mohammad, R.Zhuang, H. Chen, F. Wang, T.
a b Maskow, G. Zaray, A combination method to study
Fig. 9. SEM pictures of Bacillus cereus on ZnO thin films obtained by
different methods - chains on magnetron sputtered ZnO (a) and bacteria microbial communities and activities in zinc
after 24 hours of cultivation on ZnO thin film obtained by sol-gel method contaminated soil, J. Hazardous Materials, vol. 169, no.
(b). 1-3, 2009, pp. 875-881
The SEM images show separate cells and cell colonies in [3] D. Liu, Y. K. Chau, B. J. Dutka, Rapid toxicity
Fig. 8 and 9a. The Pseudomonas cells are intact and have assessment of water-soluble and water-insoluble
well preserved capsules (Fig. 8). There are micro colonies chemicals using a modified agar plate method, Water
formed on the smooth surface of the thin films. The Bacillus Res. vol. 23, no. 3, 1989, pp. 333-339.
cells also form a net structure on the ZnO thin films, [4] Brayner, R. Ferrari-Iliou, N. Brivois, S. Djediat, M. F.
deposited by magnetron sputtering, but they are more Benedetti, Toxicological impact studies based on

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Escherichia coli bacteria in ultrafine ZnO nanoparticles T. Peshkova, K. Papazova, C. Dushkin, Effect of the
colloidal medium, Nano Lett. 6, no. 4, 2006, 866-870. substrate om the growth of ZnO nanowires using
[5] K. H. Tam, A. B. Djurisic, C. M. N. Chan, Y. Y. Xi, C. chemical bath deposition, Nanoscience and
W. Tse, Y. H. Leung, W. K. Chan, F. C. C. Leung, D. Nanotechnology, E. Balabanova, I. Dragieva (eds.), vol.
W. T. Au, Antibacterial activity of ZnO nanorods 10, 2010, pp. 65-68
prepared by a hydrothermal method, Thin Solid Films, [12] I. Ivanova, S. Kambarev, R. A. Popova, E. G.
vol. 516, no18, 2008, pp. 6167-6174. Naumovska, K. B. Markovska, C. D. Dushkin,
[6] Z. Huang, X. Zheng, D. Yan, G. Yin, X. Liao, Y. Kang, Determination of Pseudomonas putida live cells with
Y. Yao, D. Huang, B. Hao, Toxicological effect of ZnO classic cultivation and staining with “Live/Dead
nanoparticles based on bacteria, Langmuir 24, no. 8, BacLight Bacterial Viability kit”Biotechnol. Biotechnol.
2008, 4140-4144 Eng., vol. 24 SE, 2010, pp. 567-561.
[7] О. Yamamoto, Influence of particle size on the [13] Y. B. Byaruhanga, B. H. Bester, T. G. Watson, J.
antibacterial activity of zinc oxide,Int. J. Inorg. Microbiol. Biotechnol., Growth and survival of Bacillus
Materials, vol. 3, no. 7, 2001, pp. 643-646. cereus in mageu, a sour maize beverage, 15, no.3,
[8] M. Li, S. Pokhrel, X. Jin, L. Madler, R. Damoiseaux, E. 1999, pp. 329-337.
M. V. Hoek, Stability, Bioavailability, and Bacterial [14] J. E. Bailey, D. F. Ollis, ―Biochemical Engineering
Toxicity of ZnO and Iron-doped ZnO Nanoparticles in Fundamentals‖, 2nd ed., McGraw-Hill Book Company,
Aquatic Media Environ Sci Technol., vol. 45, no. 2, New York, 1987.
2011, pp. 755-761. [15] G. Gellert, A. Stommel, Influence of microplate
[9] K. E.Sapsford, Chr. Bradburne, J. B. Delehanty, I. L. material on the sensitivity of growth inhibition tests with
Medintz, Sensors for detecting biological agents Mater. bacteria assessing toxic organic substances in water
Today, vol. 11, no. 3, 2008, pp. 38-49. and waste, Environm. Toxicology, vol. 14, no. 4, 1999,
[10] G. Applerot, N. Perkas, G. Amirian, O. Girshevitz, A. pp. 424-428.
Gedanken, Coatings of glass with ZnO via ultrasonic [16] I. Ivanova, R. Popova, A. Loukanov, O. Angelov, K.
irradiation and study of its antibacterial properties, Papasova, L. Krusteva, E. Naumovska, K. Markoska, C.
Appl. Surface Sci., vol. 256, no. 3, 2009, pp. S3-S8. Dushkin, Interaction between Bacillus cereus and
[11] D. Dimova-Malinovska, O. Angelov, H. Nichev, J. C. nanostructured thin films of zinc oxide as a transducer
Pivin, ZnO:H thin films for room temperature selective element for biosensing application, Trakia Journal of
NH3 sensors, J. Optoelectr. Adv. Mater., vol. 9, no. 2, Sciences, vol. 8, Suppll. 2, 2010, pp. 159-164.
2007, pp. 248-259. [17] A. Loukanov, I.A.Ivanova, A. Angelov, R.Popova, S.
V. Kaneva, G. G. Yordanov, C. D. Dushkin, Bratkova, S. Plochev, C. Dushkin, Nanostructured ZnO
Characterization of nanosized ZnO thin films for the as a transducer for biosensoring of sulphate-reducing
photoinitiated decolorization of malachite green in bacteria, Annual Univ. Mining &Geology, vol. 53, no.
aqueous solutions, Bulletin Mater. Sci., vol. 33, 2010, 2, 2010, pp.173-179.
pp. 111-118.
.

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DLC Biocompatible thin Films for

Cardiovascular Implants
S.T. SHISHIYANU1 , T.S. SHISHIYANU1, P.S. STEFANOV2, V.K. GUEORGUIEV3
1
Department of Microelectronics, Technical University of Moldova, 2004 Chisinau, Moldova
2
ISMA Ltd., 1138 Sofia, Bulgaria
3
Institute of Solid State Physics, Bulgarian Academy of Sciences, 1784 Sofia, Bulgaria
[email protected]
Abstract – Diamond-like carbon films (DLC films) for cardiovascular implants have successfully been
prepared by dual-target unbalanced magnetron sputtering and Rapid Photothermal Processing (RPP). It is
found that the sputtering current of target plays an important role in the DLC film deposition. Deposition
rate of 3.5 μm/h is obtained by using the sputtering current of 30 A. Rapid Photothermal Processing at 400C
essentially reduced the carbon content and have improved the surface morphology structure of deposited
coatings, which depend on the intensity of the ion impingement on the growing interface.

Index Terms – Diamond-like carbon, nanocomposite DLC, RPP.

type 316L. The morphological analyses demonstrated the

I. INTRODUCTION
essential grain enlargement. The high temperature annealing
Diamond-like carbon (DLC) films have found widespread
increase the grain size from 10 to 60 m, which is necessary
application in biological coatings for implantable medical
for the required elasticity of the arterial stents. The grain
devices, as a result of their good chemical resistance,
structure can influence the structure of the deposited
temperature stability and biocompatibility. The biological
biocompatible nanolayers, which is demonstrated further for
behavior of an implant can be tuned by modifying the
deposited at high temperatures layers on stainless steel
element composition. DLC can be easily alloyed with other
substrates.
biocompatible materials such as titanium as well as toxic
The images of the grain structure of the preetched 316L
materials such as silver, copper and vanadium by normal co-
type stainless steel annealed at high temperatures and the
deposition methods [1]. Nanocrystalline diamond-coated
initial non-annealed sample are shown in Fig. 1.
medical steel has shown a high level resistance to blood
platelet adhesion and thrombi formation [2]. Diamond and
DLC coatings have successfully been proposed for
applications as artificial heart valves, prosthetic devices,
joint replacements, catheters and stents, orthopedic pins,
roots of false teeth, surgical scalpels and dental instruments
[3-6].
II. EXPERIMENTAL
Pulsed direct current (p-DC) magnetron sputtering in
combination with an unbalanced magnetron configuration
has become a major technique in the deposition of advanced Fig. 1 (a,b). Grain structure of preetched high temperature annealed (a) and
coatings during the last decade. It has the significant non-annealed (b) 316L type stainless steel.
advantage over DC magnetron sputtering in suppressing The SEM images of the DLC layers deposited on stainless
arcing at the targets during reactive sputtering and in steel at temperatures higher than 230C . T1<T2, the RPP
sputtering non-conductive materials. was performed at 300C in vacuum, are presented in Fig. 2.
In this paper we present the results on the microstructural The thermal annealing of the stainless steel substrate
control of Ti/DLC nanocomposite coatings with pulsed during deposition at high temperatures do not change
direct current (DC) magnetron sputtering. The sputtering essential the elemental content of the substrate. Only a small
system was configured of Ti target (99.7%), and graphite oxidation is observed. But the surface and the structure of
target (99.99%). The diameter of all the targets was 3 inches. the deposited carbon layers is not smooth, as it is for layers
All the power supplies for sputtering were operated at deposited on the glass and these temperatures are not
current regulation mode via a computer-controlled system. applicable for the stents technology.
The thin metal layers were deposited on nonannealel and AFM study images of the DLC layers deposited on
annealed stainless steel. Annealing was performed according stainless steel at 250C, RPP 400C are presented in Fig. 3.
the technology sequence for stents-electropolishing and high The AFM study of DLC layers deposited at high
temperature annealing for grain enlargement and improving temperatures on nonannealed and annealed stainless steel
of the stents elasticity. A number of analytic methods were have shown that the roughness of the layers is up to 300 nm
applied SEM, AFM and EDX. on nonannealed substrates and up to 3500 nm on annealed
The Ti/DLC films were deposited onto pre-etched substrates.
nonannealed and high temperature annealed stainless steel

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much larger grain size after annealing.

TABLE 1. INFLUENCE OF RAPID PHOTOTHERMAL

PROCESSING ON THE CARBON CONTENT IN DLC.
RTP
Furnace RTP 300C
Non
400C 300C 1 min +
annealed
3 min 3 min 400C 1
min
Ele
W A W W W
me A% A% A%
% % % % %
nt
27. 39. 28. 39. 30. 42. 16. 25.
C
51 46 24 64 30 99 59 45

The RPP at 300C and the furnace annealing at 400C up

to 3 min do not change essentially the carbon content, but
RPP at higher temperature even up to 1 min change/reduce
the carbon content.
100
C Fe
O Ti
80

concentration [at.%] 60

40
Fig. 2 (a,b). SEM of RPP DLC layers on stainless steel deposited at
temperatures: a - T1, b - T2. 20

0
0 20 40 60 80 100
sputtering time [min]

Fig. 4. Auger depth analysis for 65min deposition of DLC.

Auger depth analysis of DLC layers deposited on stainless

steel for different deposition times at low plasma densities
were also carried out, and the Auger spectra are presented in
Fig. 4. The Auger analyses have shown existence of relative
thick carbon layer, thin transition C/Ti layer and thin Ti
layer.
III. CONCLUSIONS

The reliable technology for magnetron deposition of

biocompatible Ti/DLC nanolayers for coating of implantable
medical devices has been established. RPP at 300400C
improved the microstructure and properties of deposited
coatings, which strongly depend on the intensity of the
concurrent ion impingement on the growing interface.

ACKNOWLEDGEMENTS

Authors gratefully acknowledge ISMA Ltd. Sofia for

providing the magnetron sputtering system and the
cardiovascular STENTs produced by ISMA Ltd. Sofia,
Bulgaria. Authors also gratefully acknowledge Dr.
E.Monaico, Dr. M.Enachi and National Center for Materials
Study and Testing for carefully provided SEM and AFM
Fig. 3 (a,b). 2D and 3D AFM images of layer deposited at 250C on measurements.
nonannealed stainless steel.

The roughness on nonannealed samples is due to the

nonpolished surface, wile on the annealed substrates-to the

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REFERENCES
[1] I.D. Scheerder, et al., ―The Biocompatibility of [4] R. Hauert, ―A review of modified DLC coatings for
Diamond-Like Carbon Nano Films,‖ J. Invasive biological applications,‖ Diamond & Related Mater.
Cardiology, vol. 12, pp.389-394, 2000. vol. 12, Issue 3-7, pp.583-589, 2003.
[2] W. Okroj, M. Kamińska, L. Klimek, W. Szymański, B. [5] R.A. Freitas, Foresight Update, 39 Foresight Inst. Palo-
Walkowiak, ―Blood platelets in contact with Alto, CA, USA, 1999.
nanocrystalline diamond surfaces,‖ Diamond & Related P.A. Dearnley, ―A review of metallic, ceramic and
Mater., vol. 15, Issue 10, pp.1535-1539, 2006. surface treated metals used for bearing surfaces in
[3] A.Grill, ―Diamond-like carbon coatings as bio- human joint replacements,‖ Proc. of Institution of
compatible materials—an overview,‖ Diamond & Mechanical Engineers. Part H, Engineering in Medicine,
Related Mater., vol. 12, Issue 2, pp.166-170, 2003. vol. 213, pp.107-135. 1999

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Antimicrobial Polymers: from Structure Design

to Specific Properties and Applications
Madalina ZANOAGA, Fulga TANASA
“Petru Poni” Institute of Macromolecular Chemistry Iasi, Romania
[email protected]

Abstract – Microbial infection remains one of the most serious complications in several areas, particularly in
medical devices, drugs, health care and hygienic applications, water purification systems, hospital and dental
surgery equipment, textiles, food packaging, and food storage [1,2]. Antimicrobials gain interest due to their
potential to provide quality and safety benefits to many materials. However, low molecular weight
antimicrobial agents suffer from many disadvantages, such as toxicity to the environment and short-term
antimicrobial ability.
To overcome these problems associated with the low molecular weight antimicrobial agents, antimicrobial
functional groups can be introduced into polymeric macromolecules. The use of antimicrobial polymers
offers promise for enhancing the efficacy of some existing antimicrobial agents and minimizing the
environmental problems accompanying conventional antimicrobial agents by reducing the residual toxicity of
the agents, increasing their efficiency and selectivity and prolonging the lifetime. Research concerning the
development of antimicrobial polymers represents a great a challenge for both the academic world and
industry.
This article reviews some data concerning antimicrobial polymers, from the structure design to specific
properties and applications, as well as future and perspectives in the field of antimicrobial polymers.

Index Terms – antimicrobial agents, polymers synthesis, characterization, applications.

REFERENCES
[1] M. B. Patel, S. A. Patel, A. Ray and R. M. Patel, J. [2] E.-S. Park, H.-J. Lee, H.-Y. Park, M.-N. Kim, K.-H.
Appl. Polym. Sci., 89, 895-900, 2003. Chung and J.-S. Yoon, J. Appl. Polym. Sci., 80, 728-
736, 2001.

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Biocompatible and Resorbable Polymeric

Materials for Surgical Sutures
Fulga TANASĂ, Mădălina ZĂNOAGĂ
“Petru Poni” Institute of Macromolecular Chemistry
[email protected]

Abstract – As implants in human body, sutures are one of the largest groups of materials and have
been in use for many centuries. Along with the development of the synthetic resorbable polymers, i.e.
poly(glycolic acid) (PGA) in the early 1970s, a new research direction has opened on biocompatible
rebsorbable polymers for sutures.
This article reviews some of the available information with regard to developments on chemistry,
properties, biocompatibility and biodegradability, and performance of resorbable polymeric sutures.

Index Terms – suture materials, biomaterials, biocompatible polymers, resorbable polymers.

ideal for every operation, therefore surgeons and medical

I. INTRODUCTION designers have come up with sutures with varying qualities:
A suture is a biomaterial device, either natural or one may be more absorbable, but less flexible, while another
synthetic, used to link blood vessels and bring tissues may be exceedingly strong, but difficult to knot. Designers
together [1]. Thus, its major functions are to draw and hold of a new suture material have to take into account many
together tissues following their separation by surgery or factors, as follows: the rate of suture degradation, length of
trauma. Sutures are the most widely used materials in wound the suture, the knot, material elasticity, memory. Suture
closure, they have registered tremendous growth during the manufacturers use specially designed machines to test and
last two decades and have become the largest group of study sutures. New suture designs are also evaluated by
biomaterials having a huge market exceeding $1.3 billion subjecting them to chemical tests, such as soaking them in
annually [2]. various solutions, and testing on animals.
An ideal suture should have the following characteristics: Suture materials are frequently coated, especially braided
easy to handle, elicit minimal tissue reaction, does not or twisted sutures, to facilitate their handling properties,
support bacterial growth, possess high tensile strength, easy particularly to induce a significant reduction in tissue drag
to sterilize, elicit no allergic reaction, no carcinogenic effect, and increasing the ease of sliding knots during knotting.
is absorbed by human tissues after serving its function. Thus, Traditional coating materials used are bees wax, paraffin
a suture should not only be very strong, but also be able to wax, silicone, poly(tetrafluoroethylene) (PTFE), etc. The
simply dissolve into body fluids and lose strength at the trend is toward a coating material that has a chemical
same rate that the tissue gains strength. property similar to the suture to be used. The coatings
Suture materials are characterized by various methods depend on whether the suture is absorbable (Poloxamer 188
involving physical and mechanical properties, handling and calcium stearate with a copolymer of glycolic acid and
characteristics, and biological and biodegradation behavior. lactic acid) or nonabsorbable (wax, silicone, fluorocarbon,
Mechanical properties, such as tensile strength (knotted and etc.) [4].
unknotted tensile strengths), percentage elongation, modulus Absorbable natural suture materials are made of catgut or
of elasticity, stress relaxation, and creep are measured reconstituted collagen (RC), or from cotton, silk, or linen.
routinely. As capillarity is related to the ability to transport Synthetic nonabsorbable sutures may be made of PP,
bacteria, it also needs to be measured. Other parameters poly(ethylene glycol terephthalate) (PET), poly(butylene
measured are swelling and coefficient of friction, pliability, glycol terephthalate) (PBT), polyamide (PA), different types
packaging memory, knot security, knot tie-down, knot of Nylons, or Goretex®.
slippage, tissue drag, etc., and they are used to understand Catgut and regenerated collagen are the two absorbable
these suture materials functions and range of applications. natural sutures available. Catgut was the staple absorbable
Three main classes of suture materials are known: suture material through the 1930s, while physicians used silk
collagen, synthetic absorbable and nonabsorbable. They can and cotton when a nonabsorbable material was needed.
be classified as follows: Catgut sutures are well known for their great toughness and
I – silk or synthetic fibers of monofilament, twisted, or tenacity. The basic constituent of catgut is collagen, which is
braided; the main constituent of skin and the major structural protein
II – cotton or linen fibers or coated natural or synthetic found in all multicellular organisms.
fibers in which the coating contributes to suture thickness Reconstituted collagen (RC) has low immunologic
without adding strength; activity, is prepared either by enzymatic digestion of native
III – metal wire of monofilament or multifilament. collagen-rich tissues or by extraction with salt solutions. RC
Sutures are designed to meet many different needs [3]. sutures prepared from bovine long flexor tendons are similar
Sutures for abdominal surgery, for example, are different in appearance to catgut and are almost exclusively used in
from sutures used in cataract surgery. No type of suture is microsurgery. The mechanical and thermal stability of RC
fibrils can be increased by maturation in vitro when

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incubated in air, at 37°C [5]. RC sutures are used in undesirable tissue reactions. Due to the development of these
ophthalmic surgery, as well as for other applications. polymers, they have replaced natural fibers (cotton, linen
and catgut) for wounds closure. Today, surgeons have the
II. BIOCOMPATIBLE AND RESORBABLE SYNTHETIC
possibility to choose among a large number of suture
SUTURE MATERIALS
materials with various chemical, physical, mechanical and
Following the successful development of the synthetic
biological properties.
absorbable polymer, PGA in the early 1970s, a series of
Polyglycolide or poly(glycolic acid) (PGA)
polymers and copolymers based on a few cyclic lactones,
Poly(α-ester)s are thermoplastic polymers with
presented in Fig. 1, were synthesized, characterized and
hydrolytically labile aliphatic ester linkages in their
produced at commercial scale.
backbone. Although all polyesters are theoretically
degradable, only aliphatic polyesters with reasonably short
aliphatic chains between ester bonds can degrade over the
time frame required for suture materials [8].
PGA is the simplest linear aliphatic polyester. Owing to
its controllable hydrolytic degradation, PGA and its
copolymers with LA, ε-CL and TMC are widely used as
materials for the synthesis of resorbable sutures and are
being evaluated in the biomedical field [9].
PGA can be obtained through several different processes,
starting from different materials: polycondensation of GA,
ring-opening polymerization (ROP) of GL (see Fig. 1),
solid-state polycondensation (SSP) of halogenoacetates, acid
catalyzed reaction of carbon monoxide, formaldehyde, etc.
The ROP of GL in the presence of stannous octanoate and
heating is the most common synthetic method used to obtain
high molecular weight polymers (polymers with
Mw=20,000–140,000 are suitable for fiber extrusion and
suture manufacturing).
PGA is a highly crystalline polymer (≈ 45–55%), having
glass transition temperature between 35-40°C and its melting
point in the range 225–230°C; it is soluble only in highly
fluorinated solvents (i. e., hexafluoroisopropanol,
hexafluoroacetone sesquihydrate) that can be used to obtain
polymer solutions for melt spinning and film preparation.
Fibers of PGA show excellent mechanical properties (high
strength and modulus) due to the polymer high crystallinity.
A self-reinforced PGA composite is stiffer than any other
degradable polymeric system used clinically and has been
shown to exhibit a modulus of approximately 12.5 GPa [10].
Concerning its biodegradable character, PGA undergoes
hydrolytic degradation through nonspecific cleavage of the
ester backbone [11]. The degradation process is erosive and
appears to take place in several steps during which the
polymer is converted to its initial monomer GA. The first
step involves diffusion of water into the amorphous regions
of the polymer, cleaving the ester bonds; the second step
starts after the erosion of amorphous regions, leaving
Fig. 1. Monomers and polymers used for synthetic biocompatible resorbable
crystalline chains susceptible to the hydrolytic attack. Upon
sutures collapse of the crystalline regions, the polymer chain
dissolves. When exposed to physiological conditions, PGA
Thus, new surgical practice needs synthetic absorbable decomposes under enzymes (esterase type) attack and the
suture materials, such as: Dexon® (Davis & Geck Corp), degradation product, the same GA, is nontoxic and it can
Vicryl® (Ethicon), PDO (Ethicon), PDOII® (Ethicon), easily enter the tricarboxylic acid cycle, during which it is
Maxon® (Davis & Geck), Monocryl® (Ethicon) and Biosyn® gradually decomposed up to water and carbon dioxide. A
(US Surgical, Norwalk, CT). New sutures are being part of the GA is also excreted by urine. Studies carried out
developed all the time, in order to better respond to specific using sutures made from PGA have shown that the material
surgical demands. The suture materials properties are studied loses half of its strength after 2 weeks and 100% after 4
through laboratory experiments, whose results are validated weeks. Figure 2 shows the rate of the in vitro degradation of
in extensive studies and trials [6]. Absorbable sutures are PGA. The polymer is completely resorbed by the organism
now well known to behave favorably in vitro and in an in a timeframe of 4–6 months [12,13].
animal model [7]. The most important advantage of The water sorption and its penetration into the PGA, PLA
synthetic biocompatible resorbable sutures is their and their copolymers initiate the hydrolytic degradation,
reproducible degradability inside the biological environment. followed by the decay of their mechanical properties. The
This property will enable sutures to have minimum chronic tensile tests on co/terpolymers of LL, ε-CL and GL showed

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that the tensile strength was strongly dependent on the draw decreased by 12% after 28 days. In Figure 3, the rate of
ratio [14]. degradation of PLA is presented.

Fig. 2. The rate of the in vitro degradation of PGA

Fig. 3. The rate of the in vitro degradation of PLA
Comparing the biodegradability of Monocryl®
monofilaments with poly(trimethylene carbonate-ε- The diagram shows that during the hydrolytic degradation
caprolactone)-block-poly(p-dioxanone) [poly(TMC-e-CL)- of PLA, the molecular mass decreases and its distribution
block-PDO] copolymers, it was ascertained that the becomes continuously broader with the increasing
biodegradability of PDO homopolymer is much lower degradation time. The conclusion is the PLA thread is a
compared with that of the copolymer Monocryl®, probably suitable suture for wounds that require healing time up to 28
due to the presence of the GL in the copolymer structure. weeks.
PGA is particularly useful in subcutaneous and Poly(lactide-co-glycolide) (PLGA)
intracutaneous closures, abdominal and thoracic surgeries. Copolymers of GA with both LL and DL have been
With its high initial tensile strength, it has guaranteed developed for both devices and drug delivery applications.
holding power through the critical wound healing period. For suture applications, LL-co-GL copolymer must have a
high concentration of GL in order to achieve the required
Polylactide or poly(lactic acid) (PLA) mechanical and biodegradation properties. PLGA is
PLA polymers are leading biomaterials having synthesized by means of random ROP of two different
applications in biomedical and pharmaceutical industries as monomers (see Fig. 1) and, depending on the LA/GA ratio,
resorbable implant materials, wound closure, bone fixation different forms of PLGA can be synthesized. All PLGAs are
devices and vehicles for controlled drug delivery [9]. They amorphous rather than crystalline and show a glass transition
are characterized by high mechanical strength, inherent temperature in the range 40–60°C. Unlike the corresponding
biodegradability and biocompatibility. However, their homopolymers which show poor solubilities, PLGA can be
clinical applications are sometimes affected by their high dissolved by a wide range of common solvents, including
hydrophobic character and consequent poor water uptake, chlorinated solvents, tetrahydrofuran, acetone, or ethyl
which results in a slow hydrolytic degradation rate. acetate.
Copolymerization of LL (levo isomer) with other co- The PLGA biodegradability is highly related to its
monomers is used to modify the PLA properties and to crystallinity and the solution pH [18]. The copolymer PLGA
control its degradation according to the specific applications has been shown to undergo bulk erosion through the
in the field [15–17]. The synthesis of PLAs of high Mw for hydrolysis of ester bonds and the rate of degradation
suture applications can be carried out by the ring opening depends on a variety of parameters, including the LA/GA
polymerization of the cyclic diester (LL) of LA (see Fig. 1). ratio, Mw, the shape and structure of the matrix [19]. The
Due to the chiral nature of LA, several distinct forms of degradation products, LA and GA, are common by-products
polylactide exist: poly-L-lactide (PLLA or PLA in common of various metabolic processes in the body, under normal
use) which is a crystalline polymer, while the polymerization physiological conditions, and there is a minimal systemic
of a racemic mixture of L- and D-lactides (DL) usually leads toxicity associated with PLGA. The in vivo rate of
to poly-DL-lactide (PDLLA) which is amorphous. degradation depending on the LA/GA ratio is presented in
It was reported that the PLA has a crystallinity of ≈ 37%, Figure 4.
a glass transition temperature in the range 50-80°C and a
melting temperature between 173-178°C. The initial tensile
strength of the PLA fibers is lower than that of the
commercially available sutures such as PDO, Vicryl®, silk
and Ethilon® (Nylon 6 and Nylon 66 monofilament suture).
The handling characteristics of PLA sutures were found to
be superior to those of the monofilament sutures such as
PDO and Ethilon® and comparable with the multifilament
sutures such as Vicryl® and silk. A composite consisting of
PDLA and bioglass was used as a coating for degradable
sutures such as Vicryl® [9]. Fig. 4. The in vivo rate of degradation versus PLA content in the PLGA
The in vitro, in the subcutis, and in the achilles tendon of copolymer
rabbits studies revealed that, although PDLA had a lower
Experimental data show that the resistance to hydrolytic
initial tensile strength than Maxon®, it showed more
degradation is more pronounced at either end of the co-
prolonged tensile strength retention (TSR). When PLA
polymer composition. For example, a copolymer of 50% GA
sutures were exposed to physiological saline solution (0.9
and 50% DL degrades faster than either corresponding
wt% NaCl aqueous solution) at 37°C, the knotpull strength
homopolymer. Copolymers of LL with 25–70% GA are

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amorphous due to the disruption of the regularity of the The copolymer of LL with ε-CL exhibited good strength
polymer chain by the other monomer. and flexibility, suitable for monofilament sutures, and it also
showed improved handling characteristics. On the other
hand, Prolene® (PP) and poly(L-lactide-co-ε-caprolactone)
(PLA-ε-CL) sutures showed high knot-pull strength, despite
low straight pull strength. A good correlation between tanδ
and bending plasticity index was observed and the PLA-ε-
CL sutures exhibited high tanδ, high bending plasticity and
good resistance against untying [9].
Co/terpolymers of LL, ε-CL and GL are biodegradable in
the human body and, therefore, have considerable potential
for use in biomedical applications such as surgical sutures,
Fig. 5. Electrospun PLGA fibers nerve guides, bone fixation devices and drug delivery
The major advantage of these copolymers can be systems [22].
attributed to their biocompatible character, good Polydioxanone (PDO or PDS)
processibility which enables fabrication of a variety of Resorbable multifilament sutures, such as PLA and PGA,
structures and forms (electrospun PLGA fibers are shown in develop a greater amount of friction when penetrating tissues
Figure 5), controllable degradation rates and their success as and have a higher risk of infection. So, monofilament sutures
biodegradable resorbable suture materials. based on PDO having smooth and soft surface were
introduced in the 1980s [23]. PDO suture has handling
Polyglyconate (PG) properties that are acceptable for use in vascular applications
Copolymers of GA with TMC have been prepared as both and it provides adequate mechanical support for sutured
sutures (Maxon® copolymer, see Fig. 1) and as tacks and vessels to heal. In addition, PDO provides good flexibility
screws. Typically, these compounds are prepared as A–B–A due to the presence of an ether group in the polymer
block copolymers in a GL:TMC=2:1 ratio, with a GL–TMC backbone.
center block (B) and pure GL end blocks (A). These PDO is prepared by the ROP of p-dioxanone to get a
materials have a better flexibility than pure PGA and are colorless, semicrystalline polymer with a very low glass
absorbed in approximately 7 months. GL has also been transition temperature ranging from -10’0°C. Being an
copolymerized with TMC and p-dioxanone to form a aliphatic polyester, it undergoes degradation by the
terpolymer suture (Biosyn®) that is absorbed within 3–4 nonspecific cleavage of the ester bond. PDO can be
months and offers reduced stiffness compared to pure PGA considered a slow to moderate degrading polymer due to its
fibers [20]. The hydrolytic degradation of PG has been high crystallinity and hydrophobicity.
studied in vitro and it was observed that the relationship Inside the body, PDO is broken down into glycoxylate and
between polymer strength and Mw was more complex than then excreted in the urine or converted into glycine and,
expected [21]. However, data could be modeled using an subsequently, into carbon dioxide and water [24]. PDO has
empirically derived relationship between tensile strength and demonstrated no acute or toxic effects upon implantation.
number average molecular weight (Mn). Changes in other The monofilament loses 50% of its initial breaking strength
mechanical properties, such as strain at break, were also after 3 weeks and is absorbed within 6 months, providing an
found to be strongly dependent of Mn. These results advantage over Dexon® or other products for slow-healing
demonstrated that absorbable PG suture might be suitable for wounds.
microvascular anastomosis of arteries under ordinary stress Poly(Trimethylene Carbonate) (PTMC)
and under tension up to a certain level. ROP of TMC gives high molecular weight polymers with
Poly(e-Caprolactone) (PCL) flexible chains. Unlike the previously described polyesters,
PCL is produced by the ROP of ε-CL. It is a semi- PTMC undergoes surface degradation. The rate of the in vivo
crystalline polymer with a melting point of 59–64°C and a degradation was found to be much higher than the in vitro
glass-transition temperature of -60°C. The polymer has been degradation. This is presumably due to the contribution of
regarded as tissue compatible and used as a biodegradable the enzymatic attack [24]. The low mechanical performance
suture in Europe. The polymer undergoes hydrolytic of the homopolymer led to the development of several
degradation due to the presence of aliphatic ester linkages co/terpolymers with other cyclic lactones, such as Maxon®
which are hydrolytically labile under physiological and Biosyn®. A comparative study of mechanical properties
conditions [9]. of Maxon® and Biosyn® is given in Table 1.
Because the homopolymer has a degradation time of 2
TABLE 1. MECHANICAL PROPERTIES OF
years, copolymers have been synthesized in order to MAXON® AND BIOSYN®
accelerate the rate of bioabsorption. For example, Characteristic MAXON® BIOSYN®
copolymers of ε-CL with DLL have yielded in materials Diameter (mm) 0.293 0.29
with higher degradation rates. The introduction of the Knot pull strength (kg) 2.9 2.4
monofilament sutures of ε-CL and GL (Monacryl®) solved Young`s modulus (kpsi) 425 145
Straight-pull strength (kg) 3.9 3.7
many of the problems with braided sutures that relate to Elongation (%) 30 44
tissue drag and trauma, as well as the possible potentiation Tensile strength (kg/mm2) 56.2 55.3
of infection through the interstices of the braid structure. The degradation studies consider that the absorption of
these sutures was achieved through the action of
Poly(L-lactide-co-ε-caprolactone) mononuclear and multinuclear macrophages which were
confined into the implant and sequestered by the fibrous

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connective tissue capsule. These sutures thus were shown to antimicrobial activity, but also anesthetic and antineoplastic
maintain good strength with little or no absorption during the functions.
critical wound healing period and with minimal tissue
REFERENCES
reaction. Hydrolytic degradation studies showed that
[1] C.-C. Chu, J. A. von Fraunhofer and H.P. Greisler
changes in mechanical properties of the copolymer were
(eds), ―Wound Closure Biomaterials and Devices‖,
found to be strongly dependent on changes in the value of
Boca Raton, Florida, CRC Press, Inc., 1996.
Mn [9].
[2] B.S. Bloom and D. J. Goldberg, ―Suture Material in
Cosmetic Cutaneous Surgery‖, J. Cosmet. Laser Ther.,
Polyhydroxyalkanoates (PHAs)
9, 41, 2007.
PHAs are polyesters produced by microorganisms (like
[3] DemeTECH. Available at:
Alcaligenes eutrophus or Bacillus megaterium) as energy
http://www.demetech.us/suture-specs.php.
storage materials [25–27]. The most common PHA, poly(3-
[4] R. L. Williams and D. G. Armstrong, ―Wound Healing:
hydrobutyrate) (PHB), is a semicrystalline polyester
New Modalities for a New Millennium‖, Clin. Pediatr.
(structures of different PHAs are presented in Figure 6), that
Med. Surg., 15, 117, 1998.
undergoes hydrolytic degradation by surface erosion, these
[5] T. Al-Abdullah, A. C. Plint and D. Fergusson,
properties making it an attractive material for controlled
―Absorbable Versus Nonabsorbable Sutures in the
release applications. Due to its relatively high melting point
Management of Traumatic Lacerations and Surgical
and rapid crystallization, the entrapment of drug is
Wounds: A Meta-Analysis‖, Pediatr. Emerg. Care, 23,
technically difficult.
339, 2007.
[6] B. C. Benicewicz and P. K. Hopper, ―Polymers for
Absorbable Surgical Sutures – Part II‖, J. Bioact.
Compat. Polym., 6, 64, 1991.
[7] R. H. Caulfield, A. Maleki-Tabrizi, H. Patel, F.
Coldham, S. Mee and J. Nanchahal, ―Comparison of
Zones 1 to 4 Flexor Tendon Repairs Using Absorbable
and Unabsorbable Four-Strand Core Sutures‖ , J. Hand
Surg. Eur., 33, 412, 2008.
[8] L. S. Nair and C. T. Laurencin, ―Biodegradable
Polymers as Biomaterials‖, Prog. Polym. Sci., 32, 762,
2007.
[9] C. K. S. Pillai and C. P. Sharma, ―Absorbable Polymeric
Fig. 6. Structures of the most known PHAs Surgical Sutures: Chemistry, Production, Properties,
Biodegradability, and Performance‖, J. Biomater. Appl.,
The copolymers with 3-hydroxyvalerate, P(3HB-co- 25, 291, 2010.
3HV)s, have similar semicrystalline properties, though their [10] H. Planck, M. Dauner and M. Renardy (eds), ―Medical
slower rates of crystallization result in matrices with Textiles for Implantation‖, Berlin, Springer-Verlag,
different properties. PHB and P(3HB-co-3HV) matrices lose 1990.
mass very slowly when compared to bulk-degrading PGA [11] D. E. Perrin and J. P. English, ―PGA and Polylactide‖,
systems. P(3HB-co-3HV) melting point is 175°C and glass in: A. J. Domb, J. Kost and D. M. Wiseman (eds),
transition temperature 15°C, tensile strength 40MPa (close to ―Handbook of Biodegradable Polymers‖, The
that of PP). It sinks in water (while PP floats), which Netherlands, Harwood Academic Publishers, pp. 3–27,
facilitates its anaerobic biodegradation in sediments. The 1997.
biodegradation can be controlled by tuning the composition [12] J. C.Middleton and A. J. Tipton, ―Synthetic
of the copolymer [9]. The biocompatibility is good, it is fully Biodegradable Polymers as Orthopedic Devices‖,
nontoxic [28] and, hence, suitable for medical applications. Biomaterials, 21, 2335, 2000.
However, the commercialization of PHA sutures is impeded [13] J. C.Middleton and A. J. Tipton, ―Synthetic
by the high cost of production. Biodegradable Polymers as Medical Devices‖, Med.
Plast. Biomater., 30, 1998; available at:
III. CONCLUSION http://www.mddionline.com/article/synthetic-
Over the last decades, surgical suture materials have biodegradable-polymers-medicaldevices.
proved to be high competitive products of a mature industry. [14] J. Siripitayananon, R. Molloy, S. Bunkird, A. Kleawkla,
New sutures are constantly developed in order to better R. Panjakha and P. Chooprayoon, ―Effects of Hot-
respond to specific surgical needs. Basic materials are Drawing and Annealing on the Morphology and
modified depending on intended applications and to provide Mechanical Properties of Biodegradable Polyester
the surgeon with a suture material of optimal quality. The Monofilament Fibers‖, Int. Polym. Process., 23, 161,
modern surgery imposes requirements that biocompatible 2008.
resobable synthetic materials are able to fullfill, but the next [15] L.-T. Lim, R. Auras and M. Rubino, ―Processing
step necessitates further progress in this area: the production Technologies for Poly(Lactic Acid)‖, Prog. Polym. Sci.,
of novel strong and elastic threads made of biocompatible 33, 820, 2008.
absorbable natural polymers, such as polyoxyalkanoates, [16] M. Jalabert, C. Fraschini and R. E. Prud‘Homme,
collagen, chitin, alginate, etc. ―Synthesis and Characterization of Poly(L-Lactide)s and
Therefore, researchers increasingly focus on the new Poly(D-Lactide)s of Controlled Molecular Weight‖, J.
generations of sutures, materials that can achieve not only Polym. Sci., Part A: Polym. Chem., 5, 1944, 2007.

333
 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

[17] K. Takizawa, H. Nulwala, J. Hu, K. Yoshinaga and C. Copolymer of L-Lactide and ε-Caproactone for Potential
J. Hawker, ―Molecularly Defined (L)-Lactic Acid Use as an Absorbable Monofilament Surgical Suture‖, J.
Oligomers and Polymers: Synthesis and Mater. Sci. Mater. Med., 16, 699, 2005.
Characterization‖, J. Polym. Sci., Part A: Polym. Chem., [23] K.-K. Yang, X.-L. Li and Y.-Z. Wang, ―Poly(p-
46, 5977, 2008. Dioxanone) and its Copolymers‖, J. Macromol. Sci.
[18] R. A. Miller, J. M. Brady and D. E. Cutright, Polym. Rev., 42, 373, 2002.
―Degradation Rates of Oral Resorbable Implants. [24] P. B. Maurus and C. C. Kaeding, ―Bioabsorbable
Polylactates and Polyglycolates: Rate Modification Implant Material‖, Oper. Tech. Sports Med., 12, 158,
With Changes in PLA/PGA Copolymer Ratios‖, J. 2004.
Biomed. Mater. Res., 11, 711, 1977. [25] N. Jacquel, C.-W. Lo, Y.-H. Wei, H.-S. Wu and S. S.
[19] P. Gunatillake, R. Mayadunne and R. Adhikari, ―Recent Wang, ―Isolation and Purification of Bacterial Poly(3-
Developments in Biodegradable Synthetic Polymers‖, hydroxyalkanoates)‖, Biochem. Eng. J., 39, 5, 2008.
Biotechnol. Annu. Rev., 12, 301, 2006. [26] R. C. S. Rocha, L. F. Silva, M. K. Taciro and J. G. C.
[20] C. E. Astete and C. M. Sabliov, ―Synthesis and Pradella, ―Production of Poly(3-hydroxybutyrate-co-3-
Characterization of PLGA Nanoparticles‖, J. Biomater. hydroxyvalerate) P(3HB-co-3HV) with a Broad Range
Sci. Polym. Ed., 17, 247, 2006. of 3HV Content at High Yields by Burkholderia
[21] D. F. Farrar and R. K. Gillson, ―Hydrolytic Degradation sacchari IPT 189‖, World J. Microbiol. Biotechnol., 24,
of Polyglyconate B: The Relationship Between 427, 2008.
Degradation Time, Strength and Molecular Weight‖, [27] A. J. Anderson and E. A. Dawes, ―Occurrence,
Biomaterials, 23, 3905, 2002. Metabolism, Metabolic Role, and Industrial Use of
[22] Y. Baimark, R. Molloy, N. Molloy, J. Siripitayananon, Bacterial Polyhydroxyalkonoates‖, Microbiol. Rev., 54,
W. Punyodom and M. Sriyai, ―Synthesis, 450, 1990.
Characterisation and Melt Spinning of a Block [28] A. Steinbüchel, ―Biopolymers‖, Weinheim, Wiley-
VCH, vol. 10, 2002.

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Network Macromolecular Structures. The

Crosslinker Effect
Loredana E. NITA, Manuela T. NISTOR, Aurica P. CHIRIAC, Iordana NEAMTU
“Petru Poni” Institute of Macromolecular Chemistry
Grigore Ghica Voda Alley No. 41-A, 700487 IASI, Romania
[email protected]

Abstract — The study presents the possibility to prepare copolymers based on 2-hydroxyethyl methacrylate
using two variants of comonomers: ethylene glycol dimethacrylate (1) and respectively 3, 9- divinyl -2, 4, 8, 10-
tetraoxaspiro[5.5]-undecane (2) that act as crosslinkers for the methacrylate networks. All these monomers are
well known for their use in the bio- and photodegradable polymers preparation as well as to generate gel
structures. The chemical structure and composition of the copolymers – synthesized through redox
polymerization process using ammonium persulfate and N,N,N’, N’ –tetramethylethylenediamine as initiator
pair were confirmed by FT-IR spectroscopy. The transparent gel structures were prepared in ethylene glycol.
The influence of the comonomers type upon gel copolymers formation was put into evidence by the swelling
behavior of the polymeric structure. The swelling effected at 37C differentiates the crosslinker comonomers,
attributing a better performance to the 3, 9- divinyl -2, 4, 8, 10-tetraoxaspiro[5.5]-undecane. The morphological
information concerning the studied polymeric compounds by SEM evidenced the differences between the
hydrogels with respect to crosslinker type and its quantity in the monomer feed. Also the thermal stability is a
function of the type and quantity of the crosslinker. The study underlines the possibility to optimize the network
macromolecular structure using a properly crosslinker choice, taking into account the potential application in
biomedical and sensors domain.
Index Terms — biotechnological applications, crosslinker, hydrogel, network structures, poly(orthoesters)

makes this polymer compatible with water, whereas the

I. INTRODUCTION
hydrophobic methyl groups and backbone impart hydrolytic
Hydrogels are hydrophilic homopolymers or copolymers
stability and supports the mechanical strength of the polymer
with three dimensional network structures that undergo
matrix. HEMA copolymers have also been investigated as
extensive swelling in water and found a wide variety of
carriers for enzyme and protein immobilization, as
applications in medical, pharmaceutical and related fields,
absorbents for chromatographic applications, and as
e.g. artificial organs, contact lenses, wound dressings and
scavengers for removing metal ions from solution [12–15].
drug delivery systems [1 - 3]. Because of the swelling
HEMA can be polymerized and crosslinked easily and the
capacity, their structure is similar to natural tissue [4, 5].
properties of proper hydrogels are dependent upon their
Also they found an extremely favorable field of applications
method of preparation, polymer volume fraction, degree of
in agriculture, food industry, photographic technology and
crosslinking, temperature and swelling agent.
others.
Poly(orthoesters) have attracted considerable interest for
Hydrogels do not dissolve in water at physiological
the controlled delivery of therapeutic agents within
temperature and pH, but they swell considerably in an
biodegradable matrices. This interest is due primarily to
aqueous medium [6] and demonstrate extraordinary capacity
poly(orthoesters) being susceptible to acid catalysed
(>20%) for imbibing water into the network structure. Gels
hydrolysis. Hydrolysis proceeds via the protonation of an
exhibiting a phase transition in response to change in
alkoxy oxygen followed by bond cleavage, with
external conditions such as pH, ionic strength, temperature
pentaerythritol, aliphatic acid and the diol or mixture of diols
and electric currents are known as ―stimuli-responsive‖ or
as degradation products. As the hydrolysis of
―smart‖ gels [7]. Being insoluble, these three-dimensional
poly(orthoesters) requires an initial protonation, these
hydrophilic networks can retain a large amount of water that
polymers may be considered pH sensitive, being stable in
not only contributes to their good blood compatibility but
basic conditions [16].
also maintains a certain degree of structural integrity and
In this study, the effects of the two crosslinking agents :
elasticity [8]. Thus, crosslinked polymer networks formed by
ethylene glycol dimethacrylate and an orthoester type named
free radical polymerization of ethylene glycol methacrylates
3, 9-divinyl-2, 4, 8, 10 - tetraoxaspiro[5.5]-undecane) on the
and dimethacrylates have been found attractive as hydrogel
structure, water absorption, morphology of the network and
matrices since they do swell in aqueous media to certain
thermal stability of the HEMA – based hydrogels were
extend depending on the crosslinking density, but do not
investigated. The hydrogels are aimed to be matrices for
dissolve. 2-hydroxyethyl methacrylate (HEMA) based
bioactive compounds entrapment or for sensor applications.
hydrogels are inert to normal biological processes, show
resistance to degradation, are not absorbed by the body and
II. EXPERIMENTAL
can be prepared in a variety of shapes and forms. The
crosslinked 2-hydroxyethyl methacrylate hydrogels because Materials
of their hydrophilic character and potential biocompatibility 2-hydroxyethyl methacrylate (HEMA) from Aldrich
have been of great interest to biomaterial scientists for many (purity 97%) was purified by passing it through an inhibitor
years [9-11]. The presence of hydroxyl and carboxyl groups removal column (for removing hydroquinone and

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hydroquinone monomethyl ether). 3,9 – divinyl -2,4,8,10 - isothermal condition were following in nitrogen atmosphere
tetraoxaspiro[5.5]-undecane (U) (purity 98%) and ethylene with a 50 ml/min flow rate. 7.5-8 mg of polymeric mass
glycol dimethacrylate (EGDMA) (purity 99%) as were heated from 30 to 600º C.
crosslinking comonomers were purchased from Aldrich.
II. RESULTS AND DISCUSSION
Ammonium peroxodisulfate (APS, Merck) and N,N,N‘,
Polymerization techniques based on addition, such as free
N‘ –tetramethylethylenediamine (Sigma Aldrich, TEMED)
radical chain growth crosslinking copolymerization of
were used as the redox initiator pair. Ethylene glycol was
HEMA and EGDM, are usually used for the preparation of
used as reaction medium and distilled water was used in the
polymers, which are subsequently converted into hydrogels,
swelling studies.
by moderate crosslinking of the polymeric chains in fairly
Hydrogel preparation
concentrated solutions.
The hydrogels based on hydroxyethyl methacrylate were
It was evidenced in the literature that the incorporation of
prepared by simultaneous redox polymerization and
spiroacetal groups in the polymer structures improves the
crosslinking in solution of ethylene glycol. The monomers
solubility and the adhesive properties [17]. More than that,
HEMA, EGDMA or U concentration in ethylene glycol as
the polymers which include these moieties are stable in base,
reaction medium is 8%. EGDMA or U as a crosslinking
hydrolyze at very slow rates at the physiological pH of 7.4,
agent was used at two concentrations 1 and 5 wt % with
and become progressively more labile as the pH is lowered.
respect to HEMA content. APS and TEMED were used as
Also, these kinds of comonomers induce good oxidative and
initiators in a 1:1 wt ratio, at concentrations of 0.6 wt %
thermal stability, are good fiber formers, and the prepared
each of them with respect to the total amount of monomers.
films present good flexibility and tensile strength [18]. These
A typical procedure for the copolymerization can be
characteristics are attributed to the properties inherent into
described as follows: HEMA 1 ml and EGDMA (0.02 mL)
the spiroacetal ring: stiffness, which is higher than
or U (0.02 g) were dissolved in 22 mL of ethylene glycol,
cycloaliphatic rings but lower than aromatic rings;
then APS (1.2 mL water solution of 1%) and TEMED (0.016
interactions on ether oxygen such as hydrogen bonds or
mL) were added into the monomer solution mixture,
coordinate bonds with other functional groups, and
respectively. The solution was stirred until thoroughly
bulkiness. Different researchers described the developments
mixed. The samples of about 2 mL were polymerized
in synthesis of alternating poly(ester–ether)s from
stationary in 5 mL glass tubes (7 mm I.D) as the
spiroortho-esters, which were also considered biodegradable
polymerization reactors, for 24 hr at room temperature to
and useful for biomedical applications [19, 20].
ensure complete polymerization.
Fig. 1 presents the FTIR spectra for the samples oh
The copolymers samples obtained in the form of long
hydrogels based on HEMA crosslinked with EGDMA (1 and
cylinders were removed from the tubes and placed in 60 mL
5 wt % in the monomer phase) and U (1 and 5% in the
glass sample bottles filled with deionized water. Then they
monomer phase). Firstly, from the FTIR spectrum depicted
were washed within distilled water at room temperature for
in Fig. 1, the presence of the main comonomer in the
24 hours to remove any unreacted monomers and physically
hydrogel structure is confirmed by the hydroxyl and strong
entrapped reaction components and the purity is verified by
carbonyl bands appearing at 3500 cm -1 (O-H stretching) and
UV spectroscopy of the washing waters.
1730 cm-1 (C=O stretching), respectively. Also, there are
Finally the samples were dried by lyophilization. The
evidently the bands at 1172 cm-1 (O-C-C stretching), 2951
dried samples were stored in desiccator at room temperature
cm-1 (asymmetric stretching of methylene group) and 1454
until tested in experiments of swelling, spectroscopy, SEM
cm-1 (O-H bending).
and thermal stability analyses.
The FTIR spectra are used to confirm the consumption of
Fourier Transform Infra-Red Spectroscopy
C=C bonds in HEMA, EGDMA and U. In the spectra, the
FTIR spectra were recorded on a Vertex Brucker
absorbance change of the peak at 1635 cm-1 (C=C stretching)
Spectrometer in the absorption mode ranging from 400 to
estimates the conversion of vinyl bonds in the samples and
4000 cm-1, at 4 cm -1 resolution, as an average of 64 scans.
their consumption during the polymerization.
Equilibrium swelling experiments
The absorbance of the peak at 1730 cm-1 (C=O stretching)
The equilibrium swelling degree SR of the hydrogels was
was picked as standard. The spiroacetal moieties inclusion is
determined by the gravimetric method, in the buffer
also confirmed by the new strong bands in the region of
solutions: Na2HPO4 / CH3COOH for pH 5.5 and 7.4, at 22
1000 – 1200 cm-1 (due to ether C-O-C stretching and C-H
and 37C, by applying the equation (1) :
in plane bending) and at ~ 1715 cm-1 (due to C=O stretching
Wt  WO of conjugated ether). The supplementary absorption at 2887
SR  X 100 (1)
cm−1 is attributed to the -CH - CH2 -symmetric stretching
WO
from U. The carbonyl peak of the acrylate of EGDMA
where Wt is the weight of the swollen gel at time t and Wo appears at 1730 cm-1 and the lactone carbonyl at 1764 cm-1.
is the weight of the dried gel at time 0. Secondly, in a general view, the spectra of HEMA based
Scanning electron microscopy gels are almost similarly, but with the exception of a peak at
SEM microphotographs were obtained by using Quanta about 1573 cm -1 which can be assigned to the stretching of
200 with EDAX - Elemental Analysis System. The samples the COO- group [21]. As it can be seen for both crosslinking
have been cross-sectioned and the morphological structure comonomer EGDMA and U, the intensity of this peak
was investigated in an accelerating voltage of 10.60 kV and increases comparative to p(HEMA) as a function of
high vacuum. crosslinking density, respectively the increase of cross-linker
Thermal analysis concentration from 1 to 5% in the monomer phase. The
The thermal behavior of the polymers was evidenced by aspect is more evidenced for the sample hydrogel with
using a STA 449F1 Jupiter model (Netzsch-Germany) EGDMA.
system at heating rate of 10 °C/min. Experiments under non-

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p(HEMA-EGDMA) (99/5)
p(HEMA-U) (95/5)

p(HEMA-U) (99/1)

p(HEMA-EGDMA) (99/1)

p(HEMA)

p(HEMA)

4500 4000 3500 3000 2500 2000 1500 1000 500

4500 4000 3500 3000 2500 2000 1500 1000 500
-1
-1 Wavenumber, cm
Wavenumber, cm

Fig. 1. FTIR spectra for the hydrogel samples based on HEMA crosslinked with EGDMA and U

The crosslinkers have pronounced effect on the swelling and U in the feed mixture of the polymerization recipe. In
ratio. In the swelling behavior of the hydrogels, the this study we have chosen two values for the crosslinker
percentage swelling increases with time but after a while amount: 1 and 5 % from the monomer mixture. In Table 1
constant percentage swelling is observed. This value of there were presented the equilibrium swelling degrees SR
swelling percentage represents the equilibrium swelling. determined at 22 and 37 oC, for pH 5.5 and 7.4, taking into
The effect of the degree of crosslinking on the swelling account the potential applicability for the sensitive materials
was investigated by varying the concentration of EGDMA at the environmental parameters (temperature and pH).

TABLE 1 EQUILIBRIUM SWELLING DEGREE SR FOR THE HYDROGEL SAMPLES

Temperature, 1% EGDMA 5% EGDMA 1% U 5% U
o
C pH 7.4 pH 5.5 pH 7.4 pH 5.5 pH 7.4 pH 5.5 pH 7.4 pH 5.5
o
22 35.68 28.57 39.64 36.40 38.40 39.33 40.02 38
37o 29.65 17.53 34.22 39.38 46.01 33.01 47.96 45

From the data presented in Table 1 it is observed that the absorbent materials for different biotechnological
equilibrium swelling degree SR determined in buffer applications, such as drug delivery or tissue engineering.
solution increases as the extent of crosslinking grows, and its Fig. 2 presents the SEM images of the pHEMA based
values demonstrate the temperature and pH sensitivity of the hydrogel (a), crosslinked with 5%EGDMA (b) and
hydrogel samples. Also, the spiroacetal moieties in U crosslinked with (5%) U (c). In detail are the SEM
induce higher swelling degree than the hydrogel with 5 % micrographs for hydrogels crosslinked with 1% EGDMA (b)
EGDMA. Usually the swelling degree is expected to and 1% U (c).
decrease with increasing crosslinking. Surprisingly, in an As it is observed in the SEM images, the hydrogels
inherent contradiction the water absorption is more porous structure consists of distorted interconnected
significant for the relatively high degree of crosslinking spherical voids separated by walls. These walls themselves
(with 5% of EGDMA or U) than for the hydrogel with a low have an unusual nanoscale porous structure with voids from
degree of crosslinking (with 1% of EDGMA or U). These the evacuated droplets of the organic phase (ethylene
results reflect the existence of two absorption mechanisms in glycol).
the HEMA based hydrogel: absorption within the pHEMA The SEM images reflect two main conclusions: firstly, the
walls through interaction with the hydrophilic polymer and crosslinked hydrogel with 5% EGDMA and 5% U have
absorption within the porous structure through capillary structures that are reminiscent of a typical pHEMA
action. The literature also [22, 23] describes three different hydrogel. Secondly, the morphology of the hydrogels with
diffusion mechanisms for the transport of water through higher degree of crosslinking (samples with 5% of EDGMA
crosslinked pHEMA gels, which depend on the crosslinker or U) is a porous structure completely different comparative
content: a pore flow mechanism for low to pHEMA hydrogels with EGDMA 1% or U 1%.
crosslinking content, a water-matrix interaction mechanism These hydrogels are able also to swell with greater
for higher crosslinking content and an intermediate amount of water, as it is reflected by the SR values in the
mechanism at intermediate crosslinker concentration. Our swelling experiment (Table 1). The more porous structures
study on the pHEMA gels fulfills these aspects. At the same and high surface area enhance capillary action and yield the
time, the synthesis of hydrogels that combine the water large amount of water absorbed.
absorption through hydrophilic interactions and through In Table 2 are presented the main characteristic temperatures
capillary action can be used to synthesize better water- in the decomposition process of the dried hydrogel samples.

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As it can be seen from the listed results there were found differences between the thermal behaviors

Fig. 2. SEM micrographs of the pHEMA based hydrogel (a), crosslinked with 5%EGDMA (b) and crosslinked with (5%) U (c). In detail are the SEM
micrographs for hydrogels crosslinked with 1% EGDMA (b) and 1% U (c).Magnification: 1000X.
TABLE 2. THE MAIN CHARACTERISTIC TEMPERATURES IN THE DECOMPOSITION PROCESS OF THE HYDROGEL SAMPLES
Sample First process Second process Residual
Ti oC Tmax oC Tf oC Ti oC Tmax oC Tf oC mass. %
pHEMA - - - 332 362 415 0.1
p(HEMA-EGDMA 218 238 275 335 366 454 0.09
1%)
p(HEMA-EGDMA 141 208.6 242.5 335.5 368 434.3 0.76
5%)
p(HEMA-U 1%) - - - 345 372 426 0.83
p(HEMA-U 5%) 318.5 348.9 352.3 391 407 446 1.94
Ti, Tf—onset and final temperature of the thermal decomposition step, Tmax—maximum temperature of decomposition

P(HEMA) hydrogels crosslinked with 1 and 5 % EGDMA

ACKNOWLEDGEMENTS
and with 5% U present a thermal decomposition process in
This work was supported by CNCSIS-UEFISCSU-
two stages comparative with P(HEMA) and P(HEMA-U
ROMANIA, project number PN II-RU No. 53/10.08.2010,
1%) that have only one process of decomposition. As it is
code 656, entitled: New hydrogel with biomedical
expected, the presence of the crosslinking comonomer 3,9 –
aplication.
divinyl -2,4,8,10 - tetraoxaspiro[5.5]-undecane (U)
positively affects the thermal stability of the copolymers, REFERENCES
because of the spiro acetal ring that controls the thermal [1] N.A. Peppas, P. Bures, W. Leobandung, H. Ichikawa,
properties. Thus, it is observed for P(HEMA-U 5%) Tmax „Hydrogels in pharmaceutical formulations‖, European
registered an increase with about 40 o comparative to Journal of Pharmaceutics and Biopharmaceutics 50
P(HEMA) and P(HEMA-EGDMA 1 or 5%). No significant (2000) 27-46.
thermal stability results were obtained by crosslinking with [2] G.U. Ostrovidova, A.V. Makeev, M.M. Shamtsian,
EDGMA comparative to P(HEMA). ―Polyfunctional film coatings for medical use‖, J Mater
Sci Eng., 23(2003), pp. 545–50.
III. CONCLUSIONS
[3] M.R. Razaak, D. Darwis, R. Sukimo, ―Irradiation of
The study presents the synthesis of 2-hydroxyethyl
polyvinyl alcohol and polyvinyl pyrollidone blended
methacrylate based hydrogels by crosslinking with one of
hydrogel for wound dressing‖, Radiat Phys Chem 62
the two crosslinkers: ethylene glycol dimethacrylate and 3,9
(2001), pp.107–13.
– divinyl -2,4,8,10 - tetraoxaspiro[5.5]-undecane. The
[4] DG Castner, BD Ratner, ―Biomedical surface science:
hydrogels were prepared by simultaneous redox
foundation to frontiers‖, Surf Sci 500 (2002), pp. 28–
polymerization and crosslinking in solution of ethylene
60.
glycol, by using ammonium peroxodisulfate and N,N,N‘, N‘
[5] KY Lee, DJ Mooney, ―Hydrogels for tissue
–tetramethylethylenediamine as the redox initiator pair. The
engineering‖, Chem Rev 101 (2001), PP. 1869–79.
transparent gel structures were prepared in ethylene glycol.
[6] NA Peppas, Y Huang, M Torres-Lugo, JH Ward, J
The influence of the crosslinker type is estimated and the
Zhange, ―Physiochemical foundation and structure
hydrogels are characterized from the viewpoint of chemical
design of hydrogel in medicine and biology‖, Annu Rev
structure, swelling behavior, morphology and thermal
Biomed Eng 2 (2000), pp. 9–29.
stability, by FTIR spectroscopy, equilibrium swelling degree
[7] C Lingyun, T Zhigang, D Yumin, ―Synthesis and pH
SR determination, SEM and TGA.
sensitivity of carboxymethyl chitosan based
The study underlines the possibility to optimize the
polyampholyte hydrogel gel for protein carrier
network macromolecular structure using a properly
matrices‖, Biomaterials, 25 (2004), pp. 3725– 32.
crosslinker choice.
[8] Q Li, J Wang, S Shahani, DDN Sun, B Sharma, JH
Elisseeff, ―Biodegradable and photocrosslinkable

338
 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

polyphosphoester hydrogel‖, Biomaterials 27 (2006), Fritzinger, S.Y. Ng, D.W.H. Penhale, ―In vitro and in
pp. 1027–34. vivo release oflevonorgestrel from poly(ortho esters): I.
[9] C.C.R. Robert, P.A. Buri, N.A. Peppas "Influence of the Linear polymers‖, J Controlled Release, 1(3)(1985), pp.
Drug Solubility and Dissolution Medium on the Release 225-232.
from Poly(2-hydroxyethyl methacrylate) Microspheres," [16] J. Heller, J. Barr, S. Y. Ng, K. S. Abdellauoi, R. Gurny,
J. Controlled Release, 5 (1987), pp. 151-157. ―Poly(ortho esters): synthesis, characterization,
[10] K. Kejlova, J. Labsky, D. Jirova, H. Bendova, properties and uses‖, Adv. Drug Delivery Rev. 54(7),
―Hydrophilic polymers-biocompatibility testing in vitro‖ 2002, pp. 1015-1039.
Toxicol. In Vitro, 19 (2005), pp. 957-62. [17] F.V. Zalar, ―A New Spiroacetal Polymer‖,
[11] G. A. Hutcheon, C. Messiou, R. M. Wyre, M. C. Davies Macromolecules, 5 (5) (1972), pp. 539-541.
and S. Downes, ―Water absorption and surface [18] WJ Bailey, H Iwama, R Tsushima , ―Synthesis of
properties of novel poly(ethylmethacrylate) polymer elastomers by cationic polymerization with expansion in
systems for use in bone and cartilage repair‖, volume‖, J Polym Sci: Symp. 56 (1976), pp. 117–27.
Biomaterials, 22(2001), pp. 667-676. [12] M. Y. Arica, [19] T Moore, R. Adhikari, P. Gunatillake, ―Chemosynthesis
V. Hasirci, N. G. Alaeddinoglu, ―Covalent of bioresorbable poly(g-butyrolactone) by ring-opening
immobilization of α-amylase onto pHEMA polymerisation: a review‖, Biomaterials, 26 (18)
microspheres: preparation and application to fixed bed (2005), pp. 3771–3782.
reactor‖, Biomaterials, 16 (10)(1995), pp. 761-768. [20] S Zalipsky, C Gilon, A Zilkha, „Attachment of drugs to
[12] B. Salih, A. Denizli, B. Engin, E. Piskin, ―Adsorption of polyethylene glycols‖, Eur. Polym. J. 19 (12), (1983),
heavy metal ions onto dithizone-anchored poly pp. 1177–1183.
(EGDMA-HEMA) microbeads‖, Talanta, 46(5)(1998) [21] L. Ferreira, M.M. Vidal, M.H. Gil, ―Evaluation of
pp 1205-1213. poly(2-hydroxyethyl methacrylate) gels as drug delivery
[13] J. Kahovec, J. Coupek, ―Chemical Modification of systems at different pH values‖, Int J Pharmaceutics 194
Macroreticular 2-Hydroxyethyl Methacrylate (2000), pp. 169–180.
Polymers‖, React. Polym., 8(1988), pp. 105-11. [22] SJ Wisniewski, DE Gregonis, SW Kim, JD Andrade,
[14] MF Refojo, ―Hydrophobic interactions in poly(2- ―Diffusion through hydrogel membranes. 1. Permeation
hydroxyethyl methacrylate) homogeneous hydrogel‖, J of water through poly(2-hydroxyethyl methacrylate) and
Polym Sci Part A1 Polym Chem, 5(1967), pp.3103–8. related polymers‖ In: Andrade, J.D. (Ed.), Hydrogels for
[15] J Heller, DWH Penhale, RF Helwing, BK Fritzinger, Medical and Related Applications, ACS Symposium
―Release of norethindrone from poly(orthoesters)‖, Series 31, (1976) American Chemical Society,
Polym Eng Sci, 21 (1981), pp. 727-736 ; J Heller, B.K. Washington, pp. 80–87.

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Identification and Analysis of Sources Relative

to the Characteristics of Pharmaceutical
Innovation
Maia IORDATII, Alain VENOT, Catherine DUCLOS
LIM&BIO EA 3969, UFR SMBH, Université Paris 13,
74 rue Marcel Cachin, 93017 Bobigny, France
[email protected]

Abstract - Every year new drugs appear on the market. Information about the therapeutic innovation is
contained in many heterogeneous sources. A physician needs to identify easily and fast the whole of the drug
innovations relative to his sphere of activity, to understand the nature of these innovations and their potential
impacts on the practice. We analyzed the available sources and the nature of this information which can be
found after the marketing drug. We explored the American, European including French sources. We
identified the sources that constitute the base in identification of pharmaceutical innovation. We explored its
structure and format to know if they could be used in the development of therapeutic monitoring tool. We
selected the sources that help to characterize pharmaceutical innovation concerning to type of innovation and
according to impact of the new drug. We proposed a tool which identifies the drugs prescribed for pathology
―type 2 of diabetes‖ using DailyMed source. The tool allows finding the type of innovation and its impact.
This work has identified the main sources of information available at the moment of drug marketing. Each of
the described sources in this paper is important, but insufficient to characterize the pharmaceutical
innovation.

Index Terms — drug sources, information seeking, medical informatics, information resources, databases.

In France, the French Agency for Sanitary Health of the

I. INTRODUCTION Health Products (Afssaps) quantifies the actual benefit
When a drug is marketed, the physician needs to position (SMR) of each innovation. This one summarizes the benefit
it in the therapeutic arsenal for deciding the pertinence of its (disease severity, efficacy, therapeutic alternatives) and the
prescription in terms of benefit/risk. To generate this opinion risks related to use of the new drug. The ASMR measures
about the new drug, he has several sources which reveal all the improvement that the drug is likely to bring compared to
the properties of the drug (monographs), or which offer a already available drugs [2]. These indicators represent a
comparison with other drugs of the same indication. Finally, summary of what a drug brings to certain moment and
the use of new drug recommendation is completely moves in time depending on the data on which they were
formalized via clinical guidelines. The time of these founded. To appreciate fully the value of these indicators,
documents production is variable: the monograph dates since the physician always need to refer to the textual document of
the date of the drug marketing, the report of evaluation is evaluation which is long.
later and retrospective, the clinical guidelines are updated In these approaches, the innovation is seen mainly in
very infrequently. These documents, being fixed in time, terms of efficacy [3, 4, 5] which is restrictive. An important
provide information at a given time. innovation can lead to an identical efficacy associated with
Each country has its specific standards to evaluate the drug less frequent side effects or less severe effects.
impact. To build objectively its judgment on a new drug is a task
Food and Drug Administration of US provides that requires time, capacities of critical analysis, familiarity
standardized information relative to the new drugs after their with the multitude of the available documents, capacity to
marketing authorization. The information specifies if it is a identify them and reach it. For example, to form an opinion
new molecular entity, a new salt or ester, a new formulation, about the PradaxaTM, an oral anticoagulant used in the
a new combination of drugs already marketed in the United prevention of venous thrombosis after the hip surgery, the
States, a new manufacturer, a new indication for a product doctor can read the clinical guidelines on the postoperative
already marketed or it is another innovation. The therapeutic anticoagulation. The document dating from 2005 does not
benefit for the patient is classified as P (Priority review contain this new drug. He may read the evaluation report of
drug), S (Standard review drug) or O (Orphan drug) [1]. This medical department rendered issued in July 2008 and he is
manner of characterizing the innovation has the disadvantage able to position this new molecule compared to the heparin
of not indicating analytically to the physician, the real of low molecular weight, but he must also be vigilant to the
interest of this one. output of more contemporary drugs having similar
From Europe, Austria is the country that presents the most characteristics (XareltoTM whose opinion is published in
detailed characterizations of the pharmaceutical innovations, January 2009 and who is not compared to the previous
described in pharmacological and therapeutic terms [2]. molecule). Finally, he must connect to the site of clinical

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trial to identify posterior clinical tests to these 2 opinions an XML structure and a certain number of terminologies to
which could inform more. describe the contents of chapters [6] (eg, clinical conditions
If the clinical guideline gives the relevant information for are coded using the list of problems VA / KP (Veterans
the physician, the other available documents do not provide Health Administration and Kaiser Permanente), which is a
exhaustive searched information and it is necessary to cross subset of SNOMED). The monograph is structured to be
several sources to have an opinion. returned to the user in XML formalism via the website
Methods of Knowledge Engineering in Medicine provide DailyMed [7].
a base that can lead to the automated extraction of The codification of some elements of the monograph is often
information available on the Web, their synthesis and a performed by the editors of drug banks, such as in France [8]
summary for their quick apprehension by the physician. indications and contraindications are coded in CIM10.
The objective of this work is to identify sources for These editors often provide enhancements of the drug
characterizing pharmaceutical innovation, to study the information with data from the literature [9, 10] and with
feasibility of developing automated tools that could assist the monographs structuring models to feed the system
physician in his scientific monitoring. This paper presents an functionality of assistant to the prescription. This
analysis of the sources which can be queried and their information is available into the drug banks which are an
treatment modalities. important source for documenting therapeutic innovation.
II. MATERIAL AND METHODS
Current clinical trials
At first we constituted the preliminary list of sources that
The banks of clinical trials contain current or completed
are used to characterize pharmaceutical innovation from
trials. Trials may include drugs that are already available on
knowledge of experts. These experts included a Doctor of
the market or in process of the development, as well as
Medicine / Doctor of Philosophy ("MD / PhD) and a Doctor
protocols of drug combinations (eg in cancer or in treatment
of Pharmacy / Doctor of Philosophy (" Pharm. D / Ph. D ")
of HIV infection).
from the Department of Medical Information of the
The metaRegister of the Current Controlled Trials bank
Avicenne Hospital.
[11] provides access to major registers making it one of the
The sources chosen by experts correspond to those used in
largest controlled trials resources in the world. Although its
their research activities and in their daily work.
primary aim is to include information about ongoing
Subsequently, we expanded the exploration of resources.
controlled trials, the metaRegister does include information
Our research strategy included an Internet research of
about some completed trials. Research is makes by
various medical web sites, such as BioMed Central,
International Standard Randomised Controlled Trial Number
Medscape, First DataBank, the sites of drug agencies in
or by keyword. The clinical trial is described in free text
Europe and U.S.A. Similarly, we researched about
topics in which drugs or combinations tested appear in the
pharmaceutical innovation via PubMed.
title, hypotheses and interventions. The target pathology of
We explored the American sources, European including
the trial is in free text in the title and in the inclusion criteria.
French.
When a drug not yet marketed is tested, it appears as a code
Among the sources analyzed we selected those that help
name. The «study hypothesis" provides explanation for its
us to characterize pharmaceutical innovation about the type
mechanism of action. But it should be noted that trial results
of innovation (new molecule, new association, new strength,
are not recorded in the bank. Its content does not provide
new formulations, etc.) and relative to the impact of new
answers to the question posed in this paper but rather
drug in terms of efficacy and safety.
information about the existence or not of an ongoing clinical
We performed a detailed analysis of the content of
research for a given disease.
retained sources. Then, we explored the format to see if they
can be used in the construction of the computerized tool of
The information from pharmacovigilance
therapeutic monitoring..
When the drug is marketed, monographs include already
III. RESULTS the side effects observed during the completed trial. But the
1. Analysis of sources on the characteristics of therapeutic side effects are gradually supplemented by those that occur
innovation during the using of drug and by those that reported in the
We defined the basic set of sources that provide information pharmacovigilance databases [12]. Unfortunately this
on pharmaceutical innovation. We have identified two types information is not public.
of information sources that characterize innovation: those The new side effects are often described in the ―case-
which compare and which does not compare the new drug reports‖ form published in journal indexed with MeSH
treatment to other existing treatments. keywords in Medline. They can next found via
bibliographical engines like PubMed.
1.1 Sources on drug therapy without comparison to other
Drug classification
The drug monographs Drug Classifications allow classifying drugs according to
From the marketing of manufactured product, his their chemical, pharmacological, therapeutic properties.
monograph (or Summary of Product Characteristics) is Examples are the ATC (Anatomical Therapeutic Chemical
available by health authorities. This monograph is divided Classification System), the supplementary concepts of
into chapters (composition, indications, contraindications, MeSH and chemical and pharmacological classifications of
etc.); the content of these chapters is in free text with a MeSH.
requirement of structuring and coding variable from one These sources can help to qualify the novelty of a
country to another. molecule, of a mechanism of action or chemical class.
The U.S.A., for example, impose a detailed description as However, it should consider the updating time of these

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sources and how they are structured. Indeed, the introduction Current Molecule, no yes
of a new class that could call into question the structure of clinical trials combination,
mechanism of
the resource. There is a risk to find innovations in classes action, efficacy,
like "not elsewhere classified", which will not be very safety
useful. Pharmaco- safety no no
vigilance
Drug Molecule, no yes
1.2 Sources on the comparisons of drug treatments classifications combination,
pharmaco-
Results of clinical trials therapeutic
For all sources already mentioned join articles indexed in class,
mechanism of
PubMed. The summary of completed clinical trials can be action
obtained from the BioMed Central database [13]. The Results of Efficacy, safety yes yes
information is structured into 4 sections: a description of the clinical trials
trial, results, interpretation of results and conclusion. Meta- Efficacy, safety yes no
analysis
Clinical Molecule, yes no
Meta-analysis guidelines combination,
The results of the meta-analysis and synthesis of literature route of
are available in the Cochrane database [14]. But they were administration,
made later after the placing on the market the new drug. The efficacy, safety
content is presented in free text.

Clinical guidelines 2. Example of tool developing for extracting information

The clinical guidelines are developed to help the physician in from the source DailyMed
the care of the patient. They are written by the expert groups As it was mentioned the most of sources provide
of scientific societies or national agencies. The clinical information on the drug from its name. Nevertheless, the
guidelines contain the results of clinical research that are practitioner needs to find information about medicines from
graded according to level of evidence prepared by the the health problem.
experts. The clinical guidelines are based on the facts and Our goal was to build a program that allows the
their content is explicit. However, as the interval between extraction of information about a health problem to show
publications is several years, the physician is confronted that the contribution of each new drug.
with the problem of obsolescence of information. Their We selected the site DailyMed to extract the maximum
structure evolves over time and differs much from a disease information about medicines. It is a source that contains
to another. In France, for example, they are available in PDF monographs for all marketed drugs in the U.S. The files are
format, a fact which makes information extraction in XML format. We used .Net technologies to extract
impossible at present. information about the pathology "type 2 diabetes‖.
The created application can extract the drug brand name
Summary of the product marketed, the name of active ingredient, the
This analysis has led to identify the main existing sources mechanism of action and the number NDA / ANDA (New
and nature of information that we can find (Table 1). Just Drug Application / (Generic) Drug Approvals).
after the marketing of the drug, the main sources are drug For pathology "type 2 diabetes" program identifies 129
products, because the file structure is quite heterogeneous
monographs published by the agencies and already
and evolves over time. We took into consideration the
structured in drug databases. At these resources are in
structures used from 1999 because we focus on
addition the publication of clinical trial results and any
pharmaceutical innovation. The NDA may even appear
publications which can be accessed from Pubmed. many times, the fact that is linked to the existence of several
Unfortunately, all sources are not exploited in the presentations of the same product. The made program allows
construction of the characterization tool of innovation. The the user to find from the indication (diabetes type 2) the
information contained within sources on comparisons of drugs that are marketed in the U.S.A. Using the
drug treatments is not structured. Its use in the computerized Drugs@FDA Database, the NDA leads us to the type of
tool of monitoring therapeutic becomes impossible. pharmaceutical innovation and the importance of this
The research of information for most of these sources is innovation. For example, we find that the product ActosTM
made from the name of the drug. with the NDA 021073 has a new molecule (pioglitazone) as
TABLE I. THE NATURE OF INFORMATION SOURCES
the type of innovation and this treatment is classified as a
Source Nature of Compara- Information priority (P).
information tive structured This example shows the limited nature of the
information classification proposed by the FDA, because the concept of
Drug Molecule, no yes pharmaceutical innovation is much larger and not limited
monographs combination,
form, route of only to characteristics specified by FDA. Similarly, it is
administration, difficult for the practitioner to understand the reduction of
pharmaco- information about the therapeutic benefit only to priority
therapeutic treatment, standard treatment or orphan.
class,
mechanism of
action, efficacy,
safety

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IV. CONCLUSION M. Absolute benefit, number needed to treat and gain in

This work has identified the main sources of information life expectancy: which efficacy indices for measuring
available at the time of marketing of the drug, which should the treatment benefit? JCE 2003; 56: 977–982.
allow to instantiate the model for each innovation. We have [4] Bolen S et al. Systematic Review: Comparative
shown that these sources are heterogeneous relative to the Effectiveness and Safety of Oral Medications for Type 2
type of information, structure and format. We created a Diabetes Mellitus. Ann Intern Med 2007; 147 (6): 389-
program that shows the possibility to get information about 400.
the type of innovation and its impact using the data and the [5] Puntmann I, Schmacke N, Melander A, Lindberg G,
classification proposed by the FDA starting the health Muhlbauer B. EVITA: a tool for the early evaluation of
problem. pharmaceutical innovation with regard to therapeutic
To create a pertinent tool for characterization of advantage, BMC Clinical Pharmacology 2010; 10 (5):
pharmaceutical innovation is necessary to use several 1-11.
sources of information. Each described sources in this paper
is important, but insufficient to characterize the drug at a [6] U.S. Food and Drug Administration, available:
time T, hence the interest for creating computerized tool that http://www.fda.gov/ForIndustry/DataStandards/Structur
will judge the contribution of the latter. edProductLabeling/default.htm
At present our team is working on modeling of [7] DailyMed, available: http://www.dailymed.nlm.nih.gov/
pharmaceutical innovation to provide its full description. For [8] Haute Autorité de Santé, available:
further we plan to use multiple sources of information with http://www.has-
purpose to judge the drug as objectively as possible via sante.fr/portail/jcms/c_672761/agrement-des-bases-de-
computerized tool of monitoring therapeutic, which will donnees-sur-les-medicaments
allow the practitioner to deliver quality medical care in short [9] American Society of Health-System Pharmacists,
time. (ASHP), available:
http://www.ahfsdruginformation.com
REFERENCES [10] Banque de Données sur le Médicament Thériaque,
[1] Drug Information: A Guide for Pharmacists. Malone P, available: www.theriaque.org
Kier K, Stanovich J. (Eds.) New York: McGraw-Hill, [11] Current Controlled Trials, avaible:
2006; pp. 533-45. http://www.controlled-trials.com
[2] Sermet C. La prise en compte de l‘innovation [12] Eudra Vigilance, avaible:
thérapeutique dans les politiques de prix et de http://eudravigilance.emea.europa.eu/highres.htm
remboursement des médicaments. RFAS 2007; 3-4:319- [13] BioMed Central, Journal of trials, avaible:
341. http://www.trialsjournal.com/
[3] Kassai V, Gueyffier F, Boissel J-P, Boutitie F, Cucherat [14] The Cochrane Colaboration, avaible:
http://www2.cochrane.org/reviews.

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Silica Nanoparticles for Improving Efficiency of

Virus-Like Particle Based Hepatitis B Vaccine
Marina ROMANOVA1, Yury DEKHTYAR1, Anna KACHANOVSKA1, Dace SKRASTINA2, Regina
RENHOFA2, Paul PUMPENS2, Aloizijs PATMALNIEKS3
1 Riga Technical University, Institute of Biological Engineering and Nanotechnology, Latvia
[email protected]
2 Biomedical Research and Study Centre, Riga, Latvia
3 University of Latvia, Riga, Latvia

Abstract – Adherence of hepatitis B virus-like particles (VLP) to silica (SiO2) nanoparticles was explored for
immunomodulation purposes. Optical absorbance measurements, transmission electron microscopy and
fluorescence microscopy were employed to study the adherence. The results demonstrated that hepatitis B
VLP + SiO2 complexes were formed. Preliminary immunological experiments with vaccination of Balb/c mice
with the VLP only and VLP + SiO2 complexes were performed. The vaccination with VLP + SiO 2 complexes
resulted in increase in antibody production in mice blood. The amount of antibodies produced strongly
depended on the concentration of SiO2 nanoparticles. The observed results suggest that SiO 2 nanoparticles
can be considered as a promising material for improving efficiency of VLP-based vaccines against hepatitis B
viral disease.
Index Terms – hepatitis B, optical absorbance, silica nanoparticles, vaccines, virus-like particles.

To study the capability of SiO2 nanoparticles to attach

I. INTRODUCTION
VLP, the optical absorbance spectra of VLP, SiO 2
Immunomodulation can be used for viral disease
nanoparticles and VLP+SiO2 mixture in buffer solutions
prevention where vaccine with immune response-modulating
were recorded and compared. The Thermo Spectronic
agents stimulates immune system to respond effectively to a
Heλios Gamma spectrophotometer was in use to record
viral disease. Virus-like particles (VLP) can be used as
absorbance spectra at wavelengths 200 – 1090 nm. The role
immune response-modulating agents. VLP have a protein
of the buffer solution was to keep pH constant. The buffer
shell derived from a real virus but do not have any genetic
solution was prepared from 20 mM Tris-HCl pH 7.8, 5 mM
viral material inside it that means that VLP are not
EDTA, 150 mM NaCl, and 1 litre distilled water. NaCl
infectious. VLP containing vaccine is injected into blood
concentration was equal to the concentration in the
vessels and VLP are delivered by bloodstream to specific
physiological solution. The concentration of SiO2
cells where they stimulate antibody production. Treatment
nanoparticles was 1 mg in 1 ml of the buffer solution. The
efficiency is higher when concentration of VLP near the
concentration of VLP was 12 μl in 1 ml of the buffer
specific cells increases. However, high concentrations of
solution that corresponded to the optical absorbance value 1
VLP in human body might result in side effects. To
(± 5%) at wavelength 260 nm. The value 12 μl was chosen
eliminate this, high concentration of VLP can be provided
after calibration procedure. It was known from experiments
only in a vicinity of the specific cells.
that Hepatitis B VLP have the optical absorbance maximum
In order to reduce the overall concentration of VLP
at 260 nm. Therefore, to make the calibration, optical
simultaneously increasing the local concentration near the absorbance for different concentrations of VLP was recorded
specific cells, a number of VLP can be attached to a and the concentration where the optical absorbance was
nanoparticle that will act as a carrier of VLP to the specific equal to 1 at 260 nm was chosen for convenience of further
cells. It is known that electrical charge is localized at the result processing.
surface of VLP [1], therefore, the latter can be attached to To verify the VLP+SiO2 adherence, transmission electron
the nanoparticle due to the electrostatic interaction if the microscopy (TEM) and fluorescence microscopy (FM) were
nanoparticle has an opposite charge. Thus, the nanoparticle employed. JEOL JEM-1200EX microscope was in use for
must have the ability for polarization. In addition, the TEM, and Leica DMI 3000 B microscope for FM.
nanoparticle must be harmless to human body. Both To record fluorescence, VLP were marked with the green
conditions are met by SiO2 nanoparticles [2,3]. FITC agent, which forms covalent bonds with VLP amino
The aim of the study was to verify capability of SiO2 acids. Fluorescence was excited at 490 nm and detected at
nanoparticles to attach hepatitis B virus-like particles and to 515 nm.
investigate the immune response of the organism after Preliminary immunological experiments were performed
vaccination with VLP-based vaccine with added SiO2 to study humoral response of Balb/c mice after vaccination
nanoparticles. with the VLP+SiO2 complexes. The vaccination was made
on days 0, 14 and 28. Mice from the control group were
II. MATERIALS AND METHODS vaccinated with VLP only diluted into sterile phosphate-
Hepatitis B VLP were synthesized by the Latvian buffered saline. Two weeks after the 3rd immunization (on
Biomedical Research and Study Centre. Certified SiO2 the day 42) all animals were bled and anti-HBc antibody
nanoparticles were bought from the Sigma-Aldrich. Size of response was detected using the direct ELISA test.
the nanoparticles was equal to 10 – 20 nm.

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III. RESULTS AND DISCUSSION The results demonstrated that the optical absorbance of
The optical absorbance spectra of the solutions (SiO2, the SiO2 and VLP+SiO2 solutions decreased after 24 hours
VLP, VLP+SiO2) were tested on time stability. To test the and precipitations formed at the bottom of the test-tube. The
time stability, the absorbance was recorded at once after precipitations could form due to gravitation forces which
preparation of the solutions and after 24 hours (Fig.1). deflect the nanoparticles towards the bottom of the test-tube.
However, the absorbance of the VLP solution did not change
1,2 after 24 hours and no precipitations formed. Therefore, it
VLP was possible to suppose that VLP remain in suspended state
1
in the buffer solutions at least within 24 hours.
Absorbance

0,8
The optical absorbance of the VLP+SiO2 solution
0,6 recorded in the experiment was compared with the
0 hours theoretical optical absorbance value in order to see if VLP
0,4
24 hours interact with SiO2 nanoparticles. According to the
0,2 spectrophotometry laws, the experimental and theoretical
values must be equal if no interaction between the particles
0
200 230 260 290 320 350 380 410 440 470 500
exists. To calculate the theoretical value, the absorbance of
Wavelength, nm the VLP solution recorded experimentally at 260 nm was
1,6 summed up with the absorbance of the SiO2 solution
1,4 SiO2 recorded experimentally at 260 nm. Results demonstrated
1,2 difference between the theoretical and the experimental
values (Fig.2). The difference becomes more pronounced
Absorbance

0,8 when the time given for VLP and SiO2 interaction increases.
0,6
That proves that VLP adhere to SiO2 nanoparticles.
0,4 0 hours
24 hours
0,2
0
200 230 260 290 320 350 380 410 440 470 500
Wavelength, nm
2,5
VLP+SiO2
2
Absorbance

1,5

0 hours
0,5
24 hours
Fig. 2. Comparison between the experimental (solid line) and theoretical
0 (dashed line) optical absorbance (at 260 nm) of the VLP+SiO2 solution.
200 230 260 290 320 350 380 410 440 470 500
Wavelength, nm
Fig. 1. Time stability of the optical absorbance of the VLP, SiO2 and Both TEM (Fig.3) and FM (Fig.4) show the adherence of
VLP+SiO2 solutions. VLP to SiO2 nanoparticles.
In case of FM, the VLP solution without the nanoparticles
has homogeneous fluorescence. When SiO2 nanoparticles are
added, VLP adhere to them and fluorescence exists only in
areas where VLP adhere to SiO2 nanoparticles.

Fig. 3. TEM micrographs of the VLP, SiO2, VLP+SiO2 solutions.

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Fig. 4. FM micrographs of the VLP and VLP+SiO2 solutions.

The results of the preliminary immunological experiment VLP+SiO2 solution. The results demonstrated that there was
demonstrated that amount of antibodies produced in Balb/c a good linear correlation (R-squared value was equal to
mice blood depended on concentration of SiO2 nanoparticles 0,929) between concentration of SiO2 nanoparticles and
in the VLP+SiO2 solution (Fig.5). The dose of VLP in the amount of antibodies produced in mice blood.
solutions was kept constant and was equal to 25 μg but Optical absorbance and microscopy measurements prove
concentration of SiO2 nanoparticles varied thus resulting in that there is physical adherence between hepatitis B VLP and
different amounts of the VLP+SiO2 complexes. VLP without SiO2 nanoparticles. The results of the immunological
SiO2 nanoparticles induced lower antibody response than in experiment evidence that vaccination with the VLP+SiO2
case of the VLP+SiO2 solution. complexes results in positive response in blood of Balb/c
mice. It allows considering SiO2 nanoparticles to be an
effective material for efficiency improvement of VLP-based
hepatitis B vaccines.
IV. CONCLUSIONS
1. Optical absorbance measurements, transmission
electron microscopy and fluorescence microscopy
demonstrate that there is a physical adherence between
hepatitis B VLP and SiO2 nanoparticles.
2. The correlation exists between increase in
concentration of SiO2 nanoparticles in the hepatitis B VLP +
SiO2 mixture and amount of antibodies produced in blood of
Balb/c mice.
3. SiO2 nanoparticles can be considered an effective
material for efficiency improvement of VLP-based
hepatitis B vaccines but further immunological studies are
Fig. 5. Influence of concentration of SiO2 nanoparticles in the VLP+SiO2 required.
solution on antibody production in blood of Balb/c mice.
REFERENCES
Fig. 6 shows increment in amount of antibody production [1] Virus Particle Explorer, Human Hepatitis B Viral
in mice blood in dependence on concentration of SiO 2 Capsid. Available:
nanoparticles in the VLP+SiO2 solution. http://viperdb.scripps.edu/info_page.php?VDB=1qgt
[2] C. He-sheng, S. Zhen-ya, and X. Li-hui, ―Properties of
nano SiO2 modified PVF adnesive‖, Journal of Wuhan
University of Technology-Mater. Sci. Ed., vol. 19, pp.
73-75, 2004.
[3] C. Sealy, ―Silica key to drug delivery‖, Nano Today,
vol. 1, p.19, 2006.

Fig. 6. Increment in antibody production in dependence on concentration of

SiO2 nanoparticles in the VLP+SiO2 solution.

To calculate the increment value, the amount of antibody

produced after vaccination with VLP only was subtracted
from amount of antibody produced after the vaccination with

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Collagen - Isolation and Perspectives of

Application of Nature Nanomaterials
Elena MOCAN, Olga TAGADIUC, Tatiana REVENCU and Viorel NACU
State Medical and Pharmaceutical University”Nicolae Testemitanu”
[email protected]
Abstract – Through the extreme diversity of tissues and types of collagen it is difficult to develop a standard
method of extraction for all types of collagen from different tissues. Two procedures based on acid- and
enzymatic-soluble collagen isolation were combined and described some advantages and disadvantages of
methods used in the present. Our results have demonstrated relatively low concentrations of collagen in the
final solutions. There is 4,7 mg/ml from theoretically 10 mg/ml of acid-soluble fraction of collagen. Here are
discussed the possibility to utilize the collagen, as fibrous structural protein with superior mechanical
properties, that provides an intriguing example of a hierarchical biological nanomaterialas, for the
construction of nanostructures with the required dimensions.

Index Terms – collagen type I, methods of isolation and purification, nanomaterials, tissue engineering

I. INTRODUCTION
Inspired by nature‘s ability to produce supramolecular
nanostructures from the bottom-up, materials scientists have
become increasingly interested in the use of biomolecules
like DNA, peptides, or proteins as templates for the creation
of novel nanostructures and nanomaterials [1].
Collagen is an exemplary type of robust biological
nanostructure built from simple building blocks. It is the
most abundant protein in modern vertebrates, comprising
approximately 30% of the total protein content and 70% of
the dry weight of human skin. Collagen provides the three-
dimensional matrix for connective tissue types such as bone
and cartilage [5].
Numerous studies have demonstrated that collagens can
induce or regulate many cellular functions and processes
such as cells differentiation, motion, communication and
apoptosis [4, 5]. But its main function is the formation of
insoluble fibrils with high strength characteristics.
Collagen is the major component of the extracellular
matrix and more than 27 genetically isoforms have been
identified. Collagen type I, II and III are the most abundant
widely used as a plastic material in different medical Fig. 1: Nanostructure of natural bone [Rho 1998]
domains, cosmetology, and in the pharmaceutical industry as Type I collagen is trimeric [(α1)2 α 2] and exists as triple
a compound that provide drugs action [3, 4]. Type I collagen helix. The helices have the typical repeats for collagen Gly-
has been described as a natural scaffold and a potential X-Y (where X and Y are mainly Pro and Hyp). Thus,
candidate for tissue engineering and reconstructive medicine proline and hydroxyproline constitute about 23% of the total
[6]. Such diverse functions are due to physical and chemical protein sequence and structure Gly-Pro-Hyp is often founded
properties of collagen protein. [4]. Its unique tertiary structure is a right-handed triple helix
At physiological conditions, the individual collagen composed of three helical peptide strands (left-handed
molecules of approximately 300 nm length and 1.5 nm polyproline II-type).
diameter aggregate longitudinally and bilaterally to Through the extreme diversity of tissues and types of
microfibrils and further to fibrils (fig. 1). Thus it is a collagen it is difficult to develop a standard method of
nanostructured carcass with possibility to carry out the extraction for all types of collagen. The number of the
assembly of protein complexes [1]. Collagen consists of covalent intermolecular interactions in collagen structure
tropocollagen molecules that have lengths of L ~280 nm and increases in time and frequently determines almost full
diameters of ~1.5 nm, leading to an aspect ratio of ~190 [12– insolubility in solvents utilized to dissolve proteins [7].
14]. Staggered arrays of tropocollagen molecules form The main task of our study was to analyze the known
fibrils, which arrange to form collagen fibers (Fig. 1). methods of collagen isolation and purification. Obtained
solid-phase collagen could be a promising platform for
generation of new and interesting nanostructured materials
[11]

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II. MATERIAL AND METHODS fibrils and the origins of toughness remain largely unknown
The collagen source. Type I collagen was isolated from [12].
steer (3 years old) flexor bovine tendon. Fixed mass of Some experimental efforts focused on the deformation
tendon was suspended in cold distilled water at 4 0 C and mechanics of collagen fibril at nanoscale, including the
water was changed two times per day for three days. The characterization of changes of D-spacing and fibril
tendon fibers were cut into small pieces (1 cm in length) and orientation [13-15], analyses that featured x-ray diffraction
pulverized in a mill after that. Pieces were dried 24 h in the [13] and synchrotron radiation experiments [14]. Other
thermostat at 400 C. experimental studies were focused on the averaged response
Method of collagene isolation of arrays of collagen fibrils, considering nanoscale
The procedure is based on the extraction of collagen from deformation mechanisms [12, 24].
the tendon pieces in organic acid (0,5M СН3СООН) in the To develop a fundamental and quantitative understanding
presence of 5mM EDTA and pepsin with concentration 0,05 of collagen mechanics, it is critical to develop theoretical
g per 100 g of tissue, pH = 2,5 - 3,0 for 48-96 h at 40C. models encompassing the mesoscopic scales between the
atomistic and macroscopic levels [12]. There exists no
III. RESULTS AND DISCUSSION
model that links the properties of individual molecules with
After testing several collagen isolation‘ procedures [2, 4,
the overall mechanical response of fibrils or fibers,
5] we have chose the method based on acetic acid
considering the different types of chemical bonding and
dissolution of collagen fibers with some modifications. One
nanoscale mechanics and geometry. The role of the
of them is introduction of the neutral salt or low ionic
staggered structure and the reasons for the specific length
strength acidic solutions.
scales and high aspect ratio of TC molecules remain
We have combined these two procedures based on acid-
unexplained.
and neutral-salt extraction with enzymatic collagen isolation.
An improved understanding of the nanomechanics of
Several types of soluble collagen are distinguished
collagen may help in the development of biomimetic
depending on the specific protein solvent: neutral salt-
materials or for improved scaffolding materials for tissue
soluble collagen, acid-soluble collagen and enzymatic-
engineering applications [17].
soluble collagen. Thus a combined approach was developed
Buehler [12] has used a hierarchical multiscale modeling
which includes pepsin digestion in acidic solution.
scheme based on atomistic and molecular simulation to
Our results have demonstrated relatively low
describe the mechanical properties of collagen under large
concentrations of collagen in the final solutions – 4,7 mg/ml.
stretch, leading to permanent deformation or fracture. There
Although the method of extraction based on acetic acid
was shown that the key to understanding the mechanics of
and pepsin dissolution was standardized more than 40 years
collagen is to consider the interplay between the mechanics
ago, it still has two major problems.
of individual tropocollagen molecules with characteristic
First, the collagen solubility is still ill-defined due to
length scales, the intermolecular chemical interactions, and
cross-link mediated aggregation, so that the reproducibility
the mesoscopic properties arising from hundreds of
of the collagen preparations is poor. Secondly, the collagen
molecules arranged in fibrils. It was explored the mechanics
peptides, especially the short non-helical regions of collagen,
of collagen by considering different nanostructural designs,
are susceptible to proteolysis/hydrolysis during the isolation
and pay specific attention to the details of molecular and
[4, 9].
intermolecular properties and their impact on the mechanical
For this reason the utility of the acidic-extracted collagen
properties.
is limited, since the isolated material must be stored in cold
Energetic effects rather than entropic contributions govern
acetic acid solution or dried. The maximal obtainable
the elastic and fracture properties of collagen fibrils and
concentration of collagen is also limited to 10 mg/ml [4] as
fibers. The fracture strength of individual tropocollagen
estimated by wet weight and also by amino acid content. The
molecules is largely controlled by covalent polypeptide
methods of collagen isolation, purification and determination
chemistry. The shear strength between two tropocollagen
should be modified, using new strong detergents for deeper
molecules is controlled by weak dispersive and hydrogen
dilution of collagen fibers, on purpose to overcome the
bond interactions and by some intermolecular covalent
disadvantages of its partial degradation.
cross-links.
A major requirement of collagen purification the
Some studies have suggested that the length of
elimination of the antigenic components of the protein
tropocollagen molecules and strength of intermolecular
represented by the telopeptide regions of collagen type I that
interactions plays a significant role in determining the
can be more efficiently when treated with pepsin. However,
deformation mechanics, explaining some of the structural
collagen extracted from animal sources presents a small
features of collagen found in nature.
degree of antigenity, that‘s why it is considered acceptable
Key concepts that can be adopted from self-assembly
for tissue engineering in humans [4].
found in nature include molecular recognition of the single
There is an important problem to control the construction
building blocks and the formation of predictable three-
of nanostructures from collagen with the required
dimensional nanostructures [1, 9, 10].
dimensions.
Pioneered by Braun, Belcher, and their coworkers, there
Despite significant research effort over the past couple of
have been numerous examples of DNA or viruses as
decades, the geometry and typical length scales found in
scaffolds for complex nanostructured inorganic materials [8–
collagen fibrils, the deformation mechanisms under
11]. Since the nucleobase or amino acid sequence encodes
mechanical load, and, in particular, the relationship between
how these scaffolds self-assemble, a variety of programmed
those mechanisms and collegen‘s molecular and
nanostructures can be produced [1, 10, 11].
intermolecular properties, are not well understood.
Although DNA can be readily synthesized, it is composed
Moreover, the limiting factors of the strength of collagen
of a small number of similar monomers. As a result, some

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approaches have combined DNA and proteins to create [3] Miller, E.J., and K. Rhodes, R. Academic Press. p. 33-
functional nanomaterials [1]. In contrast, peptides and 64, 1982.
proteins are built from 20 proteinogenic and a wide variety [4] Rajan, N., et al., Nat. Protocols, 1, p. 2753-2758, 2007.
of non-natural amino acids. This leads to chemical diversity, [5] Xin Xiong dissertation. New Insights into Structure and
evident by the display of aliphatic, acidic, basic, or aromatic Function of Type I Collagen, p. 111, 2008.
side chains from a peptide backbone, and structural [6] Rele S., Song Y. H., Apkarian R. Qu P., Z., Conticello
complexity, manifested by the multitude of possible V. P. and Chaikof E. L., J. Am. Chem. Soc.,14, p. 129,
molecular architectures like helices, β-sheets, and tubules [1, 2007.
8]. [7] Kotch F. W. and Raines R. T., Proc. Natl. Acad. Sci. U.
Working with live systems, we can use "natural S. A., 103, p. 3028, 2006.
nanotechnology", that mean an ability to link proteins [8] Naik R. R., Stringer S. J., Agarwal G., Jones S. E. and
individually with other proteins or other substances to form Stone M. O., Nat. Mater. 1, p. 169, 2002.
complexes with desired properties. These so named [9] Ma N., Sargent E. H. and Kelley S. O., J. Mater.
collagen-binding domains can be used: Chem., 18, p. 954, 2008.
• for creating artificial surface for the cultivation of [10] Zhang S., Nat. Biotechnol., 21, p. 1171, 2003,.
eukaryotic cells; [11] Papapostolou D., Smith A. M., Atkins E. D. T., Oliver
• as drugs that accelerates wounds and burns healing; S. J., etc. Proc. Natl. Acad. Sci. U.S.A., 104, p. 10853.
• to prolong the drug effect; 2007.
• as drugs that promote early fracture consolidation; [12] Buehler M. J. PNAS. vol. 103, 33, p. 1228–1229, 2006.
• as composite materials, for implant coating [13] Hulmes, D. J. S., Wess, T. J., Prockop, D. J. & Fratzl, P.
[1, 5, 10, 11]. Biophys. J. 68, p. 1661–1670, 1995.
[14] Puxkandl, R., Zizak, I., Paris, O., Keckes, J., Tesch, W.,
IV. CONCLUSIONS
Bernstorff, S., Purslow, P. & Fratzl, P. Philos. Trans. R.
Recent studies in cell biology, nanotechnology, and
Soc. London Ser. B 357, p.191–197. 2002.
computation gave more new insights regarding the physical
[15] Sasaki, N. & Odajima, S. J. Biomech. 29, p.1131–1136,
proprieties, that in complex with the chemical one, can
1996.
regulate cell signaling and gene expression. Due to the
[16] Orgel, J. P. R. O., Irving, T. C., Miller, A. &Wess, T. J.
importance of biocompatible matrixes for tissue engineering
Proc. Natl. Acad. Sci. USA 103, p. 9001–9005, 2006.
and their application in medical technology, the availability
[17] Yung, Y. C. & Mooney, D. J., Bronozino, J. D in CRC
of native collagen should be studied by refining the
Biomedical Engineering Handbook. (CRC, Boca Raton,
collagens extraction procedure. It is very important to
FL), chap. 6, pp. 1–14, 2006.
elaborate the method of collagen isolation that give us fully
[18] Gupta, H. S., Wagermaier, W., Zickler, G. A., Aroush,
or partially soluble collagen that can be used in producing by
D. R. B., Funari, S. S., Roschger, P., Wagner, H. D. &
tissue engineering of matrices, powder, sponges, fibers or
Fratzl, P. Nano Lett. 5, p. 2108–2111, 2005.
filaments.

REFERENCES FUNDING
[1] Gottlieb D., Morin S. A., Song J. and Ronald T. J. This research work was and is supported by Academy of
Mater. Chem., 18, 3865–3870, 2008. Sciences of Moldova grants 06.420.049A,
[2] Chandrakasan, G., Torchia, D. A. and Piez, K. A., J Biol 09.819.09.02F and 11.817.09.23A
Chem, 251, p.6062-6067, 1976.

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Colloidal Nanosilver – a Product of

Nanotechnology
Corina SCUTARI1Veaceslav GONCIAR2 Ivan CEKMAN2,3 Nadejda GORCEACOVA3,4
1
Assistant professor in the department of Pharmacology and clinical pharmacy of State Medical and
Pharmaceutical University „N. Testemitanu”
E-mail: [email protected], tel. 068687788.
2
Professor, head of the department of Pharmacology and clinical pharmacy of State Medical and
Pharmaceutical University „N. Testemitanu”
3
„A.A.Bogomoleţ”, Kiev
4
Professor of the department of Pharmacology and clinical pharmacy of National Medical University

Abstract – In a review literary data and results of own investigations of colloidal nanosilver bases are
summarized. A wide range of antimicrobial action of silver, the lack of resistance to it, effective against most
pathogenic microorganisms, low toxicity, lack of data in the literature about the allergic properties , as well as
good tolerability of patients - have contributed to increased interest in silver, in many countries around the
world. Colloidal Silver is the safest and most potent natural antiseptic for the human body, that overwhelm
over 700 species of pathogens, including staphylococcus, streptococcus, bacteria dysentery, typhoid, etc. It is
proved that the water contaminated by high concentrations of bacteria became sterile after one or two hours
from the introduction of the silver in amount up to 1 mg/l and maintained for many days. The drug is actively
involved into reducing life and termination of pathogen bacteria, viruses, fungi and parasites, stimulate the
protective mechanisms of the human body. In this case, it does not affect the benefic microorganisms. Silver
by intravenous administration is successfully used for the treatment of septic arthritis, rheumatism,
rheumatic endocarditis, rheumatoid arthritis, asthma, influenza, acute respiratory infections, bronchitis,
pneumonia, purulent septic diseases, brucellosis, inside - in the treatment of gastritis, gastro-duodenal ulcers,
externally - in the treatment of sexually transmitted diseases, septic wounds and burns. The results obtained
in different studies on the effect of silver nanoparticles on the organisms are rather contradictory, but to
forget about the relevance of this issue is not worth it.

Index terms - antimicrobial activity, colloidal, nanoparticles, nanosilver, silver.

antigonorrheal effect of silver nitrate solution of 1% . This

I. INTRUDUCTION
discovery allowed to liquidate in Germany hospitals
Nanoparticles of various materials are used everywhere -
gonorrheal purulent inflammation of the eyes in the
from paint to food industry. The most "popular" are
newborn. In fact, from that moment began a new century in
nanoparticles of silicon oxide, gold, silver, zinc oxide and
the study of dangerous bacterial infections prevention [10].
titanium dioxide [1, 2].
On 23 August 1897 a German surgeon Bennett Creed,
A wide range of antimicrobial action of silver, the lack of
continuing his father's research, reported at the XII
resistance to it, efficiency against most pathogenic
International Congress of Doctors in Moscow about the
microorganisms, low toxicity, lack of data in the literature
broad possibilities of silver preparations application in
about the allergic properties of silver, as well as good
purulent surgery and some good results of septic infection
tolerability of patients - have contributed to increased
treatment by the intravenous administration. Then B. Creed
interest in silver, in many countries around the world.
and other chemists suggested preparations containing silver
Colloidal nanosilver – a product consisting of silver
in the non-ionized state: in the form of colloidal particles of
nanoparticles suspended in water and containing a colloidal
metallic silver (the drug collargol) and silver oxide solution
stabilizer system (Figure 1). The typical size of silver
(protargol), modifications which are used in medicine for
nanoparticles - 5-50 nm. The fields of application of silver
more than hundred years. In contrast to previously used
nanoparticles may be different: the spectral-selective
silver salts they had no cauterizing effect [5, 6].
coatings for solar energy absorption, as catalysts for
In Russia, colloidal silver also was appreciated by doctors
chemical reactions, microbial sterilization [2, 7]. The last
who contributed to its increased use in the military field
area of application is the most important and includes the
surgery in Russian-Japanese War in 1904. Silver by
production of various means of packaging, bandages and
intravenous administration is successfully used for the
water-based paints and enamels [3].
treatment of septic arthritis, rheumatism, rheumatic
Currently, based on some colloidal silver manufactured
endocarditis, rheumatoid arthritis, asthma, influenza, acute
products – were obtained biologically active additives with
respiratory infections, bronchitis, pneumonia, purulent septic
antibacterial, antiviral and antifungal activity. However, the
diseases, brucellosi, inside – in the treatment of gastritis,
impact of silver nanoparticles on the biological effects
gastro-duodenal ulcers, externally - in the treatment of
remains open.
sexually transmitted diseases, septic wounds and burns [6,
The study of the healing effect of colloidal silver began in
10].
the second half of the XIX century after the discovery in
70‘s years by German gynecologist Charles Creed of

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deionized water. This high technology product is obtained

by the electrolytic method [9, 10]. Typical silver
nanoparticles have dimensions of 25 nm. They have
extremely large specific surface area, which increases the
contact area of silver with the bacteria or viruses, greatly
improving its bactericidal action. Thus, the use of silver
nanoparticles allows hundreds of times lower concentration
of silver, while preserving all of bactericidal properties.
Bactericidal agent based on silver nanoparticles is one of
the latest achievements of domestic science in the field of
Fig.1. Colloidal nanosilver. nanobiotechnology. The silver‘s action is not specific for
infection (like antibiotics), and on cellular structure. Any
In 1910, the firm "Heiden", summarizing the experience cells without a chemically resistant wall (such a cellular
of the practical application of silver in medicine, produced structure are bacteria and other organisms without cell walls,
an annotation review of the treatment method of various
for example, extracellular virus) exposed to silver. Since
infections: abscesses, typhoid fever, relapsing fever,
mammalian cells have a membrane completely different type
inflammation of lungs, sinuses, middle earinfection,
(not containing peptidoglycans), silver in no way affects
gingivitis, gonococcal sepsis, diphtheria toads, dysentery,
them. Scientists have observed the silver nanoparticles
keratitis, conjunctivitis, leprosy, chancroid, mastitis, within the embryos at different developmental stages:
meningitis, epilepsy, erysipelas, anthrax, syphilitic ulcers, development, deformed and dead. According to the results of
amyelotrophy, acute articular rheumatism, trachoma, sore
observations showed that the biocompatibility and toxicity
throat, boils, cystitis, endocarditis, endometritis, chorea,
of silver nanoparticles strongly depend on the dose of
epididymitis, an ulcer of the cornea [16, 17].
nanoparticles with a critical concentration of 0.19 nm [9,
With the discovery of antibiotics and sulfonamides the
16].
interest to the drugs of silver declined slightly. But recently, Unlike other methods, a separate nanoparticle can be
the antimicrobial properties of silver began again to attract directly mapped in the developing embryos in a nanometer
attention to itself. This is due to the increase of allergic
resolution. This method offers new opportunities to study
complications caused by antibiotic therapy, the toxic effects
events in real time, leading to abnormalities in the
of antibiotics on the internal organs and immune
development of embryos.
suppression, the emergence of fungal respiratory and Physical properties of silver nanoparticles differ from
dysbiosis after prolonged antibiotic therapy, as well as the those of the same silver (eg, reducing the size of the particle
emergence of resistant strains of pathogens to antibiotics leads to a decrease in its melting temperature).Technologists
used [7].
have learned to produce nanoparticles of different sizes,
The increased interest in silver has arisen again in
shapes and chemical composition. But they do not know
connection to the identification of its action in the body as a
how to control the number and the type of defects in the
trace element necessary for normal functioning of organs nanoparticles. Therefore, the question of the influence of the
and systems, immune correcting, as well as powerful nanoparticules defects on its characteristics are unresolved.
antibacterial and antiviral properties [8].
Meanwhile, it is known that defects can lead to very
Effectiveness of bactericidal action of colloidal silver due
significant change in the properties of the nanoparticles [14,
to the ability to suppress the activity of the enzyme which
15].
provide oxygen metabolism in protozoa. Therefore, the
Scientists of the University of Maryland (University of
simplest alien microbes die in the presence of silver ions due Maryland, USA) have developed a technology that allows to
to violations of oxygen supply required for their live lihoods produce silver nanoparticles with same size, but are either
[10].
monocrystalline or contain large numbers of twins - regions
Modern studies of colloidal silver ions showed that they
with different crystallographic axes orientations. The
possess a pronounced ability to neutralize vaccinia virus,
interface between such areas are a special kind of defects
some strains of influenza virus, enterovirus and adenovirus.
(the so-called defects of twinning). This technology is based
In addition, they provide a good therapeutic effect in the on the use of nanoparticles for the synthesis of various
treatment of viral enteritis at dogs and swine. At the same polymeric precursors – silvertriphenylphosphine
time showed the advantage of colloidal silver therapy
(PPh3)33Ag-R with different functional groups (R = Cl or
compared with standard therapy [11, 12].
NO3). If, R = NO3 then from the embryos grow twinned
It was observed beneficial effects of colloidal silver ions
bass and if R = Cl - twin-free (see fig. 2). The formation of
on the healing of venous ulcers developing in poor silver nanoparticules with a specific feature includes Cl-ions,
circulation of the lower extremities. In any case, there were that block the formation of twins. The average size of
no side effects of treatment with silver. Now one of the
nanoparticles was 10.5 nm. Studies have shown that physical
fastest developing areas of modern nanotechnology - the
and chemical properties of these two types of nanoparticles
creation and use of nanoscale particles of different materials.
are significantly different. For example, in interaction with
As is known, silver is the most powerful natural antibiotic
selenium, from the twin-free nanoparticles were prepared
from all that exists on Earth. It is proved that silver can hollow nanoparticles Ag2Se, and from the twinned - solid
destroy more than 650 species of bacteria, so it was used by homogeneous nanoparticles.
humans for the destruction of various microorganisms for
This is because the difference of Ag and Se diffusion
thousands of years, indicating its stable antibiotic effect.
coefficients in the crystal lattice promotes the formation of
Colloidal nanosilver is a product consisting of microscopic
vacancies (the accumulation of which eventually forms the
silver nanoparticles suspended in demineralized and
cavity inside the NP), whereas the atoms Se, moved not by

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the lattice but along the boundaries of twins, easily penetrate wound, as shown by direct counting of the colony. In no
these boundaries of Ag, resulting in a homogeneous case was shown unwanted effects of treatment with silver.
nanoparticles Ag2Se. In twinned nanoparticles, the electronic "Silver compounds are used to treat 70% of cases of burns in
subsystem after the laser pulse is much more rapid cooled the USA.
(due to the transfer of energy to the lattice). This suggests An interesting fact is that more than half of the world's
that the twin boundaries enhance the electron-phonon airlines use water treated with silver, as a way to protect the
interaction, which can be adjusted by varying the passengers from infections such as dysentery. In many
concentration of defects in the nanoparticles. countries, colloidal silver ions are used to disinfect water in
swimming pools [11, 12].
Silver, silver ions and silver nanoparticles are generally
considered safe enough for people. Nevertheless, recent
studies have shown that nanoparticles penetrate into the cells
and damage the genotype. There is even reason to believe
that silver nanoparticles can actively enter cells by
endocytosis. Inside the cell, hydrogen peroxide formed
during cell respiration, oxidizes the silver nanoparticles and
frees them from the silver ions, thus increasing their toxicity.
Consequently, we may even suggest that silver nanoparticles
may be cyto- or genotoxic. In addition, it was shown that
silver nanoparticles penetrate the skin through pores and
Fig. 2. Growth of twin-free and twinned silver nanoparticles of different
precursors. glands. If the skin is damaged, it facilitates the penetration of
silver particles through the skin.
The Concern ―Nanoindustry‖ from Ukraine has developed The data obtained from different studies on the effect of
technology of silver nanoparticles production, stable in nanoparticles on the organisms are rather contradictory, but
solution and in adsorbed state. The resulting products have a to forget about the relevance of this issue is not worth it.
broad spectrum of antimicrobial action. Thus, appeared the Thus, it is important to continue the investigations of silver
opportunity to create a whole range of products with nanoparticles effect on living organisms and to create
antimicrobial properties with little change of technological methods for detection of nanoparticles in the environment.
process by producers of existing products.
Silver nanoparticles can be used to modify the REFERENCES
traditional and creation of new materials, coatings, [1] А.В. Бгатов. Биогенная классификация химических
disinfectants and detergents (including dental and scouring элементов// http://www.nisleda.net/…e-bgatov.htm
pastes, detergents, soaps), cosmetics. Coatings «Философия науки», 2 (6), 1999.
and materials (composite, textile, paint, carbon and [2] N. Silvestry-Rodriguez, K.R.Bright, D.R.Uhlmann,
others), modified with silver nanoparticles can be used as C.P.Gerba. ―Inactivation of Pseudomonas aeruginosa
a prophylactic antimicrobial protection agents in places and Aeromonas hydrophila by silver in tap
where an increasing danger of contamination with water‖//Environmental Science and health, 42 (11),
infections: in transportation, public catering enterprises, in 2007.
the agricultural and pastoral areas , children's, sports, and health care [3] Л.А. Кульский. Серебряная вода, Киев, 1987.
institutions. Silver nanoparticles can be used for water [4] Л.В. Григорьева. Водоподготовка и очистка
purification and destruction of pathogens in the filters of air промышленных стоков, Киев, 1973, Вып.10, c. 9–13.
conditioning systems, swimming pools, showers and other [5] В.С. Брызгунов, В.Н.Липин, В.Р. Матросова.
similar places. Сравнительная оценка бактерицидных свойств
Colloidal Silver is the safest and most potent natural серебряной воды и антибиотиков на чистых
antiseptic for the human body, that overwhelm over 700 культурах микробов и их ассоциациях//
species of pathogens, including staphylococcus, Научн.тр.Казанского мед.ин-та, 1964, т.14, c. 121–
streptococcus, bacteria dysentery, typhoid, etc. It is proved 122.
that the water contaminated by high concentrations of [6] J.B.Chappel, G.D. Greville. Effect of silver ions on
bacteria flexneri (dysentery), Ebert (typhoid fever), mitochondrial adenosinetriphosphates// Nature
staphylococcus, streptococcus, etc., became sterile after one (London). 1954, vol.174, p. 930–931.
or two hours from the introduction of the silver in amount up [7] А.В. Безлепко Кандидат медицинских наук
to 1 mg/l and maintained for many days [5, 12]. (Главный военный клинический госпиталь имени
The drug is actively involved into reducing life and академика Н. Н. Бурденко) и Гуща И. А. Кандидат
termination of pathogen bacteria, viruses, fungi and медицинских наук (ОАО «ДИОД») Инструкция по
parasites, stimulate the protective mechanisms of the human медицинскому применению ионного и коллоидного
body. In this case, it does not affect the benefic серебра.
microorganisms. At the same time, all bacteria and viruses [8] Э.Ш.Савадян, В.М.Мельникова, Г.П. Беликова.
are killed within 6 minutes of exposure to the colloidal Современные тенденции использования
silver. The medical center of the New York University, серебросодержащих антисептиков// Антибиотики и
Department of Orthopedics, were made the study of silver химиотерапия, 1989, N.11, c. 874–878.
ions action in patients with postoperative infectious [9] R.Doer, W. Zur Bergner. Oligodinamie des Silbers//
complications. From the report of the work: "For 12 out of Biochem. Zeitschr, 1922, N131, p. 351–356.
14 patients, treatment was successful, and in all 14 treatment [10] Мироненко Ю.П. Полостной электрофорез//
led to the undoubted reduction of bacterial flora in the Медицинская газета, 1971.

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[11] А.М.Войтенко Водоподготовка и очистка and effect of silver nanopracles on the antibacterial
промышленных стоков. 1973., вып.10., c.128–134. activity of different antibiotics against Staphylococcus
[12] Лот Таранов, Ирина Филиппова Серебряная вода, and Escherichia coli// Nanovedicine-Nanotechnology
Метод Таранова// Диля, 2001 г, c. 25-30 biology and medicine, 3(2): 168–171 Jun 2007.
[13] Ю.П.Ульянов, Доктор мед.наук, Зав. Лор- [16] Eric J. Rentz, DO, MSc Historic Perspectives on
отделением Медицинского Центра «АГАМИ» Clinical Use and Efficacy of Silver.
(Москва) //Проблемы серебряно-зависимых людей. [17] Rami Pedahzur, Ovadia Lev, Badri Fattal and Hillel I.
[14] Е.Родимин. Приготовление целебных медно- Shuval The interaction of silver ions and hydrogen
серебряных растворов и металлоионотерапия peroxide in the inactivation of E. coli: a preliminary
http://www.rem.org.ru/book.htm. evaluation of a new long acting residual drinking water
[15] A.R.Shahverdy, Ali Fakhimi, Sara Minaian. Synthesis disinfectant// Water Science and Technology, 1995, Vol
31, No 5–6, p. 123–129 © IWA Publishing 1995.

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Synthesis of CdSe Nanoparticles and Their

Effect on the Antioxidant Activity of Spirulina
Platensis and Porphyridium Cruentum Cells
V. RUDIC*, L. CEPOI*, L. RUDI*, T.CHIRIAC
A. NICORICI**, A. TODOSICIUC**, T. GUTSUL**
* Institute of Microbiology and Biotechnology
E-mail: [email protected]
**Institute of Electronic Engineering and Nanotechnologies "D. Ghitu"
E-mail: [email protected]
Abstract – Single-crystalline cadmium selenide nanoparticles were obtained using HTSPS synthesis. X-Ray
powder diffraction and transmission electron microscopy were used to confirm the crystallinity and
morphology of the resulting nanoparticles. To study the action of CdSe on antioxidant activity, we selected
two biotechnological important strains of microalgae: cyanobacteria Spirulina platensis and red microalga
Porphyridium cruentum. In the case of Porphyridium cruentum, the obtained results demonstrated an increase
in the productivity. For Spirulina platensis, the presence of the compound in the cultivating medium
decreased the productivity of cyanobacteria.

Keywords - CdSe nanoparticles, HTSPS synthesis, antioxidant activity, colloidal solutions

telluride (0.75 M, TOP-Se) was prepared by the complete

I. INTRODUCTION
dissolving of the necessary amount of tellurium in 50 ml of
Nanomaterials are considered promising modifiers of
TOP at 60–70°C under moderate stirring. The TOP-Se
surface structures of cells. For example, well known
solution described above was prepared and stored in a
polymers, microparticles, nanoparticles, and their possible
nitrogen glove box.
combinations are widely used in these scopes. Several
The microalgae cultivating and obtaining of extracts from
papers described the immobilization of nanoparticles on the
biomass. The strains of Porphyridium cruentum and
surface of various cells. In particular, they showed the
Spirulina platensis were cultivated under laboratory
deposition of gold nanoparticles on the surface of E. coli
conditions. Water extracts were prepared from native
cells in order to form electrical microcontacts. Complexes of
biomass by freezing, and ethanol extracts were derived with
nickel nanoparticles and the bacterial cells were obtained
70% ethanol in ratio 1/10 (w/v).
and characterized in order to design magnetic microdevices
Synthesis. The HTSP method was used as the basis for
on their basis. The surface of yeast cells Kluveromyces
preparing cadmium selenide nanoparticles. A standard
fragilis was modified with magnetic nanoparticles, resulting
synthesis of CdSe nanoparticles was performed in a round-
in effective sorbents, which were obtained on the basis of
bottom three-neck flask equipped with a magnetic stirrer, a
magnetized cells. Thus, the study of the interaction of
thermocouple, and a temperature control unit. Cadmium
nanomaterials with living cells is of particular interest and is
oleate was prepared by heating a mixture of 2 mmol
caused by the fact that hybrid systems based on
cadmium acetate, 4 mmol of oleic acid, and 20 mmol of
nanomaterials and living cells can be prepared and used to
squalane or 20–25 ml of diphenyl ether. Oleic acid was
identify the toxic properties of nanomaterials, which is
employed both for group II precursor formation and
aimed at changing the properties of cells, regulating their
nanoparticle stabilization during the synthesis intended for
physiological activity, and visualizing cellular organelles as
nucleation and reaction rate control. This solution was
well as for high-precision spectral identification of living
heated under vacuum at 75–80°C for 5–6 h in order to form
cells based on differences in biochemical composition of
cadmium oleate and remove already formed acetic acid. The
their surface structures [1]. In this connection, it is extremely
subsequent synthesis of cadmium selenide NPs was carried
urgent to find methods of the immobilization of
out by rapid injection of trioctylphosphine selenide (TOP-
nanomaterials on cell surfaces that will allow them to
Se) solution maintained at room-temperature into a
maintain physiological activity.
vigorously stirred mixture containing cadmium oleate heated
II. METHODS from 140 to 200C under N2 atmosphere. The reaction
Chemicals. Tri-n-octylphosphine (Aldrich, 90%), mixture was maintained at a fixed temperature for 10 min
amorphous selenium shot (Aldrich, 99.999%), squalane and then promptly cooled to room temperature using an ice-
(Aldrich, 99%), diphenyl ether (DPE) (Fluka, 98%), water bath. The solution quickly turned dark red during the
cadmium acetate dihydrate (Aldrich, 99.99%), and oleic acid synthesis due to the formation of CdSe colloidal solution.
(cis-9-octadecenoic acid, Aldrich, 90%) were used as The TOP-Te/lead oleate molar ratios varied from (1.5–3) to
purchased without further purification. Anhydrous ethanol, 1.
hexane, chloroform, acetone, tetrachloroethylene, and A solvent containing two parts of hexane, one part of
trichloroethylene were purchased from different companies anhydrous ethanol, and five parts of acetone was prepared to
and used without further purification. Trioctylphosphine purify the nanoparticles from unreacted precursor, excess

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surfactant, and high-boiling point solvents. A size-selective over 64 interferograms with a resolution of 1 cm-1. The
precipitation was carried out by centrifugation, using a samples for the IR measurements were prepared as pellets
polar/nonpolar solvent combination, consisting of acetone with KBr or CsI powders. The quantitative analysis of the
and either hexane or chloroform. After precipitation, the resulting nanopowders was performed with an AAS-3
CdSe nanoparticles were isolated and re-suspended in atomic absorption spectrometer using acetylene–air flame.
chloroform, hexane, and trichloroethylene followed by For the investigation of the resulting nanomaterial, the
ultrasonic treatment to form stable colloidal solutions used following synthesis parameters were selected: fixed reaction
for further preparation and characterization. The chemical temperature T = 175C, TOPSe/cadmium oleate molar ratio
analysis and atomic absorption spectroscopy confirmed the r = 2.0. Diphenyl ether was used as the high-boiling heat-
CdSe composition of the nanomaterial deposited after transfer agent. As mentioned above, the samples were
multiple purifying and re-suspension of the original solution. prepared for X-ray powder diffraction by depositing the
In order to use hydrophobic nanoparticles for biological colloidal solution onto a glass substrate dropwise.
applications, they first must be transferred into aqueous
solution. III. RESULTS AND DISCUSSION
The formation of various surface-active functional groups The typical powder diffraction patterns of resulting CdSe
(-COOH, -C=O,-OH) makes it possible to transfer to nanocrystals are shown in Fig.1. XRD revealed three broad
aqueous colloids and contributes to coordination interaction peaks positioned at 2θ = 25.37, 42.04, and 49.63° with
with necessary surfaces, for example, with biological corresponding interplanar spacings of 3.51, 2.15, and 1.83 Å,
molecules [2]. respectively. These peaks are uniquely assigned to the (002),
Methods for the modification of CdSe nanoparticles (110), and (112) planes of the wurtzite structure of CdSe.
include the processing of nanoparticles with buffer solutions, The broadening of the diffraction pattern for CdSe implies a
transferring into a soluble state, and obtaining a colloidal reduction in particle size.
solution in the presence of modifying agents such as 1-
150
thioglycerol. The subsequent deposition and re-dispersion of
nanoparticles was performed in deionized water [3].
Antioxidant activity by the ABTS+ radical cation
assay. The total antioxidant activity of extracts was 100
measured by the ABTS+ (2,2 azinobis 3-
CPS

ethylbenzothiazoline-6-sulfonic acid) radical cation

decolorization [4]. ABTS+ was generated by the oxidation of
ABTS (7mM) with potassium persulphate (2.45 mM). The 50
reaction mixture was left at room temperature overnight (12-
16 h) in the dark before use. Prior to tests, the ABTS + stock
solution was diluted to an absorbance of 0.700 ± 0.020 at
734 nm. Then 1 ml of diluted ABTS+ solution was mixed 10 20 30 40 50 60 70 80
with 10 μl of the test sample, and the absorbance was 2
measured after 6 min.
Nanocrystalline sample characterization. High- Fig. 1. Typical powder diffraction pattern of CdSe NPs.
resolution transmission electron microscopy (HRTEM), An average size of 4–4.5 nm for the CdSe nanoparticles
powder X-ray diffraction (XRD), and infrared absorption was estimated from the X-ray powder diffraction data using
spectroscopy (IR) were used to characterize the size, shape, the Scherrer equation.
structure, and composition of the CdSe nanocrystals and the The size and shape of cadmium selenide nanoparticles
optical properties of the capping layer. The powder XRD were examined using TEM methods.
data were recorded with CuKα radiation ( = 1.5406 Å) To study the action of CdSe on antioxidant activity, we
using Scintag and PANanalytical X'Pert Pro diffractometers, selected two biotechnological important strains of
both operating in the Bragg–Brentano geometry. Samples for microalgae: cyanobacteria Spirulina platensis and red
the XRD measurements were prepared by the deposition of microalga Porphyridium cruentum. The previous studies
concentrated CdSe colloidal solutions in chloroform or showed the increased adaptability of strains to changing
trichloroethylene onto a glass substrate. The 2 range cultivating conditions. The adaptation response in the
scanned from 20° to 80. A Philips CM 30 transmission majority of cases is considered to be the response to the
electron microscope (TEM) equipped with a Super-Twin stress factor, which is manifested in different modes at the
lens and LaB6 emitter was used for HRTEM measurements. mentioned strains depending on specific functional and
All the images were taken at 300-kV accelerating voltage constitutive structures [5].
and recorded with a megapixel CCD camera. The EDX One of the essential markers of adaptability is strain
spectra were collected using a Tecnai F30 TEM operating at productivity. The CdSe nanoparticles were supplemented in
an accelerated voltage of 300 kV and equipped with a the cultivating medium on the first day of life cycle to verify
Schottky field emission electron source and a Super-Twin the compound‘s toxicity level. In the case of Porphyridium
lens. Samples for the TEM were prepared by the deposition cruentum, the obtained results demonstrated the increase in
of a drop of a dilute colloidal solution in chloroform, hexane, productivity by 34-47.5% (CdSe concentration was 4.0-6.0
or trichloroethylene on a carbon-coated copper grid (200 mg/l) and by 18% in the case of the highest concentration of
mesh), allowing slow evaporation at room temperature. The 8.0 mg/l. For Spirulina platensis, the presence of the
IR absorption spectra were recorded with a VERTEX-70 compound in the cultivating medium decreased
Fourier transform spectrometer (Bruker Corp.). Each cyanobacteria productivity by 33% in the case of CdSe
spectrum was obtained at room temperature by averaging

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

concentration of 4.0 mg/l. Higher concentrations are fatal; in the antioxidant activity by 70-73% for both types of
the culture dies on the 3rd day of cultivation. extracts.

Extract hidric Extract etanolic

100

ABTS, % inhibition
80
60
40
20
0
M 2 4
CdSe, mg/L
Fig. 4. The antioxidant activity (% of ABTS inhibition) of extracts from
Spirulina platensis.

For cyanobacteria Spirulina platensis strain, the presence of

Fig. 2. High-resolution transmission electron microscopy image of small
aspect ratio CdSe NPs. CdSe particles in the cultivating medium is a strong factor
for stimulating antioxidant compound synthesis; the
Another index of culture adaptation to the cultivating limitation of its increase is a concentration of 4.0 mg/l.
conditions is the strain‘s antioxidant activity. Cyanobacteria
and microalgae synthesize the complex of substances with IV. CONCLUSIONS
antioxidant and antiradical properties [6]. Depending on Cadmium selenide nanoparticles were obtained; their
factors which induce radical accumulation, the synthesis of composition and crystallinity were confirmed. The CdSe
the necessary antioxidant compounds with the modification nanoparticles were supplemented in the cultivating medium
of antioxidative statute took place. This fact could be (cyanobacteria Spirulina platensis and red microalga
determined by the antioxidant activity tests of extracts from Porphyridium cruentum), and the change in the productivity
biomass. Two types of extracts were prepared: water and was studied.
ethanol extracts. We used the antioxidative test with ABTS The obtained results suggest the idea of different nature of
radical. adaptation mechanisms in prokaryote and eukaryote
organisms. The confirmation of this assumption on the basis
Extract hidric Extract etanolic of other phycologic objects will offer the possibility to
60 develop models for testing the nanoparticle toxicity.
ABTS, % inhibition

50 REFERENCES
40 [1] А.И. Замалеева, И.Р. Шарипова, Л.В. Шлыкова, M.
30 Kahraman, M. Culha, Р.Ф. Фахруллин
20 Иммобилизация наноматериалов на поверхности
10 клеток и их характеристика методами микроскопии /
0 IV Международная конференция ―Современные
достижения бионаноскопии‖. Сб. тезисов. – Москва.
M 2 4 6 8
CdSe, mg/L – 2010, c.26.
[2] J. M. Klostranec and W.C.W. Chan. Quantum dots in
Fig. 3. The antioxidant activity (% of ABTS inhibition) of extracts from biological and biomedical research: Recent progress and
Porphyridium cruentum biomass. present challenges. Advanced Materials, 18(15):1953-
The analyses of the results obtained for Porphyridium 1964, 2006.
cruentum biomass show the relative stability of antioxidant [3] Vladimir V. Breus, Colin D. Heyes, and G. Ulrich
activity for the two types of extracts (Fig. 3). In the case of Nienhaus Quenching of CdSe−ZnS Core−Shell
supplementing CdSe in the cultivating medium in tested Quantum Dot Luminescence by Water-Soluble
concentrations, the antioxidant activity of the water and Thiolated LigandsJ. Phys. Chem. C, 2007, 111 (50), pp
ethanol extracts oscillated identically to the control sample, 18589–18594.
without excess of accumulating antioxidants. On the other [4] . Re R., Pellegrini N., Proteggente A., Pannala A., Yang
hand, the presence of CdSe nanoparticles in the cultivating M., Rice-Evans C. Antioxidant activity applying an
medium has no essential influence on the maintenance of improved ABTS radical cation decolorization assay.
antioxidant and antiradical compounds in Porphyridium Free Radical Biology & Medicine, 1999, 26(9/10):
biomass, inducing an increase in productivity. 1231-1237.
In the case of Spirulina platensis extracts, an increase in [5] Rudic V., et al. Ficobiotehnologie-cercetări
the antioxidant activity was revealed (Fig. 4). So, for the fundamentale şi realizări practice. Chisinau 2007,
extracts obtained from the biomass cultivated with a pp.365.
supplement of 2.0 mg/l CdSe, the antioxidant activity of the [6] Cepoi L., Rudi, L., Miscu, V., Cojocari, A., Chiriac, T.,
ethanol extract increased by 25%, but the water extract Sadovnic, D. Antioxidative Activity Of Ethanol Extracts
showed the same result as the control sample. The increase From Spirulina platensis And Nostoc linckia Measured
in the CdSe concentration up to 4.0 mg/l induces an increase By Various Methods. Analele Universităţii din Oradea,
Fascicula Biologie Tom. XVI / 2, 2009, p. 43-48.

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Influence of Copper Coordination Compounds

and Cyanobacterian Remedy BioR on Bone
Collagen and Hydroxyproline Concentrations
(ontogenetic view)
Olga TAGADIUC1, Aurelian GULEA2, Valeriu RUDIC3, Valentin GUDUMAC1
1
Biochemistry Laboratory, State University of Medicine and Pharmacy „N.Testemitanu”, Moldova
[email protected]
2
Department of Inorganic Chemistry, State University of Moldova
3
Institute of Microbiology and Biotechnology, Academy of Science, Moldova

Abstract – The aim of our research was to assess the influence of copper coordination compounds CMT-28 and
CMT-67 and cyanobacterian remedy BioR on bone collagen and hydroxyproline (HYP) concentrations at
different stages of postnatal ontogenesis in normal physiological conditions and experimental osteopathy (EO).
The survey was conducted on a sample of 301 white laboratory rats of both sexes, which were divided
depending on their stage of postnatal ontogenetic development and experimental model: control; animal with
experimental osteopathy (EO); animals with EO+CMT-28 1 mg/kg body weight; animals with EO+CMT-67 1
mg/kg body weight; animals with EO+BioR 1mg/kg body weight; animals with EO+BioR 2 mg/kg body
weight; animals with EO+CMT-28+BioR (1 mg/kg body weight each); animals with EO+BioR+CMT-67 (1
mg/kg body weight each).
In physiological conditions the ontogenetic modifications of the bone collagen and HYP content are
statistically conclusive and of the same orientation, the maximum concentration was identified in adult
animals and the minimum at advanced stages of postnatal ontogenesis regardless of sex.
Experimental osteopathy is characterized by age and sex dependent changes of the collagen and
hydroxyproline concentrations in bone, the most significant changes being revealed in young females.
Copper coordination compounds, BioR and their combinations increase the turnover of the collagen in bone in
EO that is accompanied by decrease of collagen and increase of the HYP concentration that is probably a
compensatory mechanism oriented to the replacement of the damaged collagen and the restoration of its
normal nanostructure with the recovery of the bone.

Major steps of the collagen nanofibers formation are

I. INTRODUCTION hydroxylation of proline and lysine radicals and the
Nanofibers are defined as fibers with diameters less than tropocollagen cross- through oxidized lysine radicals [4].
1000 nanometers. Nature has created a variety of biological Prolyl-4-hydroxylase and prolyl-3-hydroxilase are
nanofibers with outstanding properties that are used in responsible for proline hydroxylation and formation of
different ways by the living organisms. As classic examples hydroxyproline (HYP) [4]. The lysine oxidation is catalyzed
of natural nanofibers serve elastin, collagen, keratins, fibrin, by lysyl oxidase that uses copper ions as coenzyme [5]. The
etc. necessity for copper in the formation of bone and
Collagen is the most abundant protein in the human body, maintenance of its structure is well established. There are
comprising about 25% of their total [1]. Collagen constitutes also a lot of studies that show that the lack of this mineral
90-95% of the extracellular matrix (ECM) of the bone, will lead to abnormal bone formation and fractures in
represented predominantly by type I. Types V, XI and XII newborns, infants, and sometimes even in adults [6, 7].
and FACIT forms (Fibrils Associated Collagens with Thus, the aim of our research was to assess the influence
Interrupted Triple helices) that are associated with large- of copper coordination compounds and cyanobacterian
diameter collagen fibers, constitute a minor quantity, but are remedy on bone collagen and hydroxyproline concentrations
essential for bone morphogenesis. at different stages of postnatal ontogenesis in normal
Regardless of the collagen type the molecules are an physiological conditions and experimental osteopathy.
indubitable example of a hierarchical biological II. MATERIALS AND METHODS
nanomaterial [2]. Fibers consist of tropocollagen molecules The survey was conducted on a sample of 301 white
with diameter of 1,5 nm and length of 300 nm, which are laboratory rats of both sexes without pedigree. The animals
linked by covalent cross-links and pyridinolinic links in the were divided into the following experimental groups
non-helical N-and C-terminal regions to form collagen [3]. depending on ontogenetic stage of postnatal development
Collagen synthesis and degradation are continuous phasic and experimental model.
processes that are vital for maintaining normal  Group I - 90 young rats before sexual maturity (two
concentrations of components and specific nanostructure of months);
the extracellular matrix of the bone and its mineralization.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

 Group II - 78 adult rats in the reproductive period (six III. RESULTS AND DISCUSSION
months); The results of the study show the same orientation of the
 Group III - 54 old, postmenopausal rats (18 months); ontogenetic changes of free HYP and collagen content in the
 Group IV - 33 senile rats (24 months). bone tissue in the postnatal period (Table 1).
Animals from groups I-III were divided into the following
TABLE 1.ONTOGENETIC CHANGES OF HYDROXYPROLINE (HYP)
subgroups: control (intact animals), animals with EO
AND COLLAGEN CONCENTRATIONS IN BONE TISSUE IN
induced by administration of 0,1 ml of 50% CCl 4 in olive oil NORMAL PHYSIOLOGICAL CONDITIONS AND EO
per 100 g body weight twice a week for 8 weeks; animals POS Sex Group HYP Colagen
EO+BioR 1mg/kg body weight; animals with EO+BioR 2
mg/kg body weight, animals with EO+CMT-28 1 mg/kg Control 110,46±5,03 2,45±0,13
body weight; animals with OE+CMT-67 1 mg/kg body M
105,99±4,32 2,74±0,33

Young
EO
weight; animals with OE+BioR+CMT-28 (each 1 mg/kg
body weight); animals with EO+BioR+CMT-67 (each 1 Control 104,66±5,48 3,59±0,17####
mg/kg body weight). F
The remedy BioR obtained from the biomass of EO 126,46±5,63§# 2,98±0,18§
cyanobacterium Spirulina platensis was provided by Valeriu
Control 135,46±5,90***T 4,44±0,23****T
Rudic, professor, director of the Institute of Microbiology M
and Biotechnology of the Academy of Sciences of Modova EO 137,27±7,34*T 5,02±0,32**T

Adult
and copper coordination compounds (CC) CMT-28 and
CMT-67 - by Aurelian Gulea, professor, Head of the Control 128,67±5,78 4,83±0,18****T
Inorganic Chemistry Department of MSU. F
BioR was diluted with sterile 0,9% NaCl until the final EO 116,07±4,45# 4,59±0,16****T
concentration of 1 mg/ml and was injected intramuscularly Control 54,80±1,46***A 2,82±0,17****A
each 0,1 ml/100 g body weight (1 mg/kg body weight) and M
0,2 ml/100 g body weight (2 mg/kg body weight) for 10 EO 52,94±6,54**A 2,71±0,21**A
Old

consecutive days. Coordination copper compounds CMT-28

and CMT-67 were diluted in 10% sol. of propilenglicol until Control 57,69±5,17****A 2,79±0,17****A
F
the final concentration of 1 mg/ml and injected EO 51,54±3,87***A 2,96±0,11****A
subcutaneously each 0,1 ml/100 g body weight (1 mg/kg
body weight) for 10 consecutive days. M Control 85,14±2,78****B 2,04±0,06****B
Senile

At 24 hours after the last administration the animals were

euthanized under light narcosis with sulfuric ether. The F Control 75,54±2,40***B# 2,73±0,08
femoral bones were removed, cleaned from adjacent tissues a) Each value represents X  m
and the bone marrow removed by repeated washings with ice b) POS – postnatal ontogenetic stages
solution of 0,9% NaCl. Femoral bones were then frozen in c) Statistical significance between different ontogenetic stages
liquid nitrogen, grinded to the state of powder and weighed according to U Mann-Whitney: * p<0,05;** p<0,01; *** p<0,001;
on torsion balance. **** p<0,0001
Determination of collagen content was performed after the d) Statistical significance between male and female rats according
to U Mann-Whitney: # p<0,05; ## p<0,01
dissolution in 0,43 M trichloroacetic acid of a sample of
e) Statistical significance compared with control group according to
bone tissue triturated in liquid nitrogen until the state of U Mann-Whitney: § – p<0,05; §§ – p<0,01; §§§ – p<0,001.
powder (20 mg). Determination of collagen in bone tissue
was performed according to the procedure described [9]. The The research has established that the concentration of
method is based on the preliminary transformation of the collagen is significantly higher in adult animals compared
native bone collagen in soluble gelatin by processing the with all other groups studied, the amount of the collagen
biological material with a heated to 90°C solution of peaks at this stage of ontogenetic development, regardless of
trichloroacetic acid (ATA), sedimentation of non-collagenic animal sex. Thus, collagen concentration is higher in adult
proteins by centrifugation and determination of the gelatin males with 81% (p<0,001) and females - 36% (p<0,001)
concentration by classical Lowry assay. The amount of compared with the young rats. At later stages collagen levels
collagen was expressed in milligrams of collagen per gram gradually decreased. In old males the collagen content is
of bone (mg/g). 42% (p<0,001) lower than in adults, and in senile with 27%
Hydroxiproline content in bone was determined by (p<0,001) lower than in the old one.
Шараев П.Н. (1981) method in modification of [9]. The In females it was established the same trend of
method is based on the oxidation of HYP to pyrol which decreasing the collagen content, but statistically reliable
interacts in acidic environment with p- were only changes of collagen concentration in old rats
dimetilaminobenzaldehyde (DMBA) and form a colored compared to adult animals (reduction by 39%, p<0,001).
product that is assayed spectrophotometrically. The amount It was established that the content of the free HYP
of HYP is expressed in mmol/g tissue. increased in young males versus adult (23%, p<0,005),
For testing the significance of the differences between the decreased in the old compared to young (50%, p<0,001) and
studied groups the non-parametric statistical test Mann- adult (45%, p<0,005), and then again increased in the senile
Whitney were applied. Statistical evaluation of data obtained versus old (55%, p<0,001). Similar changes have been
was performed with computer program Statistical Software identified in females, but statistically significant in this case
"StatsDirect" (2001) were only the differences between the free HYP content in
adult and old animals (reduction by 55%, p<0,001), and the

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old and senile one (31%, p<0,005). The maximum TABLE 2IINFLUENCE OF COPPER COORDINATION COMPOUNDS
CMT-28 AND CMT-67 ON THE CONCENTRATION OF
concentration of free HYP was identified in adult animals,
HYDROXYPROLINE (HYP) AND COLLAGEN IN THE BONE OF
and the minimum in old animals regardless of sex. ANIMALS WITH EO AT POSTNATAL ONTOGENETIC STAGES
Statistically reliable sex differences of the concentration
POS Group HYP Collagen
of free HYP were recorded only in senile rats, the level of
the compound is lower for females (11%, p<0,05) compared Control 104,66±5,48 3,59±0,17

Young
to males. EO 126,46±5,63§ 2,98±0,18§
It was found that EO induced by CCl4 administration EO+CMT-28 123,46±5,54§ 2,89±0,29
caused statistically reliable changes in the level of collagen
EO+CMT-67 140,77±13,41§ 3,34±0,29
only in young females, in which an 17% decrease (p<0,05)
Control 128,67±5,78 4,83±0,18
compared with controls were depicted (Table 1).
116,07±4,45 4,59±0,16

Adult
EO
Ontogenetic dynamics of the level of collagen in bone
tissue of animals with the EO is similar to that determined in EO+CMT-28 #
144,16±8,91 ##
3,65±0,16§§§§
control animals. Both in males and females with EO the EO+CMT-67 115,09±6,91 4,44±0,26
concentration of collagen increases in adult animals Control 57,69±5,17 2,79±0,17
EO 51,54±3,87 2,96±0,11

Old
compared with young by 83% (p<0,01), respectively, 54%
(p<0,001), and then decreases in the old compared to the EO+CMT-28 65,91±7,46 3,12±0,18
adult by 46% (p<0,01) and 35% (p<0,001), respectively. EO+CMT-67 72,27±11,28 3,25±0,18
There were no sex-dependent differences in the level of a) Each value represents X  m
collagen in animals with EO, regardless of the ontogenetic b) POS – postnatal ontogenetic stages
stage of development. c) Statistical significance between different ontogenetic stages according to
U Mann-Whitney: * p<0,05; ** p<0,01; *** p<0,001; **** p<0,0001;
It was established that in EO the concentration of free d) Statistical significance compared with EO group according to U Mann-
HYP in the bone of young males did not change statistically Whitney: # – p<0,05; ## – p<0,01; ### – p<0,005, #### – p<0,001;
conclusive. In young females, by contrast, it was established e) Statistical significance compared with control group according to U
a 21% increase (p<0,05) compared to the control group. In Mann-Whitney: § – p<0,05; §§ – p<0,01; §§§ – p<0,001.
males was identified an ontogenetic dynamics of the free
HYP concentration similar to that specific to control The results of the research show that cyanobacterial
animals. Thus, the HYP concentration in adult rats were by remedy BioR in both doses did not alter the concentration of
30% (p<0,05) higher than in young rats and hydroxyproline free HYP in the bone of rats with EO regardless of
content in the old animals were by 42% (p<0,01) lower than ontogenetic development stage (Table 3).
in the adults. In females with EO were established a Only a slight tendency of increase of the HYP content
progressive decrease in bone level of free HYP: HYP were revealed in young animals compared with the control
content of adult animals show a tendency to decrease by 8% and EO specific levels after the administration of 2 mg/kg
compared to young animals and in those old values were by BioR, in adult animals after the administration of BioR in
56% (p<0,001) lower compared with those specific for the both doses and in old one after the administration of 1 mg/kg
adult animals. BioR.
Gender differences had been established in young and Collagen levels were not statistically significant changed
adult animals with EO – in young males HYP concentration after the administration of BioR regardless of dose or age of
was by 19% (p<0,05) lower than in females, and in adults by the animals. Nevertheless, administration of 1 mg/kg of
15% (p<0,05) higher than the values in females. BioR induced a trend of increase in old animals by 17%
It was founded that the medication with copper compared with animals with EO. This amount of collagen
coordination compounds CMT-28 and CMT-67 does not was higher then the control levels by 12%.
induce statistically conclusive changes in the concentration This data revealed that BioR is conserving the collagen
of collagen in bone tissue of experimental animals with EO. content in the bone of the animals with EO. Possible the high
Only in adult animals copper coordination compound CMT- content of active compounds in the cyanobacterial remedy
28 reduced collagen concentration compared with controls BioR (aminoacids, oligopeptides, polysaccharides,
(24%, p<0,001), as well as with EO (20%, p<0,001) (Table microelements etc.) create favorable environment for
2). optimization of bone metabolism and adaptation to
Copper coordination compounds CMT-28 and CMT-67 pathological conditions in EO.
did not induce statistically conclusive changes in the The combination BioR+CMT-28 reduced the
concentration of free HYP in bone compared with EO group concentration of collagen in young (18%, p<0,05) and adult
level, with the exception of adult ones. In this group CMT- (19%, p<0,01) animals compared with the control, and in the
28 increases the level of free HYP by 24% (p<0,05) adult (15%, p<0,01) and old (12%, p<0,05) animals
compared to EO animals. compared EO group. The combination BioR+CMT-67
Thus, in adult animals the copper coordination compound changed statistically conclusive the collagen concentration
CMT-28 is decreasing the collagen content and at the same only in adult animals (decrease by 19%, p<0,05) compared
time increasing the amount of free HYP in bone. This can be with the group with EO (Fig. 1 and 2).
an evidence of increased breakdown of damaged collagen in Administration of the cyanobacterial remedy BioR in
the bone of adult animals with EO. This process is a stage of combination with the copper coordination compounds CMT-
the restoration of the collagen content and structure in the 28 and CMT-67 produced significant changes in the
bone that precedes the biosynthesis of normal collagen concentration of free HYP in young animals with EO.
fibers.

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TABLE 3.IINFLUENCE OF CYANOBACTERIAN REMEDY BIOR ON EO animals, but changes are not statistical reliable. None of
THE CONCENTRATION OF HYDROXYPROLINE (HYP) AND
the studied combinations produced statistically reliable
COLLAGEN IN THE BONE OF ANIMALS WITH EO AT POSTNATAL
ONTOGENETIC STAGES changes in old animals with EO.
POS Group HYP Collagen
16 #
Control 110,46±5,03 2,45±0,13 14
§#
HYP
105,99±4,32 2,74±0,33
Young

EO 12 Collagen

BioR 1mg/kg 105,99±4,32 2,76±0,14 10

BioR 2 8

mg/kg 120,67±10,15 2,74±0,17 6

Control 135,46±5,90***T 4,44±0,23****T 4

EO 137,27±7,34*T 5,02±0,32**T 2
Adult

0
BioR 1
146,67±4,76 5,02±0,22

EO

EO

EO
CMT-67 + BioR

CMT-67 + BioR

CMT-67 + BioR
Control

Control

Control
mg/kg
BioR 2
mg/kg 149,05±9,20 4,55±0,06
A
Control 54,80±1,46*** 2,82±0,17****A Young Adult Old

EO 52,94±6,54**A 2,71±0,21**A Figure 2. Iinfluence of cyanobacterial remedy BioR and copper

Old

BioR 1 coordination compound CMT-28 on the concentrations of

mg/kg 63,29±3,92 3,16±0,08 hydroxyproline (HYP) and collagen in the bone of animals with
BioR 2 experimental osteopathy (EO) at postnatal ontogenetic stages.
mg/kg 54,03±7,40 2,85±0,24
a) Statistical significance compared with EO group according to U
a) Each value represents X  m Mann-Whitney: # – p<0,05; ## – p<0,01; ### – p<0,001,
b) POS – postnatal ontogenetic stages b) Statistical significance compared with control group according to
c) Statistical significance between different ontogenetic stages according to U Mann-Whitney: § – p<0,05; §§ – p<0,01; §§§ – p<0,001.
U Mann-Whitney: * p<0,05; ** p<0,01; *** p<0,001; **** p<0,0001,
d) Statistical significance compared with EO group according to U Mann- Combined administration of the copper coordination
Whitney: # – p<0,05; ## – p<0,01; ### – p<0,001,
e) Statistical significance compared with control group according to U compounds CMT-28 and CMT-67 with the cyanobacterial
Mann-Whitney: § – p<0,05; §§ – p<0,01; §§§ – p<0,001. remedy BioR is characterized by potentiation of the drug
influence on bone metabolism.
The combined administration to the young animals of The increased content of HYP that is correlated with a
BioR+CMT-28 increased the bone content of free HYP decreased amount of collagen that we reveal in our study can
compared with control values by 35% (p<0,05) and BioR+ be a sign of the enhanced collagen turnover in EO.
CMT-67 – by 30% (p<0,05), while compared with animals Prolonged administration of CCl4 triggered free radical
from the EO group the free HYP content was modified only production and oxidative damage of cellular and
by the combination BioR+CMT-67 (35%, p<0,05). extracellular compounds [9]. Damaged proteins, including
collagen, are removed from the tissues and replaced with
16
§ ## HYP normal one. Possible, the decrease of collagen concentration
14
Collagen
and increase of HYP – marker of bone resorption, is
12 reflecting the efforts of the tissue to compensate the
10
deterioration caused by the EO by degrading the abnormal
8
collagen and replacing it with proper fibers that will restore
§§
the normal structure on the extracellular network.
6
## Previous studies revealed that the properties of collagen
4 § # are scale-dependent and that the strength of the
2 tropocollagen molecules differs from the strength of the
0 collagen fibril. The late depends on the number of the cross-
EO

EO

EO
Control

CMT-28 +

Control

CMT-28 +

Control

CMT-28 +

links in the fibril, on the fibril length, etc. Thus, the

BioR

BioR

BioR

nanostructure of collagen may provide either a strong bone

Young Adult Old or a brittle one [2].
Figure 1. Iinfluence of cyanobacterial remedy BioR and copper Our results prove the ability of the copper coordination
coordination compound CMT-28 on the concentrations of compounds CMT-28 and CMT-67 and cyanobacterial
hydroxyproline (HYP) and collagen in the bone of animals with
experimental osteopathy (EO) at postnatal ontogenetic stages remedy BioR to intervene in the metabolism of collagen
nanofibers at the essential stages. The magnitude of the
a) Statistical significance compared with EO group according to U
tissue response is depending on the postnatal ontogenetic
Mann-Whitney: # – p<0,05; ## – p<0,01; ### – p<0,001,
b) Statistical significance compared with control group according to stage. Copper coordination compounds and cyanobacterial
U Mann-Whitney: § – p<0,05; §§ – p<0,01; §§§ – p<0,001. remedy can induce the correction of the damage caused by
the CCl4 to the collagen fibers and provide the restoration of
In adult animals the combination BioR+CMT-28 its physiological nanostructure with the recovery of the bone
increased the concentration of free HYP by 22% (p<0,01) structure and properties.
compared with the values observed in animals with EO,
IV. CONCLUSIONS
bringing it to 10% higher values (p>0,05) than the control.
1. In physiological conditions the ontogenetic
The combination BioR+CMT-67 also enhanced the
modifications of the content of bone collagen and HYP
content of HYP over control values and those specific for the
are statistically conclusive and of the same orientation,

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the maximum concentration of collagen and free HYP [3] П.Г. Роби, Биохимия кости. В: Остеопороз.
was identified in adult animals and the minimum at Этиология, диагностика, лечение. Под ред. Риггз
advanced stages of postnatal ontogenesis regardless of Б.Л., Мелтон III Л.Дж.. СПб, "Издательство
sex. БИНОМ", "Невский диалект", 2000, стр. 57-84
2. Experimental osteopathy is characterized by age and sex [4] L. Koláčná, J. Bakeśova , F. Varga et al. Biochemical
dependent changes of the collagen and hydroxyproline and Biophysical Aspects of Collagen Nanostructure in
concentrations in bone, the most significant changes the Extracellular Matrix. Physiol. Res., no. 56, suppl. 1,
being revealed in young females. 2007, pp. S52-S60.
3. Copper coordination compounds (CMT-28 and CMT-
67), cyanobacterial remedy BioR and their combinations [5] R.B. Rucker, J. Murray, Cross-linking amino acids in
increase the turnover of the collagen in bone in collagen and elastin. American Journal of Clinical
experimental osteopathy, that is accompanied by Nutrition, no. 31, 1978, pp. 1221-1236.
decrease of collagen concentration and increase of the [6] Y.L. Lai, M. Yamaguchi. Effects of Copper on Bone
hydroxyproline amount. Component in the Femoral Tissues of Rats: Anabolic
4. The increase of the turnover of the collagen in bone in Effect of Zinc Is Weakened by Copper. Biol. Pharm.
experimental osteopathy induced by copper Bull., vol. 28, no. 12, 2005, pp. 2296-2301.
coordination compounds (CMT-28 and CMT-67), [7] D. Conlan, R. Korula, D. Tallentire, Serum copper
cyanobacterial remedy BioR and their combinations is levels in elderly patients with femoral-neck fractures.
probably a compensatory mechanism oriented to the Age and Ageing, vol. 19, 1990, pp. 212-214.
replacement of the abnormal collagen and the [8] V. Gudumac, O. Tagadiuc, V. Rîvneac et al. Investigaţii
restoration of its normal nanostructure with the recovery biochimice. Elaborare metodică. Micrometode. Vol.II.
of the bone. Ch.: Elena V. I. SRL, 2010. 104 p.
[9] M.I. Díaz Gómez, J.A. Castro, Covalent binding of
REFERENCES carbon tetrachloride metabolites to liver nuclear DNA,
[1] M.K. Gordon, R.A. Hahn, Collagens, Cell Tissue Res., protein and lipids. Toxicol Appl Pharmacol, no. 56,
vol. 339, no. 1, 2010, pp. 247-257. 1980, pp. 199-206.
[2] M.J.Buehler, Nature designs tough collagen: Explaining This work was supported by the Moldavian Academy of
the nanostructure of collagen fibrils. PNAS, vol. 103, Science institutional project 06.420.017F "Concepts of bone
no. 33, 2006, pp. 12285-12290. metabolism in normal postnatal ontogenesis and experimental
osteoporosis"

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Comparative Study Of The Mechanical

Characteristics Of Dental Implants Made From
Biomaterials Covered With DLC Depositions
Stanca COMŞA, Adrian PACIOGA, Doina GHEORGHIU, Stefan MARIA
[email protected],
National Institute of Research & Development for Mechatronics and Measurement Technique, 6-8 Str.
Pantelimon, Bucharest, Romania.
Abstract – Nanostructures and nanostructured materials development has opened important expectative in
multiple fields, however, one of them, with important direct impact on the society is the medicine.
In this paper is presented a comparative study of the mechanical properties of titanium used for dental
implants covered or not with an ultra thin DLC (Diamond Like Carbon) film deposition. Evaluation was
focused on determining the number of cycles until failure in dynamic fatigue testing according to SR EN ISO
14801: 2008 and static compression strength according to SR EN ISO 6892-1:2010, for dental implants made
of pure titanium covered/not covered with a layer of DLC. In order to make a comparison between covered
and uncovered specimens, two of them were covered with DLC depositions, and other two without deposition.
The obtained results show the improvement of the mechanical properties.

Keywords – biomaterials, mechanical properties, nanodepositions.

osseointegration process. So it is necessary to have a porous

I. INTRODUCTION
surface to permit the osteoblasts cells proliferations better
Bone is one of the most replaced parts in the human body.
than the osteofibre ones.
The current treatment option is implantation. Implants with
Studies show that classic biomaterials with carbon nano
scaffolds have to provide anchorage of cells and play an
depositions present acceleration of bone cell function in
important role in bone regeneration. The materials need to be
comparison with materials without such covering. [3]
biocompatible and provide appropriate mechanical support
The deposition of the DLC film was made using
similar to the natural bone.
thermionic vacuum arc method (TVA).
Austenitic stainless steel, titanium and its alloys are
The method (TVA) is based on evaporating the coating
widely used for biomedical applications, including devices
material by an indirectly heated cathode surrounded by a
for bone fixation and partial/total joint replacement because
Wehnelt cylinder. [4]
they are corrosion resistant metals with the required
The evaporation material state is obtained by heating it
mechanical strength and biocompatibility. They are referred
with thermal electrons generated by the circular shape
as ―first generation of biomaterials‖ [1] in the technical
filament indirectly heated and situated above the anode. The
studies.
used anode was a carbon rod with a 6mm diameter.
These biomaterials for implants are not osseoconductive
Due to large energy dissipated in the plasma volume, the
and their surface does not have structural and functional
deposited material is completely dispersed without drops.
connection with the living bone that can enable reaction with
The obtained film is very fine and under certain conditions
the surrounding tissues, referred as osseointegration.
appears as a nanostructures deposition.
Furthermore, they tend to release a high concentration of
The thickness of deposited layer was 150nm, and the
metal ions into the body, which is likely to have toxic effects
deposition was made at Ovidius Constanta University.
on bone cells, leading to failure and may inhibit formation of
bone (osteogenesis). II. MATERIALS PROPERTIES
―The second generation of biomaterials‖ are bio-active The ideals proprieties of materials for implants are:
ceramics such as calcium phosphate and bioactive glass and - Hard resistance at static and dynamics loads which
was developed as possible alternative to the first generation appears in the implant place;
of metallic biomaterials. These materials have the ability to - Resistance at alternative bending tests;
promote bone apposition with bone tissues without fibrous - Wear resistance;
encapsulation, thereby leading to osseointegration. - Corrosion resistance at the body fluids;
One of these materials is calcium carbonate-containing - Chemical and thermal stability;
apatite layer (CA) which is chemically similar to the - Unaffected by X ray radiation;
inorganic mineral phase of a natural bone and is considered - Undistorted by manufactured process;
important for the osseointegration process. However, this - Low price;
class of bioceramics exhibits low bending strength (42–200 - To be reproducible;
MPa) and is brittle, restricting their use in load bearing - Non-toxic and no-allergenic in contact with body
applications [2]. fluids;
The implant must interact with the adjacent tissue, to - Bio tolerant at the interface tissue-materials.
permit the bone regeneration and the growth of osteogenic
III. TEST SPECIMENS
cells.
In order to characterize the mechanical properties of
The texture of surface implants is very important in the

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coatings with nanostructured materials obtained by DLC 3. Connecting part (abutment);

deposition, dental implants were used as samples (see fig. 1), 4. Hemispherical loading member;
made from pure titanium material, which is one of the most 5. Dental implant body;
used materials for implants manufacturing. 6. Clamping device.
For the tests were use four specimens, two uncovered and Dental implant assembly with no pre-angled connecting
two with ultra thin DLC deposition using thermionic vacuum part and hemispherical member must be clamped so that its
arc method (TVA). axis makes an angle of 30   2  with the loading direction
The used dental implants consisted of tapping component of the testing machine (see fig. 3.)
with a diameter of 3.2mm and 13.2 mm long and abutment
with conical surface (at an angle of 10), for connecting with
the assembly, total length of 9.5 mm and M2 threaded
fastener (see fig.2). The parts were made of pure titanium
99.9 %.

Fig. 1: Dental implant assembly

Fig.4: Clamping and positioning device

According to the scheme in Figure 3, load center "C" is at

the intersection between the longitudinal axis of the
assembly and loading axis of the testing machine and must
Fig. 2: Tapping component and abutment be at a distance l=11 mm from the surface of the clamping
device.
In order to ensure the requirements of SR EN ISO
14801:2008 a clamping and positioning device for the
sample was designed (see fig. 4.).
V. MECHANICAL PROPRIETIES EVALUATION
The testing method applied to specimens in order to
characterize the mechanical properties is fatigue test.
Failure of biomedical implants is dominated by fatigue or
fatigue related failure such as fretting fatigue which is
affected by various factors (mean stress, frequency or stress
cycling, etc.).
For determination of mechanical resistance the dental
implants specimens were submitted to dynamic fatigue tests.
The purpose of this comparative study is to determine the
number of cycles until failure in fatigue testing according to
SR EN ISO 14801: 2008 and static compression strength
according to SR EN ISO 6892-1:2010, for dental implants
made of pure titanium covered/not covered with a layer of
DLC.
The obtained results were compared in order to observe
Fig. 3: Testing configuration according to SR EN ISO 14801:2008 the influence of the covering with nanostructured layers
IV. LOADING GEOMETRY upon mechanical characteristics of the tested parts.
Fatigue testing was performed by simulation of the To determine the value of maximum loading force for
functional loading on the endosseous dental implant, with dynamic fatigue tests, the standard recommends first a static
abutment and tapping component, in the worst possible test to determine the compression strength of the sample,
operating conditions. which is oriented in the same position as in the case of
To comply with the requirements of the fatigue test dynamic application.
method specified by EN ISO 14801:2008, a hemispherical For the compression strength determination, tests were
part with a radius of 2.5 mm was mounted on the implants made on a static testing machine Hounsfield H10KT type
subjected to this test and the assembly was fixed on the (fig.5 a) and the dynamic fatigue tests were made on an
machine‘s table Instron 8872 type in the configuration Instron 8872 testing machine (fig.5 b).
presented in figure 3. VI. RESULTS AND DISCUSSION
Notations in the figure are: The characteristic curves obtained in compression strength
1. Loading device which should allow free movement determination are presented in the figure 6.
transverse to loading direction;
2. Nominal bone level;

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a) Static testing machine Hounsfield H10KT

Fig. 6: Characteristic curves in the compression test1-uncovered specimen;

2- DLC covered specimen

In order to prevent this inconvenience a ultra thin layer of

DLC can be deposited on the implant, improving also the
wear resistance and lowering the friction coefficient.
From the obtained results we can see that by surface
treating due to nanometric deposition of carbon fibres,
endurance limit and compressive strength shows a slight
improvement. DLC coatings with biocompatible properties
lead to improved endurance limits of the endosseous
implants.
b) Dynamic testing machine Instron 8872
Another improvement achieved by coating with DLC film
Fig. 5: Testing machines is the increase of the elasticity range observed on the
The maximum loading force was 318,4N for the characteristic curves for the compression test.
uncovered specimen while, for the DLC covered specimen, All these specific properties of DLC coatings are very
the force increased up to 332N. suitable for improving the performance of medical devices
On the characteristic curves the absence of the material and micro-mechanical devices for biomedical applications.
yielding can be observed for the specimen with The aim of dental implant is to achieve at least the same
nanostructured layer deposition, suggesting an improvement percentage of elongation under the same stress in an implant-
of the elastic properties. bone-combination. The increase of the implant elasticity in
For the dynamic test the maximum loading force was order to be similar to that of the bone is the most promising
established to 200N representing about 63% of maximum way to achieve the desired adapted implant elasticity.
strength obtained from static loading. Due to the mentioned above considerations the obtained
Force was applied unidirectional and varied sinusoidal increased elasticity of the specimens is a favourable effect.
and was ranged between 200 N and 20N (minimum value This can lead to the increase of the implant‘s life-time [5].
equal to 10% of maximum value) in order not to lose contact In the present paper the possibility of improving
between the loading device and the sample. The loading mechanical properties of the conventional biomaterials was
frequency was set at 15 Hz. demonstrated by mechanical testing of coated and uncoated
The test ended at the sample failure and the software of specimens leading to greater elasticity, compression strength
the testing machine recorded automatically the cycle number and better fatigue strength.
at which failure occurred. The future researches can be orientated to improve the
The recorded number of cycles for the uncovered sample surface depositing process in order to obtain a better
was 1,282,736 and for DLC covered sample was 1,346,424 homogeneity of the specimen and repeatability of the results.
cycles. ACKNOWLEDGEMENT
VII. CONCLUSIONS We want to thank to Ovidius Constanta University,
The mechanical strength of the implant scaffolds is rather especially to Nanodepositions Laboratory that helped us
important in applications where load bearing is required, with nanostructured deposition on the dental implant
such as matrices to promote bone tissue growth. specimens and gave us the opportunity to make the
A major problem with titanium implants is that comparative study presented in the present paper.
osseointegration by way of its natural oxide TiO2 is a long REFERENCES
process. S. Mali, R.D.K. Misra, M.C. Somani, L.P. Karjalainen:
As a result, implant fixation takes place through an Biomimetic nanostructured coatings on nano - grained
accumulation of fibrous soft tissue (rather than hard bone),
which over time results in loosening of the implant, causing
discomfort and eventual failure.

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Using Nonconventional Structures as Protective

Colloids in the Dispersion Polymerization of 2 -
Hydroxyethyl Methacrylate with a Comonomer
with Spiroacetal Moiety
Aurica P. CHIRIAC, Loredana E. NITA, Manuela T. NISTOR
“Petru Poni” Institute of Macromolecular Chemistry,
Grigore Ghica Voda Alley No. 41-A, 700487 IASI, Romania
[email protected]
Abstract – The study reports the synthesis of a copolymer based on 2-hydroxyethyl methacrylate and
3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro (5.5) undecane acquired through radical polymerization in the presence
of 2, 2'-Azobis (2-methylpropionitrile). The polymerization process was conducted in the presence of a classic
ionic surfactant – sodium lauryl sulfate (SLS) – and comparatively using two variants of protective colloid: 
cyclodextrin (CD) and poly(aspartic acid)(PAS) respectively. The polymers compositions were confirmed by
FTIR spectra. SEM and AFM investigations of the polymer morphology are also presented. It was concluded
on the proper critical micellar concentration for used tensioactive substances, respectively attributing a
mixed mode of particle nucleation (micellar and homogeneous nucleation) in case of synthesis with SLS and
an entropic mechanism of stabilization with CD and PAS as stabilizers. The mean particle size and size
distribution, as well as zeta potential and conductivity determination on the prepared polymeric particles
attest a relatively monodisperse distribution for the particle size; particles with negatively charged surfaces
and copolymers conductivity prepared in the presence of PAS or CD increased by several orders against
homopolymer.

Index Terms – five key words or phrases arranged alphabetically and separated by commas.

cyclodextrin and poly(aspartic acid), respectively. AFM

I. INTRODUCTION
investigations of the polymer morphology are also presented.
The improvement of the p(HEMA) properties as for
The poly(aspartic acid), belonging to the family of synthetic
example the mechanical properties, permeability,
polypeptides, is a typical biocompatible, biodegradable with
temperature responsive characteristics, and degree of
dispersing activity water-soluble polymer, which can be used
hydration or extent of hydrogel network swelling, for more
as dispersant, antiscalant, or superabsorber, for home
favorable biological responses, it was taken into study. Thus,
detergents, water treatment chemicals, and oil field treatment
by synthesizing amphiphilic materials, combining HEMA
additives, for a variety of organic and inorganic solids and
with hydrophobic components, one can expect the
scales dispersal, in medicines, cosmetics, and food. It is
improvement of the mechanical strength of the obtained
considered to be a sustainable, environmentally compatible
materials, and in this context, the copolymerization is mainly
chemical product and its biodegradability makes it
used to improve mechanical properties of polyHEMA, the
particularly valuable from the point of view of
affinity for water, oxygen permeability etc. [1–4]
environmental acceptability and waste disposal. At the same
Bailey et al. [5] in 1976 described developments in the
time, no toxic or mutagenic effects have been reported for
synthesis of alternating poly(ester–ether)s from spiroortho-
polyaspartic acid. Its derivatives starting from
esters. These are considered biodegradable and useful for
polysuccinimide are reported in the literature as carrier
biomedical applications. [6] In this context, spiroacetals are
component in drug-polymer conjugates for non-steroidal,
key structural elements in many bioactive polyketide natural
antineoplastic or other antiviral agents (acyclovir,
products and related analogues. [7-11] The incorporation of
zidovudine, paclitaxel, methotrexate, amphotericin B). [13]
spiroacetal groups in the polymers structures also, improves
Also, a useful method for increasing the water solubility of
the solubility and the adhesive properties. [12] These
organic compounds is to use cyclodextrin (CD) to form
polymers induce also good oxidative and thermal stability,
inclusion compounds with the guest hydrophobic species.
are good fiber formers, and films with good flexibility and
[14, 15] In this context -cyclodextrin was investigated in
tensile strength. [12] These characteristics are owing to the
emulsion polymerization and the first successful application
spiroacetal ring presence.
as protective colloid belongs to the group of Rimmer. [16]
The present study reports the synthesis of a copolymer
based on HEMA and 3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro II. EXPERIMENTAL PART
(5.5) undecane (U) acquired through radical aqueous The continuous radical polymerization processes between
dispersion polymerization in the presence of AIBN. The 2 - hydroxyethyl methacrylate (HEMA) and 3, 9-divinyl-2,
attempt was to have a solid content as high as 10 wt.-percent 4, 8, 10-tetraoxaspiro[5.5]undecane – (U) were initiated by
and in this context the process was conducted in the presence 2, 2'-Azo bis(2-methylpropionitrile) (AIBN) and conducted
of a classic ionic surfactant – sodium lauryl sulfate (SLS) – under nitrogen atmosphere, at 700C, in a constant
and comparatively using two variants of protective colloid:  temperature bath, with a stirring rate of 250rpm, for 8h,

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using sodium lauryl sulfate (C12H25O4SNa) – (SLS) as at ~1730cm−1 was attributed to  (C=O) group; at ~2940
tensioactive, or poly(aspartic acid) (PAS)(poly (a, b) -D, L cm−1 to  (C–H) stretching of -CH3, and also at ~1270cm−1
aspartic acid sodium salt, Mw= 8100) or  cyclodextrin to  (C–O) stretching vibration. The spiroacetal moieties
(Mw=1135) as protective colloid. The water used in all inclusion was also confirmed by the FTIR spectra. Thus,
experiments was purified using an Ultra Clear TWF UV FTIR spectra of the copolymers presented some new strong
System. The attempt was to have a solid content as high as bands in the region of 1000 – 1200cm-1 (due to esteric C-O-
10 wt.-percent and in this context the process was conducted C stretching) and at ~1715cm -1 (due to C=O stretching of
in the presence of the classic ionic surfactant – sodium lauryl conjugated ester). The relative thermal stability of the
sulfate (SLS) – and comparatively using two variants of homopolymer and copolymers are illustrated in Figure 2.
protective colloid:  cyclodextrin and poly(aspartic acid), According the results the homopolymer and copolymers
respectively. After synthesis the polymeric particles were shows a high mass lost until 4600C. By using thermal
precipitated three times with methanol from water solution analysis (TG) it was found that the copolymerization process
and finally freeze-dried by lyophilization during 24 h. proceeds slowly decrease of thermal stability. Increasing the
The the zeta potential () and the conductivity were intermolecular space, induced by the copolymerization of 2-
estimated by using a dynamic light scattering technique hydroxylethyl methacrylate with 3,9-divinyl-2,4,8,10-
(Zetasizer model Nano ZS, with red laser 633 nm He/ Ne; tetraoxaspiro[5.5] undecane, leads to form a polymeric
Malvern Instruments, UK). The determinations were made structure with a less thermal stability, modified slightly
on 2 ml sample of latexes without dilution. The sampling compared to homopolymer, where the polymeric chains are
was done directly from the reaction vessel and was placed in well wrapped through intramolecular attractive interactions
the cell. All measurements were carried out at 25C. especially hydrogen bonds.
The mean particle size and size distribution of as-prepared
latex polymer particles were also measured by laser
diffraction. Mastersizer Hydro 2000 S (Malvern Instruments,
UK with the whole measuring range from 0.02µm to
2000µm) was used to control the particles size in aqueous
dispersion. Measurements of the particle size of the
copolymers and homopolymer were performed with a pre-
measurement treatment of 10 seconds at 1200 rpm in an
ultrasonic bath built into the Malvern system for a better
dispersion of the sample.
The thermal analysis of P(HEMA) and P(HEMA-co-U)
copolymers has been carried in inert atmosphere at heating
rate of 100C per minute up to 600 0C with a termobalance
from Netzsch, Germany. Non-isothermal experiments were
performed used an average sample weight to 7.5 mg and the
nitrogen flow rate was 50 ml/min.
SEM studies were performed on samples fixed by means
of colloidal copper supports. The samples were covered by
sputtering with a thin layer of gold (EMITECH K 550x).
The coated surface was examined by using an
Environmental Scanning Electron Microscope (ESEM) type Fig. 2. The behavior during thermal decomposition for the studied
Quanta 200 operating at 30 kV with secondary electrons in polymeric samples: (a) P(HEMA), (b) P(HEMA–co–U)DBS, (c) P(HEMA–
high vacuum mode. co–U)C, (d) P(HEMA–co–U)PAS

III. RESULTS AND DISCUSSIONS The inclusion of the oligosaccharides in the synthesis, like
The idealized reaction of the copolymerization process is cyclodextrin also, leads to decrease the initial
illustrated in Figure 1. decomposition temperature, owing to the hydroxyl groups
that are border outside of the ring. The same behavior is
experienced for the copolymer synthesized in the presence of
PAS as protective colloid. This slight decrease in the thermal
stability did not significant affect system stability, offset by
the other improved properties conferred by achieving a
network structure for example. At the same time, based on
the maximum temperature decomposition, the copolymers
show an increase of the thermal stability with 300C until 50
0
C (Table 1). Figure 1 shows that each DTG curve of
homopolymer and copolymers has two or three peaks which
Fig. 1. Idealized copolymerization process is usually interpreted as the decomposition of the sample in
the first step and for the second one is due to a less stable
The structure of the new synthesized copolymers was intermediate product. It can be concluded that the presence
confirmed by FT-IR spectra. Thus, the (O–H) stretching of the comonomer positively affects the thermal behavior of
vibration in PHEMA was registered in the 3400–3500 cm−1 the copolymer as it can be observed from the DTG curves.
range as broad absorptions, and a strong band at ~ 2950cm−1 TABLE I. DATA RESULTED FROM TG AND DTG CURVES OF THE
and ~ 2970cm−1 indicated the  (C–H). Another strong band STUDIED POLYMERS

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Sample W Tonset Tpeak, Tendset, T10

P(HEMA) 94.5 282 372 472 333
P(HEMA–co–U)DBS 94.6 279 423.7 484 326

P(HEMA–co–U)C 94 279 405 482 315

P(HEMA–co–U)PAS 94 235 399 468 317
W - %; T - 0C;

Compared data concerning the dispersion dimensions and

their zeta potential were also obtained onto the lyophilized
particles (Figure 3 and Table 2). From the size distribution
results (Figure 3) it is obviously the influence of the
stabilizer type used in the synthesis. Even strange, it results
the better performance of PAS and CD as stabilizer then that
of the classical one SLS. Thus, the broadness of the resultant
particle size distribution in decreasing order is : P(HEMA-
co-U)DBS  P(HEMA)  P(HEMA-co-U)CD  P(HEMA-co-
U)PAS.

Figure 4. SEM micrographs of the studied polymers PHEMA (a),P(HEMA–

co–U)DBS (b), P(HEMA–co–U)CD (c), P(HEMA–co–U)PAS (d)

IV. CONCLUSION
Taking into account the special effects which may be
generated by both comonomers – network formation,
Figure 3. The particles size distribution after the volume biodegradability and biocompatibility, gel formation
distribution for P(HEMA) (1), P(HEMA-co-U)DBS (2), capacity, binding properties, amphilicity, good oxidative and
P(HEMA-co-U)CD (3), P(HEMA-co-U)PAS (4) thermal stability, good films formers, acid pH sensitivity –
the interest in the development of these new polymeric
TABLE 2. THE ZETA POTENTIAL AND CONDUCTIVITY OF THE
SYNTHESIZED POLYMERIC PARTICLES
structures with emphasis on theoretical aspects is thoroughly
Sample name , mV Conductivity, mS/m justified. In this context further investigation are in course.
P(HEMA) -0.295 ± 0.01 0.353 ± 0.002 ACKNOWLEDGMENTS
P(HEMA-co-U)DBS -7.6 ± 1.04 0.207 ± 0.003
This work was supported by CNCSIS–UEFISCSU,
P(HEMA-co-U)PAS -1.923 ± 0.41 0.970 ± 0.01 project number 466 PNII—IDEI code_995/2009: Researches
P(HEMA-co-U)CD -0.39 ± 0.24 0.573 ± 0.001 in the Field of Polymeric Matrices Design for Sensitive
Structures Romania.
From the determinations it results all particle surfaces REFERENCES
were negatively charged, and also the surfactant nature [1] Cretua A, Gattina R, Brachaisa L, Barbier-Baudrya D.
significantly influences the surface charges, due to the Synthesis and degradation of poly (2-hydroxyethyl
functional groups. The zeta potential results indicate a low methacrylate)-graft-poly (-caprolactone) copolymers.
surface charge for the homopolymer, followed by the Polymer Degradation and Stability; 83 (3): 399–404,
P(HEMA-co-U)CD  P(HEMA-co-U)PAS and finally 2004
P(HEMA-co-U)DBS. The conductivity of the copolymers [2] Barakat I, Dubois Ph, Grandfils C, Jerome R.
prepared in the presence of PAS or CD was found to be Macromolecular engineering of polylactones and
increased by several orders against homopolymer. polylactides. XXV. Synthesis and characterization of
Morphological information concerning the studied bioerodible amphiphilic networks and their use as
polymeric compounds utilizing SEM is presented in Figures controlled drug delivery systems. J Polym Sci A: Polym
4 a – d. The structural and compositional characteristics of Chem; 37:2401–11, 1999
the surfaces are evidenced and differences between the [3] Eschbach F, Huang S. Hydrophilic-hydrophobic binary
synthesized homopolymer (Figure 4a) and the copolymers systems of poly(2-hydroxyethyl methacrylate) and
(Figures 4b-d) are proof. SEM micrographs show that the polycprolactone. Part I. Synthesis and characterization. J
polymers prepared with different stabilizers possess a Bioact Compat Polym; 9: 29–54, 1994
distinct structure. The homopolymer seems to have more [4] Eschbach F, Huang S, Cameron J. Hydrophilic-
homogeneous structure instead of the copolymers that hydrophobic binary systems of poly(2-
appear with an internal lamellar structure in case of using hydroxyethylmethacrylate) and polycprolactone. Part II.
CD as protective colloid, like a lace when PAS is the Degradation. J Bioact Compat Polym; 9: 210–21, 1994.
stabilizer, and a little bit inhomogeneous structure in case of [5] Bailey WJ, Iwama H, Tsushima R. Synthesis of
SLS. elastomers by cationic polymerization with expansion in
volume. J Polym Sci: Symp; 56:117–27, 1976.

367
 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

[6] Moorea T, Adhikaria R, Gunatillakea P. Oikawa H. The spiroketals containing a

Chemosynthesis of bioresorbable poly(g-butyrolactone) benzyloxymethyl moiety at C8 position showed the
by ring-opening polymerisation: a review. Biomaterials; most potent apoptosis-inducing activity. Bioorg Med
26 (18): 3771–3782; 2005 Chem Lett; 9(14): 2007-2012; 1999.
[7] O‘Hagan D. The Polyketide Metabolites, Ellis [13] Polymeric materials encyclopedia. Ed by Joseph C.
Horwood, Chichester, 1991; O‘Hagan D. Biosynthesis Salamone; Spiroacetal backbone polymers; p. 7858,
of fatty acid and polyketide metabolites. Nat Prod Rep; 1996;
12: 1; 1995; [14] Ehtezazi T, Govender T, Stolnik S. Hydrogen Bonding
[8] Norcross RD, Paterson I. Total Synthesis of Bioactive and Electrostatic Interaction Contributions to the
Marine Macrolides. Chem Rev; 95: 2041; 1995. Interaction of a Cationic Drug with Polyaspartic Acid.
[9] Pettit GR, Chicacz ZA, Gao F, Herald CL, Boyd MR, Pharm Res 17: 871-877; 2000.
Schmidt JM, Hooper JN A. Antineoplastic agents. 257. [15] Saenger W. Cyclodextrin Inclusion Compounds in
Isolation and structure of spongistatin 1. J Org Chem; Research and Industry. Angew Chem Int Ed; 19:344;
58(6): 1302-1304; 1993; 1980
[10] Kobayashi M, Aoki S, Sakai H, Kawazoe K, Kihara N, [16] Wenz G. Cyclodextrins as Building Blocks for
Sasaki T, Kitagawa I. Altohyrtin A a potent anti-tumor Supramolecular Structures and Functional Units. Angew
macrolide from the Okinawan marine sponge Hyrtios Chem Int Ed; 33:803; 1994.
altum. Tetrahedron Lett; 34 (17): 2795-2798; 1993. [17] Rimmer S, Tattersall P. The inclusion of b cyclodextrin
[11] Kulkarni BA, Roth GP, Lobkovsky E, Porco JA. provides a supramolecular solution to the problem of
Combinatorial Synthesis of Natural Product-like polymerization of dodecyl and octadecyl methacrylates
Molecules Using a First-Generation Spiroketal Scaffold in aqueous emulsion. Polymer 1999; 40: 5729–5731.
J Comb Chem; 4(1) 56-72; 2002; Trump RP, Bartlett Rimmer S, Tattersall PI. Emulsion polymerizations in
PA. the presence of -cyclodextrin. Polymer; 40: 6673–
[12] Amino Acid-Derived Heterocycles as Combinatorial 6677; 1999
Library Targets: Spirocyclic Ketal Lactones. J Comb
Chem; 5(3): 285-291; 2003; Mitsuhashi S, Shima H,
Kawamura T, Kikuchi K, Oikawa M, Ichihara A,

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Innovative Realizations in the Research of

Dental Implants
Gheorghe GRANCIUC
[email protected]
Faculty of Dental Medicine, State University of Medicine and Pharmacy „N. Testemitanu”, Moldova

Abstract – This article describes a method that can be used in experimental dentistry for investigations of
osteointegration processes of dental implants. The procedure was patented (Patent BOPI AGEPI MD
nr.12.2010). The researches accomplished below represent a component part of the subject area consecrated
to the Evaluation of coordinative compounds of Zink and Vanadium at the stimulation of osteo-regenerative
processes in periodontal tissues and at the application of dental implants. The experimental investigation
included experiments carried out on 280 white rats. There were taken for the study 24 substances that
contained Zink, Vanadium and Nickel. Testing of the influence of some new coordinative compounds of
transitive metals (Zn, V, Ni) on osteo-regenerative processes in normal physiological conditions was
determined in bone tissues of periodontium and femoral bones were extracted later on used for the
determination of principal biochemical indices of bone tissue. There has been determined the most active
biologic coordinative compound Zn(CF3CO2)2(γPic)2 (Patent Nr. 950188 AGEPI MD) in regenerative
processes of periodontal tissues during the modeling of experimental periodontitis. The detailed study of the
influence of the coordinative compounds of Zn and V that have a better biological activity was executed on
the rats that had been inserted dental implants made out of Titan. Before the application of the treatment and
at the end of the treatment with the above mentioned compounds, there were made blood tests of every rat on
hemolymphogram of hematologic analyzer PCE-170 ERMA Japan. There was elaborated a new method of
modeling experimental periodontitis at laboratory animals (Patent Nr. 5388 din 2008.01.14, RM). There were
studied the following biochemical parameters: alkaline phosphatase, acid phosphatase, substances with
medium and small molecular mass (SMSM), necrotic substances (NS), carnosine, nitric oxide, adenosine
deaminase, adenylate deaminase. There were accomplished radiovisiographic densitograms.
Investigational methods of patients with periodontal diseases and dental implants. The examination was
carried out in accordance with the algorithm of estimation of contraindications and indications suggested by
us while inserting dental implants. The elaboration of the algorithm became possible on the base of the
experience in insertion of implants Alpha Bio; MIS; Alpha Dent; CeraRoot Zirconium Oxide Dental
Implants; and the procedures elaborated by us (patent Nr. 2379 from 2004.02.29; patent Nr.8,AGEPI MD
from 2008-02-18).
57 patients with diverse periodontal diseases were subjected to the study. A profound investigation of
biochemical indices of 27 patients was accomplished; out of them 15 patients were inserted dental implants.
Zink picolinate was administrated per os 1 x 3 times a day before meals. The duration of the treatment was
30 days.

surgical interference, the major risk of inflammation of the

I. INTRODUCTION:
wound, the development of inflammatory reactions, sepsis
One of the most important problems of modern
and other complications that influence negatively the results
implantology is the bone integration of dental implants
of the investigation. Successful attempts of dental
including the management of its process. The essential stage
extractions at rats are impossible, because anatomic
is the surgical one; the insertion of the implant in the
maxillary dental peculiarities of theses animals, as well as
alveolar socket and obtaining the adherence of the bone to
those of rabbits or dogs will lead to maxillary fractions or
the implant and achieve a direct bone implant surface
other complications.
without involving connective tissue layer. Branemark‘s
We have elaborated a new experimental model of bone
concepts of bone integration of the implants are based on
regeneration at the use of which are removed all the above
clinical and experimental studies, describing the complexity
mentioned shortcomings (Invention BOPI MD, nr.12. 2010).
of the process of bone integration of the implants. His
The principal stages of the implementation are schematically
postulates confirm that until now the research assures
represented in figure 1.
clinical efficacy of implant use, but nevertheless require
The advantages of the presented procedure in comparison
continued research [1, 2, 6]. Hystomorphological data of
with the known procedure consists in the removal of the
osteointegration process of dental implants are in continuous
major trauma in the area of the surgical operation where the
research [3, 4, 5, 7], in this way the studies of the
implant is to be inserted, as well as in the prevention of the
microscopic structure of the implant-bone contact surfaces
risk of the appearance of inflammatory processes, the
require a better examination.
preservation of the crown part of the central incisor,
II. MATERIAL AND METHODS. maximum possible preservation of bone and soft tissues due
In general, the procedures of insertion of implants in to the adaptation of the procedure to the real conditions and
maxillary bones of known laboratory animals are related to a the optimum choice of the place of the insertion of the
massive traumatism of periodontal tissues as a result of implant namely there, where the anatomic place of the tooth
root can be found.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

the titanium implant with the surrounding tissue structures,

including the dynamics of their formation.
Results: Groups of control. Mandibular bone plus implant
film were made 15 days later after the experiment had been
done (Fig. 2, b) from the moment of the insertion of the
implant where existed a powerful intensification of the
process of bone regeneration.

a b

c d
Fig. 2 (a, b, c, d). Microphotograms. Haematoxylin eosin stain. Images of
the implants with surrounding tissue in the control group 2 weeks (a, b)
from the surgery of insertion of the implant. The new young bone tissue
covered the area directly bordering the implant. The tissue maturation is a
continuous process, fibrous tissue is noticed on the bordering of the implant
(a), bone only rarely adhere to the implant surface (a, b). Histology images
(c, d)-images had been taken 1 month later after the surgery.

The structure of newly regenerated trabecular bone

surrounds the whole surface of the implant. The tissue is
partially separated from the implant surface by a few
Fig.1. Schematic representation of the principle stages of the
accomplishment of the experimental model of the investigation in the elongated cells like fibroblasts (fig. 2b). The preparations
process of bone regeneration : 1) rat‘s mandibulae and teeth ; 2) the and photos made in 30 days do not show any big changes in
appearance of bone deffect in the apical portion of alveolus ; 3) the removal comparison with those, taken after 15 days, the process of
of the apical root portion of the incisive ; 4) the insertion of the implant and tissue maturation has not progressed further. The
of the investigational remedy in the dental alveolus in the root part and the
crown one which remained, there was realised devitalixation and development and maturation of essential components of
obstruction. fibroblast cells is observed at the edge of the implant surface
and new bone formation, but rarely the last more compact
The animals were put to sleep with the intervals of 2 adhere to the implant surface (Fig. 2c, d). There are
weeks and 1 month with a light anesthesia overdose. During incomplete spaces between the implant and the bone is more
the surgical operation the mandibles were realized the limited, highlights rich blood vascularity.
preparations of the implants with the surrounding bone Groups of vertebrates with implants inserted into the bone
tissues. Hemi-mandibular samples were kept for 10 days in which were given TS-1Z. Histological examination 2 weeks
10% formalin solution and then 2 days in 70% alcohol, ethyl after surgery (3 a, b) the defect is observed, the periphery of
alcohol 90% 2 days, 2 days 96% alcohol, absolute alcohol which is occupied by granulation tissue rich in cells and
one week, 24 hours a mixture of ethanol + acetone (1:1) blood vessels. Mandibular bone is traumatized by
100% acetone for a week with daily changes of acetone. trepanation of bone creating a cavity for insertion of the
After these procedures, the portion of jaw bone where the implant (Fig 3a), but no inflammatory phenomenon had been
implant had been inserted and placed into a propylene resin observed. Also, the microscope image (Fig. 3b) highlights
solution. Solidification of the preparations lasted one week. the implant-bone postsurgical area with bone trabeculae
The slice cuts of the preparations on the limit bone-implant since implant insertion and that image show precursors of
were performed at different depths and parts of the implant tissue cells transformed into cells recruited osseoblastic bone
and haematoxylin-eosin staining was performed. formation process - osteoinduction.
III. PURPOSE OF THE RESEARCH: After 1 month of surgical intervention (Fig. 3c, d) on
a comparative histological examination of the potential of mandible bone defect caused by insertion of the implant in
osteointegrated implants in different groups of rats which cavity is regenerated with bone structure, which replaced
have been given coordinative compounds Zn (LH) 2, Zn (LH) fibrous tissue. The junction between implant and adjacent
etazol, [VO (L-H) etazol] 2SO4 respectively with indices bone is completely renewed and implant is completely
TS-1Z, 2Z-TS, TS-9V, in this way getting the opportunity to anchored into the bone.
study the contact area between the surface of the substrate of

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

a b
a b
Fig.5 (a, b). Microphotograms 2 weeks since the implant insertion. Group
that was administered TS-9V. At the implant-bone boundary is revealed
reduced bone tissue regeneration (a) on the implant surface there are bone
trabeculae with irregular outline (b).

c d
Fig.3 (a, b, c, d). Microphotograms (hematoxilin eosin staining) The group
which were given TS-1Z. The results obtained in 2 weeks (a, b) after
surgery.Bone implant is surrounded by fibrous tissue which may be
substituted by bone tissue (c, d) - histology results in 1 month after the
surgery. a b
We can notice the thin structure of bone trabeculae and
newly formed bone, with a network which is mostly fibrous
tissue.

c d

Fig.6 (a, b, c, d). Microphotograms. Implant-bone group preparations on

a b mandible, which has been administered TS-9V. Hematoxylin eosin stain.
Osteogenesis in 1 month after the implantion. Regeneration of the bone is
anchoring on the implant surface flowing uniformly throughout the
perimeter area of the implant. Osteoconduction of osteoblastic cells prevail.

Analysis of junction surface bone to implant after 1 month

of implant insertion time (Fig. 4c, d) and (Fig. 4d, e) showed
that there are areas where the trabeculae grow in size and
regenerate bone in a lamellar structure in comparison to
osteointegration processes after 15 days (Fig. 3, b).
c d
Formation of direct contact between bone and implant with
connective tissue layer is considered low as a morphological
manifestation process of osteointegration. Directly on the
implant surface was formed bone, presence of fibrous tissue.
Groups of prepares implant + bone of animals which were
administered TS-9V. Histological analysis of preparations of
this studied group demonstrated that TS-9V preparation
e f stimulates the regeneration of bone tissue comparing to
experiment with compounds administered in previous
Fig. 4 (a, b, c, d, e, f) Microphotograms. Hematoxylin- eosin stain. groups, but the process starts a little later. The images (Fig. 5
Histological implant-bone preparations of rats that received the TS-2Z for 2 a, b) - in 15 days on implant surface there is newly formed
weeks (a, b) since implant insertion. On the implant surface we can notice bone present, continuing maturation, portions of connective
roughness which is due to sandblasting. Rich in blood vascularity. The
implant is surrounded by a capsule mostly fibrocellular (a, b) in image (b)
tissue, the consequences of posttraumatic cavity formation in
the right to see the regeneration of new bone. Image (c, d) of preparation the stage insertion of the implant. After 1 month implant
implant + bone after 1 month since implant insertion. (e, f) - another insertion (Fig. 6, b, c, d) - osteogenesis in evolution. The
preparation from the same group - image after 1 month-final stage of area around postsurgical implant bone defects are restored
osteointegration.
by a new bone structure, the osteointegrated implant is
Groups of preparate animal implant + bone which were formed. The process has a satisfactory result.
given TS-2Z. The administration of coordinative compounds The comparison of the radiovisiographic
TS-2Z showed that the defect is replaced by spongy bone, densitograms of the rats‘ mandibles, which were operated
newly formed bone trabeculae and presence of osteoblasts and inserted titanium implants, made two weeks and a month
(Fig. 4, b). In none of the histological preparations were after the operation under the influence of the most active
observed inflammatory processes, changes in the prevalence coordinative compounds Zn(L-H)-etazol, Zn(L-2H)-
of destructive or fibrous tissue. sulfadimizin, Zn(NH₂-C₆H₄-CH₂-C₆H₄-NH₂)₂SO₄ and

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Zn(CH₃COO)₂•4H₂O) show a high intensity of The results of this study also come up with arguments of
osteointegration activity of the edges of the bone cavity guidance on the use of dental implants with administering of
surrounding the implant (photo 7, 8, 9, 10). The most coordinative compounds of Zn. There are coordinative
relevant results were registered during the application of the compounds that can be used in implantology and there is a
necessity to make direct studies of implant-bone interface
compound Zn(NH₂-C₆H₄-CH₂-C₆H₄-NH₂)₂SO₄, this involving molecular medicine studies. Histological analysis
indicates the fact of a more pronounced osteoinductive of the preparations which received the compounds
action of this substance in the graphic image (figure 11). mentioned above, in comparison with the control group,
demonstrated success of the guided tissue and bone
formation in intimate contact with implant surface but also
its penetration into the pores of the implant. Bone integration
of the implants were observed in most unique comparative
analysis between group of study and the administration of
TS-2Z compound, but TS-1Z compounds, TS-9V that
stimulated bone regeneration. Histological results confirm
the benefic results with biochemical and hematological
indices which improved after the implant application at the
animals that were administered coordinative compounds Zn
(LH) 2, Zn (LH) etazol, [VO (L-H) etazol] 2SO4.
Foto 7. Control in two weeks. Foto 8. Control in a month.
BIBLIOGRAPHY
[1] COOPER, L. F. Biologic determinants of bone
formation for osseointegration: clues for future clinical
improvements // J Prosthet Dent. – 1998. – Vol. 80, Nr.
4. – P. 439-449.
[2] EARTHMAN J. C., Y. LI , L. R., Van SCHOIACK, et
al. Reconstructive materials and bone tissue engineering
in implant dentistry // Dent Clin North Am. -2006. –
Vol. 50, Nr. 2. – P. 229-244.
[3] Granciuc Gh., Ciuntu O. Action du remede stimulant
l‘osteogenese sur l‘application des implants de titane
chez les rats blancs. V Congres de l‘Entente Medicale
Foto 9.(Zn(NH₂-C₆H₄-CH₂-C₆H₄- Foto 10.(Zn(NH₂-C₆H₄-CH₂- Mediterranienne et XXII Semaine medicale Balkanique.
NH₂)₂SO₄ (after two weeks). C₆H₄-NH₂)₂SO₄ (after a month). Istambul, Turcia, 1994.
[4] Granciuc Gh., Ciuntu O. La normalisation des
dereglements metabolique presentes a la paradontite
200 experimentale a l‘aide d‘une nouvelle preparate. XXIII-
e Semaine Medicale Balkanique. Constanţa, Romînia,
150
2 weeks
1992.
100 [5] Granciuc Gh., Ciuntu O. La normalisation des
1 month dereglements metabolique presentes a la paradontite
50
experimentale a l‘aide d‘une nouvelle preparate. XXIII-
0 e Semaine Medicale Balkanique. Constanţa, Romînia,
1 2 3 4 1992.
[6] Granciuc Gh., Nastas I., Gulea A. Influenţa unor
Fig.11. Statistic comparison of densitograms preparate noi de zinc si vanadiu asupra proceselor
two weeks and a month after the the insertion of the implants out of titan osteoregenerative in parodonţiu. Anale Ştiinţifice ale
and the administration of the most active coordinative compounds : 1 – Universităţii de Stat de Medicină şi Farmacie „N.
Zn(L-H)-etazol; 2 – Zn(L-2H)-sulphadimizyn; 3 – Zn(NH₂-C₆H₄-CH₂- Testemiţanu‖, Vol. 1: Probleme medico – biologice şi
C₆H₄-NH₂)₂SO₄; 4 – Zn(CH₃COO)₂•4H₂O. farmaceutice, Chişinău, 2005, pp. 336-339.
[7] TRIPLETT R. G., U. FROHBERG, N. SYKARAS, R.
D. WOODY. Implant materials, design, and surface
IV. CONCLUSIONS:
topographies: their influence on osteointegration of
Analyzing the histological examination with the results
dental implants. // J Long Term Eff Med Implants. –
we conclude that the best indicators of osteointegration
2003. – Vol. 13, Nr. 6. – P. 485-501.
process are found in all groups which have been given
coordinative compounds Zn(LH)2, Zn(LH)etazol, [VO(L-
H)etazol]2SO4.

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Advanced EEG Signal Processing

Rodica STRUNGARU, G. Mihaela UNGUREANU
Politehnica University of Bucharest, Iuliu Maniu 1-3, Bucharest, Romania, RO-061071
[email protected], [email protected]

Abstract – The study investigates the performance of some EEG signal processing methods in detecting the
signal variations within the Event-Related Potential (ERP) and in extracting the EEG effective connectivity,
and the obtained results are discussed. The advantage of applying the Independent Component Analysis
(ICA) in EEG analysis is also considered. The EEG data are recorded in the framework of BCI 2005
competition, during a motor imager task, and includes segments of Event-Related (De)synchronization,
revealed be the proposed signal processing methods: Event-Related Spectral Perturbation, , the Inter-Trial
Phase Coherence, the Inter-Trial Linear Coherence and the Event Related Cross- Coherence. The effective
connectivity is analyzed in time and frequency domain, by applying the Granger Causality Index (GCI) and
the Partial-Directed Coherence (PDC) respectively, as time-variant or time-invariant methods.

Index Terms – EEG, effective connectivity, ERP, ICA.

ERP).
I. INTRODUCTION The frequency-domain analysis usually investigates the
The brain behavior is still unknown and lately a lot of variations of the spectral components, relatively to a period
efforts are done to reveal i) its anatomical connectivity (AC), of relaxation, when the ERP is supposed not to be relevant (a
determined by the anatomical links, ii) its functional short period before the stimulus application). The most
connectivity (FC) obtained when analyzing the statistical applied frequency-domain methods are: the Event Related
dependencies among the EEG signals, or iii) its effective Spectral Perturbation, the Inter-Trial Phase Coherence, the
brain connectivity (EC), which represents the instantaneous Inter-Trial Linear Coherence and the Event Related Cross-
information flow within the brain [1]. The effective Coherence.
connectivity is to be extracted in time or in frequency
Event Related Spectral Perturbation (ERSP)
domain, by using the Granger Causality Index or the Partial
Directed Coherence. Both methods need a good EEG The event related spectral perturbation allows scientist to
channel selection in order to have a high performance. The observe when the spectral components are (much) reduced
EEG channel selection is usually done after a deep channel after a certain event, which is reported in literature as Event-
analysis, in time and/or frequency domain, after Related Desynchronization (ERD) or to notice whether the
investigating the functional connectivity. The current study neurons are getting synchronized, generating some
shows a typical EEG signal processing when investigating additional frequency components, which is known as Event-
the EEG effective connectivity. Related Synchronization (ERS) [3].
The method performs an average over all the similar trials,
II. DATA DESCRIPTION in frequency-domain, to get the information relevant for the
The EEG dataset consist of EEG segments lasting for 7 analyzed EEG task:
s, recorded during a tongue motor imagery task. The first 2 s 1 n

2
are used to extract the EEG characteristics corresponding to ERSP ( f , t )  Fk ( f , t ) (1)
n k 1
the resting state, before the stimuli are applied. A beep
fixation cross makes the subjects concentrate on the EEG where n represents the number of EEG segments, Fk(f,t) is
task; it lasts on the screen for 1 s. An arrow appears then, the spectral component at frequency f, computed at time t,
indicating the subjects to imagine the motor task, during a for the k-th analyzed EEG segment. Fk(f,t) can be computed
period of 4 s (Fig. 1) [2]. by applying the Short-Time-Fourier Transform (STFT) and
Wavelet Transform.

Inter-Trial Phase Coherence (ITPC)

The Inter-Trial Phase Coherence (ITPC) reveals the phase

synchronization, relatively to the resting state, when
Fig. 1. Paradigm description considering different trials:
III. SIGNAL PROCESSING METHODS 1 n Fk ( f , t )
Most of the EEG studies analyze the signal behavior in ITPC ( f , t )  
n k 1 Fk ( f , t )
(2)
time or in frequency domain, when considering some
particular stimuli that generate the Event-Related Potential When the phase coherence is determined based on the
(ERP). Since the non-stationary EEG signal has a low spectrum averaging, normalized by the averaged spectrum,
amplitude, decreasing exponentially with frequency, the we get the Inter-Trial Linear Coherence:
time-domain analysis consists in averaging the
corresponding EEG segments, which allows the localization
of paradigms (i.e. P300, or P3 represents a positive peak in

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n It is the most applied ICA algorithm and uses the fourth

 Fk ( f , t ) cumulant to compute the kurtosis. The steps of the algorithm
k 1
ITLC( f , t )  (3) are:
n
1. Initialization (data whitening):
n Fk ( f , t )
2

k 1 W

 1
1
 1 
ˆ  diag   ˆ 2 2 ,, q  ˆ 2 2 ,0,,0 VT
  
 
Event Related Cross- Coherence (ERCOH) ˆ x and,
with yˆ  W
Event Related Phase Cross-Coherence (ERCOH) 1 q
determines the relation between two different event types, by ˆ 2    
p  q j  p 1 j
analyzing the phase of the corresponding computed spectra.
with q  p .
1 n Fka ( f , t ) Fkb ( f , t )*
ERPCOH a,b ( f , t )  
n k 1 Fka ( f , t ) Fkb ( f , t )
(4) 2. Computation of the Kurtosis for ŷ ; the set of the

When the averaging doesn‘t include the normalization,

fourth cumulants, Qiy , is obtained.  
which extracts only the phase, the Event Related Linear 3. Optimize an orthogonal contrast: the matrix V has
Cross-Coherence (ERLCOH) is computed: to be estimated so that the contrast function is minimized:
n  JADE   Qijkl
y
  off VT Qiy V  
 Fka ( f , t ) Fkb ( f , t )* ijkl  ijkl i

ERLCOH a ,b ( f , t )  k 1
(5) where off A  are the nondiagonal elements:
n n
 Fka ( f , t )  Fkb ( f , t ) off (A)   aij
2 2

k 1 k 1 i j
The matrix V is computed using the Jacobian.
Independent Component Analysis (ICA) 4. Mixing matrix estimation:
ˆ  WT V
A
ICA extracts the components that are not only
decorrelated but also independent. It considers the 5. The extraction of the independent components:
computation of higher order moments (3 rd and 4th moment) s  sˆ  VT y  VT W x
and is suitable for signals that have no more than one
Gaussian component [4]. The algorithm is briefly described
IV. EFFECTIVE CONNECTIVITY DETECTION
in the figure bellow:
The effective connectivity can be estimated based on the
linear multivariate auto-regressive model. When the model
parameters are time-varying, the Granger Causality Index
and the Partial Directed Coherence are time-variant;
otherwise, they are computed as time-invariant measures of
Fig. 2. ICA model - BSS extraction of p signals
effective connectivity.
ICA extracts the signal sources by applying the matrix
inverse: Granger Causality Index
s  A1x (6) Let us consider the full MVAR(p) model with regard to y
Two of the most representative ICA algorithms reported with time-dependent parameters and with the prediction
in the literature are: i) the one developed by J. F. Cardoso error:
and Antoine Souloumiac, JADE (joint approximate p
diagonalization of eigen-matrices) (Cardoso & Souloumiac, y n    A k n   y n  k    y n ,
1993); ii) FastICA, developed by Hyvärinen; it is based on a k 1 (9)
fixed-point iteration scheme maximizing non-Gaussianity as A k n ,  y n   N
a measure of statistical independence. The idea of ICA is to
extract the vector sources, s, with q components, from the The reduced MVAR(p) model is so:
p
recorded vector x, including p channels:
v i n    Bk n  v i n  k    vi n ,
x  As  n (7) (10)
k 1
A is the mixing matrix, n represents the additive noise. B k n ,  vi n    N 1
,
The following assumptions must be met in order to apply
ICA: with:
1. A has linear independent columns (satisfied for real
signals usually) v i   y1 , yi 1 , yi 1 ,, yM T
2. x contains independent variables
3. n and x are independent. Multivariate Time-variant Granger Causality (MVAR
Under these assumptions the mixing matrix can be tvGCI) from i to j is defined by:
estimated and the sources are extracted:  var j ( i (n)) 
ˆ 1x
s  sˆ  A  (i  j )( n)  log  (11)
(8)  var j ( y (n)) 
 
ICA (JADE)

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When only pairs of signals are considered, we have Component 1-2 Phase Coherence
0.51
the Bivariate Time-Variant Granger Causality Index (BIV 10
0.38

Freq. (Hz)
tvGCI). 20
0.25
30
Partial Directed Coherence 40 0.13

0.5 0

coh.
0 0.2
The PDS is evaluated by: coh.
0

Aij  
-2000 -1000 0 1000 2000 3000

 ij   
Time (ms)
(12) 180

a Hj   1a j  
10
90

Freq. (Hz)
20
0
30
where: -90

A   1  A  
40
50 -180
-2000 -1000 0 1000 2000 3000

 a1   a2    aM  
Time (ms)

and Fig. 4. ERPCOH for the 1st and 2nd ICA components.
p

Akl     kl   akl ,r e ir
r 1
The performance in EC estimation depends mainly on
improving the parameter estimation for the group EC
analysis.
V. RESULTS AND DISCUSSIONS
Figure 3 shows the ERD starting at 1.5 s after the stimulus
application, in the beta frequency band. An ERS appears just
after the stimuli application, at about 0.5 s, in alpha band.
The ITC has no relevant information for the analyzed motor
imagery task. Even when the ICA is applied, the ITC is not
relevant for the study (see Fig. 4). Contrary, ICA improves
the EEG analysis in frequency domain, when considering the
ERSP (see Fig. 5).
The ERP is presented in Fig. 6, for all the analyzed trials.
Fig. 5. ERSP and ITC of the 6th and 7th ICA components, when considering
The spectral maps for different spectral components are the tongue motor imagery task
shown in Fig. 7.

Channel C6 pow er and inter-trial phase coherence (k3btongue) ERSP (dB)

10 4
Frequency (Hz)

20 2

30 0
-2
40
-4
4
0 20
dB

dB -4
-500 0 500 1000 1500 2000 2500
Time (ms) ITC
0.6
10
Frequency (Hz)

20 0.4
30
0.2
40

10 0
0.1 0.2
uV

ERP -5
-500 0 500 1000 1500 2000 2500
Fig. 6. ERP for all trials (Channel 28 – C5)
Time (ms)

Fig. 3. ERSP (up) and ITC (down), for channel C6, analyzed during the
tongue motor imagery task. The ERD/ERS is to be noticed at about 30 Hz/
10 Hz.

Figure 8 presents the variation of the EEG maps in time.

The effective connectivity, shown in Fig. 9, reveals an
effective connection from channel 5 to the others, by
applying the tvGCI. When the signal is assumed to be
stationary (the time-invariant PDC), which is not correctly
describing the analyzed EEG signal, no connection is
identified.

Fig. 7. Pseudocolor spectral maps for different frequency bands.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

b)
Fig. 9. Estimation of EEG effective connectivity: a) tv-GCI; b) PDC

ACKNOWLEDGMENTS
The work was funded by the Sectorial Operational
Programme Human Resources Development 2007-2013 of
the Romanian Ministry of Labor, Family and Social
Protection through the Financial Agreement
POSDRU/6/1.5/S/19.

REFERENCES
[1] D. Hemmelmann, M. Ungureanu, W. Hesse, T.
Wüstenberg, J. R. Reichenbach, O. W. Witte, H. Witte,
L. Leistritz, ―Modelling and analysis of time-variant
directed interrelations between brain regions based on
BOLD-signals,‖ Neuroimage, vol. 45(3), pp. 722-37,
2009 Apr 15.
[2] A. Schlogl, F. Lee, H. Bischof, G. Pfurtscheller,
Fig. 8. The variation of pseudocolor spectrum maps in time (tongue motor ―Characterization of four-class motor imagery EEG data
imagery task) for the BCI-competition 2005,‖ J. Neural Eng. 2 L14–
L22, 2005
[3] G Pfurtscheller, F. H. Lopes da Silva, ―Event-related
EEG/MEG synchronization and desynchronization:
basic principles,‖ Clin. Neurophys., vol. 110, pp. 1842-
1857, 1999.
[4] A. Hyvarinen, J. Karhunen, E. Oja, Independent
Component Analysis, John Wiley & Sons, 2001.

a)

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Polarization-Singular Processing of Biological

Layers Laser Images in Order to Diagnose and
Classify their Optical Properties
Alexander G. USHENKO, Alexander V. DUBOLAZOV, Artem O. KARACHEVTSEV
Chernivtsi National University
[email protected]
Abstract – Presented in this work are the results of investigations aimed at analysis of coordinate
distributions of the fourth Stokes vector parameter in laser images of three types of phase-inhomogeneous
layers, namely: rough, ground and bulk scattering layers. To characterize this parameter for all the types of
phase-inhomogeneous layers, the authors have offered to use three groups of parameters: statistic moments
of the first to fourth orders, autocorrelation functions, logarithmic dependences for power spectra.
Ascertained are the criteria for diagnostics and classification of phase-inhomogeneous layers optical
properties.
Index Terms – polarization, singularity, birefringence, autocorrelation, Stokes vector, Jones matrix.

tissues biopsy. From the above reasoning, it seems topical to

I. INTRODUCTION
search new, additional parameters for laser diagnostics of
By tradition, the processes of transforming optical
optically anisotropic structures in biological fluids.
radiation of phase-inhomogeneous objects and media are
This work is aimed at ascertaining the possibilities to
considered, as a rule, in a statistic approach (theory of
diagnose and classify phase-inhomogeneous layers (PhIL) of
radiation transfer [1], Monte-Carlo modeling [2]). Among
various types (surface-scattering, subsurface-scattering and
the most spread traditional methods for studying the
bulk-scattering ones) by determination values and ranges for
scattered light fields, one can separate the following
changing the statistic (moments of the 1-st to the 4-th
independent directions: ―scalar‖ (photometry and
orders), correlation (autocorrelation functions) and fractal
spectrophotometry) [3, 4] and ―vector‖ (polarization
(logarithmic dependences for power spectra) parameters that
nephelometry, Mueller-matrix optics) [5 - 16]. Using these
characterize coordinate distributions for polarization-
approaches, determined are interrelations between the sets of
singular states in PhIL laser images.
statistic moments of the 1-st to the 4-th orders [6, 7, 11, 15],
correlation functions [5, 8, 9, 14], fractal dimensions [5-7] II. MODEL CONCEPTION
that characterize phase-inhomogeneous or rough surfaces As a base for analytical description of processes providing
and coordinate distributions for phases [15, 16], azimuths formation of polarization-inhomogeneous images for various
and ellipticity of polarization in their laser images [6 - 16]. types of PhIL, we have used the model conceptions
In parallel with traditional statistic investigations, formed developed in the works [5-8]:
in recent 10 to 15 years is the new optical approach to  surface-scattering PhIL is a rough surface (superficial
describe a structure of polarizationally inhomogeneous fields layer of the skin epithelium) consisting of an ensemble of
in the case of scattered coherent radiation. The main feature quasi-plane, chaotically oriented micro-areas with optical
of this approach is the analysis of definite polarization states dimensions l   - group 1;
to determine the whole structure of coordinate distributions  PhIL with surface and subsurface scattering – ground
for azimuths and ellipticities of polarization. The so-called glass with rough external and subsurface (the layer of
polarization singularities are commonly used as these states collagen fibrils of the skin derma) components - group 2;
[15, 17, 18]:  PhIL with bulk scattering – optically thick layer of the
 states with linear polarization when the direction skin derma of a various optical thickness - group 3.
of rotation for the electric field vector is Mechanisms providing formation of polarization-
indefinite, the so-called L-points; inhomogeneous images for rough surface
 circularly-polarized states when the azimuth of Optical properties of each micro-area of rough layer of
polarization for the electric field vector is the epithelium are exhaustively characterized with the Jones
indefinite, the so-called C-points. operator of the following look
It is noteworthy that there exists a widespread group of
1 0
optically anisotropic biological objects for which the R  0 p y . (1)
methods of laser polarimetric diagnostics are not so efficient. px
Optically-thin (coefficient of extinction   0.1 ) layers of
various biological fluids (bile, urine, liquor, synovial fluid, It is possible to show that within the sizes ( x, y ) of one
blood plasma, etc.) can be related to these objects. All these micro-area there takes place the change of polarization
layers possess considerably less optical anisotropy (the azimuth  inherent to the refracted plane-polarized laser
possibility of C-points forming is sufficiently small) of the wave with the initial azimuth  0
biological component matter as compared with birefringent
biological tissue structures [5]. On the other hand, the
 p yU 0 y
 x, y   arctg 

pxU 0 x 
  
 arctg pxy tg 0 , (2)

biological fluids are more available for a direct laboratory
analysis as compared to traumatic methods of biological

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

where U 0x , U 0 y are orthogonal components of the Having calculated the set of Jones matrix elements  qg
amplitude U 0 , p x , p y - Fresnel amplitude coefficients for for an optically-thick PhIL, one can define analytical
transmission [5]. expressions (like to (7) – (8)) to find L and C polarization
Thus, in the approach of single scattering the polarization states in the laser image
image of rough surface may be considered as coordinate- L    x, y   q , q  1,2,... (10)
distributed parts of L-polarized states [9, 10].
 C   tg x, y  

Model structure of PhIL with surface and subsurface
(11)
components – ground surfaces    x, y    22 x, y  
  

2

 sin 2 arctg  21  tg  
 11 x, y   12 x, y  
The process providing formation of a local polarization  0

 
2
state can be considered as superposition of ―influences‖ of  
an optically strained subsurface of optically anisotropic layer Thus, the above analytical consideration (relations (1) to
of collagen fibrils as well as the surface rough micro-relief (11)) for various scenarios of transformation of laser
one disposed in sequence. From the analytical viewpoint, radiation by PhIL in all the cases enabled to reveal the
this scenario can be described by superposition F  of the principled possibility of formation of polarization-singular
Jones matrix operators for these partial layers (subsurface states (   0,     ) in respective laser images.
T  and surface R ) 4
In this work, to describe coordinate x, y  distributions for
f11 f 12 r11t11  r12t 21 ;
r11t12  r12t 22 ; , (3)
F   RT    polarization-singular ( L, C ) states in laser images for all
f 21 f 22 r21t11  r22t 21 ;
r21t12  r22t 22 
cos   sin  exp i ; cos  sin  exp i ; .(4)
2 2 the types of PhIL [7, 15]
V4 x, y   0  L  0;
t11 t12
T    
cos  sin  exp i ; sin 2   cos 2  exp i 
 
t 21 t 22
 (12)
Here,  is the direction of the optical axis of fibril; V x, y   1  C     .
 4 4
 - phase shift between orthogonal components ( U x , U y )
III. EXPERIMENTAL SETUP
of the amplitude ( U ) of laser wave with the wavelength  Our study of polarization-inhomogeneous laser images
that arises as a consequence of birefringence in the matter inherent to PhIL was performed using the optical scheme of
n . a laser polarimeter (figure 1) [5, 15]
If taking into account the relations (1), (3) and (4), it
follows that within the limits x, y  of a local bulk formed
is an elliptically polarized part of the object field with the
following parameters
  Fig. 1. Optical scheme of the polarimeter: 1 – He-Ne laser; 2 – collimator;
  (5)
  3, 5, 8 – quarter-wave plates; 4, 9 – polarizer and analyzer, respectively; 6 –
sin 
 x, y   arccos
~   object under investigation; 7 – micro-objective; 10 – CCD camera; 11 –
    f 21  f 22 2     personal computer
 cos 2 arctg  2 
tg 0   
 
   f11  f12     
 Illumination was performed using a parallel beam (Ø =
  10 4 µm) from a Hе-Nе laser (λ = 0.6328 µm) 1. The
  (6)
 
 polarization illuminator (quarter-wave plates 3 and 5 as well
 x, y   arcsin 
~ tg 
    f 21  f 22 2     as polarizer 4) were used to form various polarization states

 sin 2 arctg  tg 0   
2  in the laser beam. Polarization images of PhIL 6 were



   f11  f12     
projected using the micro-objective 7 into the plane of the
As it follows from the analytical relations (5) and (6), light-sensitive area ( 800 pix  600 pix ) in CCD-camera 10.
interaction of the plane-polarized (  0 ) wave with the PhIL Turning the transmission axis of the analyzer 9 by the angles
of this type provides formation of a polarization-
 450 relatively to the direction of the highest velocity axis
inhomogeneous laser image. Among the whole set of values
  ~
~,  , formation of L and C polarization states seems to
for the quarter-wave plate 8, wee could determine the
intensities of right ( I  ) and left ( I  ) circularly polarized
be very probable [7, 15] components for each separated pixel of CCD camera 10. It

L   x, y  q , q  1,2,... (7)  served as a base to calculate coordinate distributions of the
 C   tg x, y   fourth parameter in the Stokes vector V4 m  n ) describing
the laser image of PhIL, if using the relation
   f x, y   f 22 x, y    
2 (8)
 sin 2 arctg  21  I r   I  rik 
  V4 rmn    ik
tg
   f11 x, y   f12 x, y    
0 . (13)
I  rik   I  rik 
2

Polarization structure of laser fields inherent to PhIL with The two-dimensional array (13) was scanned along the
bulk scattering horizontal direction x  1, ..., m with the step x  1 pix .
 (k 1,2,...,m) ,
When analyzing the processes of interaction of laser
radiation with these PhIL, we have used the method of Within the limits of each local sample 1pix  n pix
superposition of the Jones matrix operators (3) for the set of we calculated the amount ( N ) of characteristic values
V4 k   0 , - ( N Lk  ) and V4 k   1 , - ( N kC ).
sequentially disposed optically-thin layers
 
   p   p 1  ... 1 .    (9)

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Thus, we determined the dependences The dependences  

log J N L,C x   log d 1 are
N L x   ( N L , N L
(1) ( 2)
, ..., N L ( m)
) and approximated using the least-squares method into the curves
N  C x   ( N  C (1) , N  C (2) , ..., N  C ( m) ) for amounts of   , straight parts of which serve to determine the slope
polarization-singular L and C  points within the limits angles  and calculate fractal F dimensions by using the
of a laser image for PhIL. relations [6, 15]
FL,C  3  tg . (19)
IV. ESTIMATION CRITERIA FOR POLARIZATION
IMAGES OF PHIL Classification of coordinate distributions N L,C x  should
Distributions N L,C ( x) for the amount of polarization- be performed using the following criteria [14, 15]:
singular states in laser images of PhIL are characterized with  they are fractal on the condition of a constant slope
the set of statistic moments of the 1-st to the 4-th orders angle value   const for 2 to 3 decades of changing sizes
Z j 1,2,3, 4 calculated using the following relations [6, 7] d;
 they are multi-fractal, if several slope angles   are
 
M M


1 1 2
available;
Z1  N L(i,)C ( x) , Z2  N L(i,)C ( x) ,
M i 1
M i 1 (14)  they are random when any stable slope angles are

   
M M
1 1 2 1 1 4 absent within the whole range of changing sizes d .
Z1  3 N L(i,)C ( x) , Z4  4 N L(i,)C ( x) .
Z2 M Z2 M In the latter case, the distributions
 
i 1 i 1
where N  800 600 is the amount of pixels in CCD log J N L,C x   log d 1
are characterized with the
camera 10 (Fig. 1). dispersion
Our analysis of the coordinate structure for N L ,  C x 
 log J N xi   log d 1 
m
1 2
Dz  L, C . (20)
distributions was based on the autocorrelation method by m i 1
using the function [15]
nm
K L,  C m 
1
2 
X t   X t  m   . (15)
(n  m) t 1 V. THE INVESTIGATION OBJECTS
Here, n is the length of discrete sampling CHARACTERISTICS
( 100 pix  50 pix )
N L, C x   X1 , X 2 ,..., X n ;  - average value,  2 - the
Fig. 1 illustrates coordinate
distributions of the fourth parameter for the Stokes vector
dispersion; m, n - positive integers; m  1 pix  is the step V4 m  n inherent to laser images of PhIL in all the groups.
for changing the coordinate x 1  m .
As correlation parameters that characterize the
dependences K L,C x  , we chose:
 correlation area S L, C
m
Fig. 1. Coordinate distributions of V4 m  n of laser images inherent to
S L ,  C   K L ,  C m dm, (16)
PhIL
1

 normalized fourth statistic moment QL ,  C that Our qualitative analysis of coordinate distributions
V4 m  n for laser images of PhIL (figure 1) enabled to
determine the kurtosis of the autocorrelation function
K L,  C m
reveal:
 Practically all the images of the rough surface of skin
(figure 1a) are linearly polarized field V4 m  n  0
 K mi4 ; (17)
N
N
QL ,  C  2 L,C
 2  i 1
  K L ,  C m i 
N
(relations (1) and (2)). Availability of a small amount of the
 i 1  parts V4 m  n  0 polarized otherwise can be related with
The fractal analysis of the distributions N L,C x  was interferential effects of multiple interaction of coherent
waves with adjacent micro-roughnesses.
performed using the calculation of logarithmic dependences
 The image of the rough skin surface with a subsurface
 
log J N L,C x   log d 1 for the power spectra layer of the derma (figure 1b) is characterized with a
J N L,  C x  which was calculated as a discrete Fourier developed polarization-inhomogeneous structure formed
both by linearly ( V4 m  n  0 ) and elliptically
transform of the corresponding autocorrelation function
( V4 m  n  0 ) polarized states, including the circularly
K L,  C m using the MatLab software
( V4 m  n  1 ) polarized ones (relations (5) to (8)).
J N L ,  C x   S xx ( w)   K L,  C me jm , (18)
n
 The images of the optically thick layer of skin (figure
m 1 1c) are characterized with the widest range of changing the
where  are the normalized frequencies, which azimuth and polarization due to multiple bulk scattering
correspond to a spatial frequencies (   d ) that are
1 (relations (10-12)),  1  V4 m  n  1 .
determined by geometrical sizes ( d ) of PhIL structural
elements.

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VI. RESULTS [3] M. J. Everett, K. Shoenenberger, B. W. Colston and L. B. da

The performed analysis of results for statistic ( Z Lj,1,C2,3,4 ), Silva, ―Birefringence characterization of biological tissue by
use of optical coherence tomography,‖ Opt. Lett. 23, 228-230,
correlation ( S L,C , Q L, C ) and fractal ( F L, C , D L,C ) 1998.
[4] J. Shuliang, Yu. Wurong, G. Stoica and V. Lihong, ―Optical
parameters has shown:
fiber based Mueller optical coherence tomography,‖ Opt. Lett.
 Statistic parameters. The most sensitive appears 28, 1206-1208, 2003.
to be both the 1st and the 2nd statistic moments, which [5] Alexander G. Ushenko and Vasilii P. Pishak, ―Laser
characterize the distributions of L  polarization Polarimetry of Biological Tissue: Principles and
states, and the 3rd and the 4th statistic moments, which Applications‖, in Handbook of Coherent-Domain Optical
characterize the distributions of C  polarization Methods: Biomedical Diagnostics, Environmental and
states. The difference between of them reaches 2-3 Material Science, Valery V. Tuchin, ed. (Boston: Kluwer
times for L  states and 5-7 times for C  states; Academic Publishers, 2004), pp. 93-138.
 Correlation parameters. The most sensitive [6] O. V. Angelsky, A. G. Ushenko, Yu. A. Ushenko, V. P.
Pishak, ―Statistical and Fractal Structure of Biological Tissue
appears to be the normalized fourth statistic moment
Mueller Matrix Images‖, in Optical Correlation Techniques
QL ,  C that determine the kurtosis of the and Applications, Oleg V. Angelsky, ed. (Washington: Society
K L,  C m . The intergroup
of Photo-Optical Instrumentation Engineers, 2007), pp. 213-
autocorrelation function 266.
difference reaches one order of magnitude as for [7] O.V. Angelsky, A.G. Ushenko, Yu.A. Ushenko, V.P. Pishak,
L  states as for C  states; and A.P. Peresunko, ―Statistical, Correlation, and Topological
Approaches in Diagnostics of the Structure and Physiological
 Fractal parameters. The fractal analysis appears
State of Birefringent Biological Tissues‖, in Handbook of
to be effective in differentiation of optical properties Photonics for Biomedical Science, Valery V. Tuchin, ed.
of different PhIL too. The difference between the (USA, CRC Press, 2010), pp. 21-67.
C
dispersion D values reaches 2 times; [8] Alexander G. Ushenko, ―Polarization structure of laser
The possibility to differentiate ―group‖ optical properties scattering fields,‖ Opt. Eng. 34, 1088-1093, 1995.
of PhIL with surface, subsurface and bulk light scattering is [9] A.G. Ushenko, ―Stokes-correlometry of biotissues,‖ Laser
illustrated in Table 1. Phys. 10, 1286-1292, 2000.
TABLE I. THE DIFFERENTIATION POSSIBILITIES [10] A.G. Ushenko, ―The Vector Structure of Laser Biospeckle
PhIL Groups 1 – 3 Fields and Polarization Diagnostics of Collagen Skin
Parameters NL N C Structures,‖ Laser Phys. 10, 1143-1149, 2000.
[11] A.G. Ushenko, ―Laser polarimetry of polarization-phase
Z1   statistical moments of the object field of optically anisotropic
Z2   scattering layers,‖ Optics and Spectroscopy 91, 313-316, 2001.
Z3   [12] O.V. Angelsky, A.G. Ushenko, Ye.G. Ushenko, ―2-D Stokes
Z4   Polarimetry of Biospeckle Tissues Images in Pre-Clinic
Diagnostics of Their Pre-Cancer States,‖ J. Holography
S   Speckle 2, 26-33, 2005.
Q   [13] Oleg V. Angelsky, Alexander G. Ushenko, and Yevheniya G.
F   Ushenko, ―Complex degree of mutual polarization of
D   biological tissue coherent images for the diagnostics of their
Note:  - here differentiation is impossible;  - possible. physiological state,‖ J. Biomed. Opt. 10, 060502, 2005.
[14] O. V. Angelsky, A. G. Ushenko, and Ye. G. Ushenko,
VII. CONCLUSION ―Investigation of the correlation structure of biological tissue
1. Analyzed in this work are the main physical polarization images during the diagnostics of their oncological
mechanisms providing formation of polarization changes,‖ Phys. Med. Biol. 50, 4811-4822, 2005.
singularities in laser images of PhIL with surface, subsurface [15] Oleg V. Angelsky, Alexander G. Ushenko, Yevheniya G.
and bulk light scattering. Ushenko, Yuriy Y. Tomka, ―Polarization singularities of
2. Offered are statistical, correlation and fractal biological tissues images,‖ J. Biomed. Opt. 11, 054030, 2006.
parameters for polarization-singular estimating the optical [16] A.G. Ushenko, I. Z.Misevich, V. Istratiy, I. Bachyns‘ka, A. P.
Peresunko, Omar Kamal Numan, and T. G. Moiysuk,
properties inherent to PhIL of all types. ―Evolution of Statistic Moments of 2D-
3. Determined are the ranges for changing the set of [17] Distributions of Biological Liquid Crystal Net Mueller Matrix
criteria that characterize distributions of the amount of Elements in the Process of Their Birefringent Structure
polarization-singular states in laser images, which enabled us Changes,‖ Advances in Optical Technologies 2010, 423145,
to realize both ―intergroup‖ classification and differentiation 2010.
of optical properties related to PhIL of various types. [18] A I. Konukhov and L.A. Melnikov, ―Optical vortices in a
vector field: the general definition based on the analogy with
REFERENCES topological solitons in a 2D ferromagnet, and examples from
[1] W.-F. Cheong, S. A. Prahl, A. J. Welch, ―A Review of the the transverse polarization patterns of lasers,‖ J. Opt. B:
Optical Properties of Biological Tissues,‖ IEEE J. Quantum. Quantum Semiclass. Opt. 3, S139-S144, 2001.
Electron. 26, 2166-2185, 1990. [19] J. F. Nye, ―Lines of circular polarization in electromagnetic
[2] S. A. Prahl, M. Keijzer, S. L. Jacques, A. J. Welch, ―A Monte wave fields,‖ Proc. R. Soc. A 389, 279-290, 1983.
Carlo model of light propagation in tissue,‖ in SPIE
Proceedings of Dosimetry of Laser Radiation in Medicine and
Biology, G. J. Müller and D. H. Sliney, eds. IS 5, 102-111,
1989.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

An Optimized Compounding Approach to

Ultrasound Imaging
Yair KERNER and Moshe PORAT
Technion, Haifa 32000, Israel
E-mail: [email protected], [email protected]

Abstract – We develop an optimized approach to exploit pairs of ultrasound scans of the same image plane
with the aim of enhancing the quality of ultrasound imaging. Each image pair is assumed to be co-registered
with 90° separation between the two insonification directions. Using multi-channel image restoration, the
proposed approach provides significant improvement to the quality of ultrasound imaging. Enhanced images
are presented, and the advantages of this new approach over presently available methods are discussed.

Index Terms – Blind Deconvolution, Image Restoration, Medical Imaging, Spatial Compounding, Ultrasound.

To the best of our knowledge no algorithm was

I. INTRODUCTION
developed to exploit both deconvolution and compounding
In medical ultrasound imaging, short pulses are emitted
for ultrasound image applications. It should be also noted
from an array of resonant elements with a center frequency
that the above-mentioned algorithms for multi-channel
typically in the range of 2-10 MHz. Such two-dimensional
restoration were developed for photographic images. When
(or B-mode) scans undergo two types of blur before the echo
considering these algorithms for the field of ultrasound
returns to the transducer: In the axial (longitudinal) direction
images, one must note fundamental differences in several
the blur results from the envelope of the acoustic wave and
characteristics of the problem: the blur transfer function has
from properties of the tissue through which the wave
band-pass behavior in one dimension rather than low-pass in
propagates; In the lateral (transverse) direction the blur is
both dimensions, the sampling intervals are different in each
affected by the width and apodization of the transmission
direction, and non-linear operations are involved in the
and reception apertures as well as the distance of the imaged
display procedure.
object from the focus and medium-related distortions. The
The research presented in this paper aims at improving
model that is commonly used in ultrasound imaging research
the quality of ultrasound images through exploiting pairs of
for the relation between the received signal and the tissue
ultrasound scans of the same plane. Each image pair is
reflectivity is of a linear space-invariant system (LSI).
assumed to be co-registered with 90° separation between the
Handling space variations of the Point Spread Function
two-insonification directions.
(PSF) is usually through partitioning the imaged plane to
smaller regions with approximately invariant PSF. II. MODEL OF THE PROBLEM
For more than two decades various algorithms have been A. Notation
suggested to sharpen the images, either by deconvolution A 2-D spatial location in the imaging plane is denoted as
assuming the PSF is known [1], [2], or through blind (x, z), where x is the coordinate in the lateral direction and z
deconvolution [3]-[10]. The prevalent approach in blind is the coordinate in the axial direction. In the frequency
deconvolution is to use the LSI method of the Wiener filter domain ( x, z) represents the spatial frequency in radians.
to recover the reflectivity image, and therefore most of the Whenever matrix representation is used the axial direction is
effort is concentrated in estimating the PSF. It is worth column-wise unless stated otherwise. When matrix
noting that while a few algorithms used the video image as coordinates appear in parentheses the first parameter
their input [1], [2], in most of the published work specifies the horizontal coordinate A(m, n) = Anm in order to
deconvolution is applied to the RF image [3]-[10]. keep consistency between matrix and 2-D signal or image
In recent years several authors [11]-[14] developed formulations.
algorithms for compounding of ultrasound images of the The matrix R indicates the unknown tissue reflectivity
same region from different angles. In parallel, researchers in the imaging plane. The matrix S denotes the observed RF
who sought ways to overcome blur phenomena of image, which is the collection of sampled signals from all
photographic images developed algorithms for multi-channel the transducer elements during a single scan.
image restoration. Ghiglia [15] presented a constrained B. Tissue reflectivity and degradation
least-squares algorithm for image restoration given several The tissue reflectivity can be considered as resulting from
blurred images of the same object, each corresponding with an assembly of reflectors and scatterers [7], [10]. A reflector
a different PSF. Later, Katsaggelos et al. [16] presented a is an interface, large compared with the wavelength of the
systematic framework for performing multi-channel image ultrasonic pulse, while scatterers are objects, small compared
restoration in the frequency domain. In the field of medical with the wavelength and typically inducing a speckle
imaging this method was applied to dual-radionuclide pattern. For that reason, and following [7], the tissue
imaging [17]. Tom et al. [18] established a maximum- reflectivity is modeled in this work as the sum of a
likelihood formulation for the general problem of multi- deterministic function D representing the specular reflections
channel image restoration, and utilized the expectation- and a zero-mean Gaussian stochastic process U
maximization algorithm to solve it. corresponding with the speckle component:

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R(x, z) = D(x, z) + U(x, z). )1( transform (DFT), rotation should be given special attention
because straightforward 90 rotation results with phase shift
in the frequency domain. This is alleviated if the definition
The interaction of the ultrasonic pressure field with the of 90 rotation utilizes the periodicity of the DFT:
tissue is 3-dimensional, but its observation in B-mode
imaging is a 2-D space. Subject to customary assumptions, B(m‘, n‘)  TA = A(n‘, [N–m‘]mod N) , )5(
the formation process of the RF image can generally be
modeled as a 2-D spatial linear filtering operation with a
spatially variant point-spread function [5], [6], [19], [20]. It m‘ = 0, 1 … N–1
is possible to segment the image into regions for which the
PSF is approximately constant and simple convolution where A(m, n) is a matrix with N rows. This is equivalent to
describes with good accuracy the image formation: column-wise inversion excluding the first row followed by
transposition.
S(x, z) = P(x, z)  R(x, z) + N(x, z), )2(
D. Sampling grid
We assume that the ultrasonic B-mode scan is
where  denotes 2-D convolution, P represents the PSF and performed with a linear array transducer. Hence, the
N represents additive noise. The noise term is modeled as a sampling grid is rectangular, but the sampling intervals are
white zero-mean Gaussian random process that is different in each direction. The lateral sampling interval dL
independent of the tissue reflectivity and the PSF [5]-[7]. is a consequent of the spacing between the piezoelectric
The system response in the frequency domain P( x, z) crystals, which is in the region of few hundreds of m. The
is related to the PSF through 2-D Fourier transform. The axial sampling interval dA is related to the sampling
resolution in the lateral direction is significantly worse than frequency fS at the receiver and the speed of sound v within
the axial resolution; therefore the PSF has wide extent the tissue:
laterally and narrow support axially. Equivalently, the
bandwidth of the system response is much smaller in the dA = ½ v / fS. )6(
lateral dimension than in the axial dimension.

C. Rotation For example, if v  1,540 m/sec and fS = 20 MHz [2]-

Rotation is treated as positive when its direction is from [4], then dA  38.5 m, and assuming dL = 500 m [1], the
the positive ray of the x-axis toward the positive ray of the z- ratio between the lateral and axial sampling intervals is about
axis, and as negative when it is in the opposite direction. 13:1. If fS = 10.5 MHz [8] and the crystal spacing is
This implies that if conventional matrix coordinates are approximately 200 m[12], this ratio drops off to around
employed then positive rotation is clockwise. 3:1.
Let A1 and A2 denote two RF images that were recorded Taking into account the different sampling intervals and
with A2 taken after the transducer was turned by –90 treating the matrices of the reflectivity R and the PSF P as
relative to its direction during the recording of A1. The samples on a square grid with intervals dA in both directions,
superscript rot is used to indicate 90 rotation, while inv-rot the discrete-space LSI model for the generation of the 2
indicates –90 rotation. Assuming that the tissue reflectivity source images SV and SH from the tissue reflectivity R is:
R is the same for both recordings, then:
SV = (P1  R) HK + N1 )7(
A1 = P 1  R + Na )3(
SH = (P2rot  R) VK + N2,
A2 = P 2  R inv-rot
+ Nb,

where HK denotes horizontal decimation by factor K and

where P1 P2 denote the system‘s PSF in each case and Na, VK stands for vertical decimation.
Nb denote the additive noise. Rotating A2 in (3) by 90 and
substituting: SV  A1, SH  A2rot, N1  Na and N2  Nbrot, E. Frequency domain
yields: DFT of (7) with proper zero-padding gives:

SV = P1  R + N1 )4(
SV( x, z) = P1( x, z) R( x,z) + N1( x, z) )8(

SH = P2rot  R + N2.
SH( x, z) = P2( z, – x) R( x,z) + N2( x, z)
In other words, the blur is treated as rotated by 90
instead of regarding the image as rotated by –90. Note that
where SV, SH, P1, P2, R, N1 and N2 are respectively the 2-
for SV the axial direction coalesces with the vertical
D DFT‘s of SV, SH, P1, P2, R, N1 and N2. The zero padding
direction, while for SH it is horizontal. Therefore, according
is performed in a way such that all the elements in (8) are
to the degradation model, R is more blurred horizontally to
generate SV and more blurred vertically to generate SH. square matrices of size NDFT  NDFT.
When dealing with matrices and discrete Fourier Using the vector notation sk,l  [SV(x, z), SH( x, z)]T,
hk,l  [P1(x, z), P2( z,–x)]T, rk,l  R(x, z), and

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nk,l  [N1(x, z), N2( x, z)]T, with x = 2πk/NDFT and z = Q(|[n]) = E[ln{ fy(y|) }|s,[n]]. )12(
2πl/NDFT, (8) can be compactly written as:
sk,l = hk,l rk,l + nk,l . )9(
In the M step the expectation Q(|[n]) is maximized with
respect to  to provide a new estimation of the parameters:
The variable rk,l is stochastic with mean dk,l  D(x, z) [n+1] = arg max Q(|[n]). )13(
and variance u, and is assumed to have Gaussian probability 
density function (PDF) [7]. The noise term nk,l is a random
vector with zero mean and a diagonal 2  2 covariance B. Steps of the algorithm
matrix , where the diagonal elements are the variances 1 After (11) is substituted for fy(y|) in (12), it follows that
and 2 of N1(x, z) and N2( x,z) respectively. maximization of Q(|[n]) is equivalent to minimization of:

J(|[n]) = ∑ ∑ Jk,l(|[n]) )14(

III. BLUR ESTIMATION k l
A. The algorithm
The blind deconvolution problem is solved in two steps:
1. Estimation of the blur function. Jk,l(|[n]) = ln(u12) + u–1 | E[rk,l|s,[n]] – dk,l |2
2. Image reconstruction assuming this estimated function + (sk,l – hk,l E[rk,l|s,[n]])† –1
is the true blur and image compounding. (sk,l – hk,l E[rk,l|s,[n]])
+ Var[rk,l|s, ] (u + hk,l† –1 hk,l).
[n] –1

The estimation of the blur function can be viewed as an

optimization problem where we search for the unknown
parameters of a PDF and for which the maximum-likelihood In order to find the conditional expectation and variance
(ML) approach can be applied. Employing optimization of of rk,l given s and [n], we need to look at the conditional
the direct likelihood function yields a difficult minimization probability density. Using the complete-probability formula
problem since the unknown quantities of reflectivity and blur fr(rk,l | s,[n]) = fy(yk,l | [n]) / fs(sk,l | [n]), it follows:
are coupled through multiplication. The expectation-
maximization (EM) algorithm is an iterative technique that E[rk,l|s,[n]] = [1–1 P1(x, z) SV( x, z) + )15(
greatly simplifies the ML problem. 2–1 P2( z, –x) SH( x, z) + u–1 dk,l] /
According to the EM method, the complete data y is not [1–1 |P1( x, z)|2 + 2–1 |P2( z,– x)|2 + u–1].
observed directly, but only by means of the observed data s,
which is related to y through a non-invertible linear
mapping. Applying to the problem at hand, we define: yk,l = Var[rk,l|s,[n]] = 1/ )16(
[sk,lT, rk,l]T, so the mapping is: sk,l = [I, 0]T yk,l. The unknown [1–1 |P1( x, z)|2 + 2–1 |P2( z,– x)|2 + u–1].
quantity rk,l within the complete data is referred to as the
hidden data. The PDF of the complete data is fy(y|), where
 is the set of unknown parameters of the PDF:  = [hT, d, Note the expression in (15) is similar to the vector Wiener
u, 1, 2]T. filter [16]. For each of the parameters in (15) and (16) the
According to the complete-probability formula: current estimation is substituted, though the superscript [n] is
suppressed for brevity.
fy(yk,l|) = fr(rk,l|) fs(sk,l|rk,l,). )11( Now, we take from (14) only the terms that involve hk,l
and use the identity (v† A w) = tr(A w v†), where A is a
matrix of size N  N, v, w are vectors of size N  1 and
Due to the assumption that the stochastic terms are white, tr{A} denotes the trace of A:
fy(y|) is the product of fy(yk,l|) over all possible
combinations of k and l. Hence the likelihood of the Jh(|[n]) = ∑ ∑ tr{–1 (Var[rk,l|s,[n]] hk,l hk,l† + )17(
k l
complete data is:

L() = ln{fy(y|)} = ∑ ∑ Lk,l() )11( (sk,l – hk,l E[rk,l|s,[n]]) (sk,l – hk,l E[rk,l|s,[n]])†)}.
k l

Lk,l() = – 3/2 ln(2π) – 1/2 ln(u12) Since  is a diagonal matrix, we obtain from the
expression in (17):

– 1/2u–1|rk,l – dk,l|2 hk,l[n+1] = E[rk,l|s,[n]]sk,l / )18(

(|E[rk,l|s,[n]]|2 + Var[rk,l|s,[n]]).
– 1/2 (sk,l – hk,l rk,l)† –1 (sk,l – hk,l rk,l).
Explicitly, the update of the estimation of the blur is:
In the EM algorithm each iteration is composed of two
P1( x, z)[n+1] = E[rk,l|s,[n]] SV( x, z) / )19(
steps: expectation (E step) and maximization (M step). In
the E step the conditional expectation of ln{fy(y|)}, using
the current estimates of the parameters [n] and conditioned
upon the observed data, is calculated:

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E[|rk,l|2|s,[n]] / (E[|rk,l|2|s,[n]] + E[|r– l,k|2|s,[n]])

P2( z,– x)[n+1] = E[rk,l|s,[n]] SH( x, z) / C. Initialization and constraints
E[|rk,l|2|s,[n]] Being highly non-linear the likelihood function L() has
multiple maxima, and therefore the initial conditions [0]
have a great effect on the ability of the EM algorithm to
where we used for E[|rk,l|2|s,[n]] the identity: converge to a good estimation. We found that P1[0] and P2[0]
should have the same value at all frequencies, that is they
E[|rk,l|2|s,[n]] = | E[rk,l|s,[n]] |2 + Var[rk,l|s,[n]]. )21( should be the DFT of an impulse at the origin. Also, a
plausible initialization for d[0] is the average of SV and SH.
For the noise variance the initial estimate was higher than
Next, we take from (14) only terms related to : the true value, as it was found in [18] to produce better
results. In the initial iterations the estimation of the
J(|[n]) = ∑ ∑ ln(12) + Jh(|[n]) )21( variances is unreliable, thus the estimation much improves if
k l
u in (15) and (16) is limited such that 1/u and 2/u are
not too large or small relatively to max|P1( x,z)|2 and
Substituting (18) for hk,l, the values of 1 and 2 that max|P2( x,z)|2 respectively.
minimize (21) are:
IV. IMAGE COMPUNDING
1[n+1] = NDFT–2 ∑ ∑{Var[rk,l|s,[n]] |P( x, z)[n+1]|2 )22( According to the approach of multi-channel image
k l
restoration the restored image is computed from (15).
However, in ultrasound imaging the resulting image would
+ |SV( x, z) – E[rk,l|s,[n]] P(x, z)[n+1]|2}
contain oscillations, as is the case with RF images due to the
band-pass character of the ultrasonic blur. Consequently
there would be required envelope detection.
2[n+1] = NDFT–2 ∑ ∑{Var[rk,l|s,[n]] |P( z,– x)[n+1]|2 When handling single RF images, where the oscillations
k l
+ |SH( x, z) – E[rk,l|s,[n]] P(z, – x)[n+1]|2}. are along just one axis, the envelope can be detected through
demodulation, followed by absolute value calculation. But,
the image of (15) has oscillations along both axes, thus
Then, for the minimization J(|[n]) with respect to dk,l, demodulation or Hilbert filtered cannot be utilized. In
we take from (14) only the terms that depend on dk,l: addition, the frequency support regions of P1( x, z) and
P2( z,– x) are far from overlapping. This inhibits the
Jd(|[n]) = u–1 | E[rk,l|s,[n]] – dk,l |2 )23( benefit of (15) over a single-channel Wiener filter, which is
the ability to get weighted average in the intersection of the
support regions while retaining the best of the single-channel
It is simple to see that the value of dk,l that minimizes (23) is: restorations at any other frequency.
The conclusion is that the compound image should be
dk,l[n+1] = E[rk,l|s,[n]] )24( generated through the following steps:
1. Calculation of the 2 separate Wiener filter solutions
using (15) and substituting 0 for 1–1 or 2–1
Finally, we substitute (24) for dk,l in (14) then take only
respectively.
the terms that depend on u: 2. Envelope detection of each resulting image.
3. Computation of the average of the 2 envelope detected
Ju(|[n]) = ∑ ∑ (ln(u) + u–1 Var[rk,l|s,[n]]). )25(
k l images [11], [12].
V. EXPERIMENTAL RESULTS
The minimum of (25) is achieved when the value of u is: Since the estimation of the blur can be accurate up to a
gain factor, it is required to restore the scaling before
u[n+1] = NDFT–2 ∑ ∑ Var[rk,l|s,[n]]. )26( comparing the estimation with the true blur. We used the
k l
least squares method for this purpose:
Jg = ||g P̂ – P||2. )28(
If we assume that the noise variance is the same in both
RF images, then the average of the 2 expressions in (22)
should be used to update the variance. If we assume We used normalized mean squared error (NMSE) as a
identical blur in both scans P1 = P2 = P, (19) should be quality metric to evaluate the PSF estimation. The MSE is
replaced with: the right-hand side of (28) and the normalization is with
P( z, x)[n+1] = ( E[rk,l|s,[n]] SV( x, z) + )27( respect to ||P||2. When substituting for g the value that
minimizes (28) the quality measure becomes:
E[r–l,k|s,[n]] SH(– z,x) ) NMSE{P} = 1 – Re( P̂ † P)2 / (|| P̂ ||2 ||P||2) )29(

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the identification task, but Wiener restoration was found to

be inappropriate for compounding in the case of ultrasound
imaging with 90 separated views. The algorithm in this
work is based on registration of the two input images, and
exploits both deconvolution and compounding to provide an
enhanced output image. The simulation experiments that we
conducted show that the quality of the compound image can
be enhanced compared to the usage of algebraic average
without Wiener filtering. Further research is planned so as
to adapt the algorithm for angles different than 90 and for
multi-angle compounding [21].
REFERENCES
[1] E.E. Hundt and E.A. Trautenberg, ―Digital processing of
ultrasonic data by deconvolution‖, IEEE Trans. Sonics.
Ultrason., vol. 27, no. 5, pp. 249-252, Sep. 1980.
[2] C.N. Liu, M. Fatemi and R.C. Waag, ―Digital
processing for improvement of ultrasonic abdominal
images‖, IEEE Trans. Med. Imaging., vol. 2, no. 2, pp.
66-75, June 1983.
a)
[3] J.A. Jensen and S. Leeman, ―Nonparametric estimation
of ultrasound pulses‖, IEEE Trans. Biomed. Eng., vol.
41, no. 10, pp. 929-936, Oct. 1994.
[4] J.A. Jensen, ―Estimation of in vivo pulses in medical
ultrasound‖, Ultrasonic Imaging, vol. 16, pp. 190-203,
1994.
[5] T. Taxt, ―Restoration of medical ultrasound images
using two-dimensional homomorphic deconvolution‖,
IEEE Trans. Ultrason., Ferroelect., vol. 42, no. 4, pp.
543-554, July 1995.
[6] U.R. Abeyratne, A.P. Petropulu and J.M. Reid, ―Higher
order spectra based deconvolution of ultrasound
images‖, IEEE Trans. Ultrason., Ferroelect., vol. 42,
pp. 1064-1075, 1995.
[7] J.H. Hokland and P.A. Kelly, ―Markov models of
specular and diffuse scattering in restoration of medical
ultrasound images‖, IEEE Trans. Ultrason., Ferroelect.,
Freq. Contr., vol. 43, pp. 660-669, 1996.
[8] T. Taxt and G.V. Frolova, ―Noise robust one-
dimensional blind deconvolution of medical ultrasound
b) images‖, IEEE Trans. Ultrason., Ferroelect., vol. 46,
Figure 1. The output: compound images. a)– with the proposed algorithm; no. 2, pp. 291-299, 1999.
b)– with averaging the 2 envelope-detected images [9] T. Taxt and J. Strand, ―Two-dimensional noise-robust
We tested the algorithm with several artificial reflectivity blind deconvolution of ultrasound images‖, IEEE Trans.
maps. Their size was 512  512 pixels, which corresponds Ultrason., Ferroelect., Freq. Contr., vol. 48, no. 4, pp.
approximately with 20  20 mm for a sampling interval of 861-866, 2001.
about 40 m. In the example that is presented in this paper [10] D. Adam and O. Michailovich, ―Blind deconvolution of
there are 4 series of bright dots simulating wire targets that ultrasound sequences using nonparametric local
are separated by 0.5, 1, 2 and 3 mm. polynomial estimates of the pulse‖, IEEE Trans.
The blur in the example in this paper was according to the Biomed. Eng., vol. 49, no. 2, pp. 118-131, Feb. 2002.
non-separable model that was given in [20]. The parameters [11] P. He, K. Xue and Y. Wang, ―Effects of spatial
for this blur function corresponded with a linear-array compounding upon image resolution‖, Int. Conf. IEEE
transducer having width of 25 mm without apodization and Eng. Medic. Bio. Society, pp. 598-600, Oct. 1997.
focus depth of 50 mm, using 4 MHz ultrasonic pulses with [12] S. K. Jespersen, J. E. Wilhjelm and H. Sillesen,
envelope having full width at half maximum (FWHM) of ―Ultrasound spatial compound scanner for improved
visualization in vascular imaging‖, 1998 IEEE Ultrason.
about 0.3 sec. Compounding with the suggested algorithm
Symposium, pp. 1623-1626, 1998.
is compared in Figure 1 to compounding with only
[13] D. F. Leotta and R. W. Martin, ―Three-dimensional
averaging the envelope-detected and log-compressed
spatial compounding of ultrasound scans with incidence
images.
angle weighting‖, IEEE Ultrason. Symposium, pp. 1605-
VI. CONCLUSIONS 1608, 1999.
We developed an algorithm for blind identification of [14] R. E. Shenhar and M. Porat, "A Dual Transducer
ultrasonic blur and for ultrasound image compounding. The Approach to Ultrasound Imaging and Spatial
approach of multi-channel image restoration was adopted for

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Deformations", IEEE International Conference on [18] B.C. Tom, K.T. Lay and A.K. Katsaggelos,
Image Processing, 2000. ―Multichannel image identification and restoration using
[15] D.C. Ghiglia, ―Space-invariant deblurring Given N the expectation-maximization algorithm‖, Opt. Eng.,
independently blurred images of a common object‖, J. vol. 35, no. 1, pp. 241-254, Jan. 1996.
Opt. Soc. Amer. A, vol. 1, no. 4, pp. 398-402, April [19] D. Iraca, L. Landini and L. Verrazzani, ―Power
1984. spectrum equalization for ultrasonic image restoration‖,
[16] A.K. Katsaggelos, K.T. Lay and N.P. Galatsanos, ―A IEEE Trans. Ultrason., Ferroelect., vol. 36, no. 2, pp.
general framework for frequency domain multi-channel 216-222, March 1989.
signal processing‖, IEEE Trans. Image Proc., vol. 2, no. [20] W.F. Walker and G.E. Trahey, ―The application of K-
3, pp. 417-420, 1993. space in pulse echo ultrasound‖, IEEE Trans. Ultrason.,
[17] J.M. Links, J.L. Prince and S.N. Gupta, ―A vector Ferroelect., Freq. Contr., vol. 45, no. 3, pp. 541-558,
Wiener filter for dual-radionuclide imaging‖, IEEE May 1998.
Trans. Med. Imaging, vol. 15 , pp. 700-709, Oct. 1996. [21] H. Kirshner and M. Porat, "On the Role of Exponential
Splines in Image Interpolation", IEEE Trans. on Image
Processing, vol. 18, pp. 2198-2208, 2009.

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Elastography - New Imagistic Method for

Assessment of Liver Structure in Children
MARGINEAN Oana1, BRANZANIUC Klara2, MARGINEAN C., PITEA Ana Maria 1, AZAMFIREI
Leonard4, LUDMILA Bologa5, LUDMILA Cerempei5, NINEL Revenco5
1
University of Medicine and Pharmacy Tg.-Mures, Pediatry
2
University of Medicine and Pharmacy Tg.-Mures, Anatomy
3
University of Medicine and Pharmacy Tg.-Mures, Ginecology
4
University of Medicine and Pharmacy Tg.-Mures, Anestiology
5
University of Medicine Nicolae Testemițeanu, Chișinău, Pediatrics Departement

Abstract- Elastography is a new method based on ultrasound imaging, which allows assessment of tissue
structure in terms of their stiffness, useful in exploring various organs and systems.
Objectives and aim Study of liver tissue elasticity in children by real-time elastography in normal (healthy
children) and in the context of certain disease.
Material and method Our study (prospective type) was carried out at the Ist Pediatric Clinic Tg.-Mures,
Romania in the period 2010, September - 2011, April. An ultrasound machine Siemens S 2000 with an up-to-
date soft was used for the elastographic assessment of liver by ARFI (Acustic Radiation Force Impulse
Imaging) tehnique, using ―Virtual Touch (VT) Tissue Quantification‖ technology (for quantification of
fibrosis) in children: a lot of different conditions (various liver injuries) and a control group (healthy). The
degree of tissue stiffness was expressed as a numerical value called SWV (shear wave velocity), measuring at
the level of 8 and 1 liver segments, to highlight differences depending on anatomical structure, but also
differentiated on pathology (ie healthy versus those with particular injuries). Measurement data were
correlated with biochemical parameters.
Results. Higher SWV-values were found in group with liver-damage (p=0,04). Aspartate transaminase and
alanine transaminase were statistically significant different between the groups; transaminases increased
parallel with SWV (fibrosis degree) in children with liver damage.
Conclusion: Elastography completes diagnostic possibilities, providing information on the degree of hepatic
elasticity (even degree of fibrosis), with special importance in liver imaging in adults, but also in pediatric
practice.
Key words: elastography, ultrasound, liver, children

chronic liver disease the reported results were the same

I. INTRODUCTION
[6].The main difference between ARFI and TE elastography
Ultrasound elastography have the potential to measure the
is that it is integrated into a conventional ultrasound device
mechanical properties of the tissue displacement through
[6].
imaging (strain) while under tension [1].
Liver injury in children, in evolution of chronical diseases,
Newly, acoustic radiation force impulse (ARFI)
including malignacies, viral or autoimmune chronic hepatitis
elastography has been introduced as a noninvasive tech-
(with B, C, D, E hepatitic virus or cytomegalovirus), alfa-1-
nique for evaluating liver fibrosis [2,3,4].
antitripsin deficiency, the Wilson disease, as well as liver
The ARFI imaging technique uses high-intensity, short-
damages in context of obesity (non-alcohoolic fatty liver
duration acoustic pulses to produce shear-wave propagation
disease, NAFLD) and drug-related hepatotoxicity are
in the targeted tissue [5,6]. Shear-wave velocity are
important concerns for practicing pediatricians.
measured by repeating push pulses and detection pulses
The evaluation of liver damage (which could be of
across a user defined ROI (the region of interest) [6,7].
hepatocellular-type, cholestatic or mixed) implies the
The elastographic ARFI tehnology can be used to measure
clinical findings (signs of liver damage as nausea, fatigue,
a numerical value of the wave speed SWV (shear wave
anorexia, cholestatic signs as jaundice, pruritus), laboratory
velocity) by implementing the Virtual Touch tissue
investigations (increased transaminases and increased
quantification; an image of the used soft-ware is a qualitative
alkaline phosphatase, bilirubin and albumin levels
gray-scale map of the relative tissue stiffness (elastogram)
determination) [8], imagistic tests, (abdominal
for a ROI. The smaller the liver tissue elasticity, the higher
ultrasonography and computerised tomography), the flow on
the SWV. Thus, on elastograma the shining regions
portal vein evaluation.
correspond to the tissue which is more elastic (less stiff) and
Liver biopsy has been the gold standard for fibrosis
the dark regions correspond to the stiff tissue [7].
staging. However, this invasive method, with a lot of
According to recent reports, ARFI elastography results
secondory effects which can cause serious complications
were similar to transient elastography (TE) regarding
such as intraperitoneal bleeding and mortality is about 1 in
correlation with fibrosis stage (histologicaly) and for
1000 [6,9], hardly accepted by children and parents [3].
diagnosis of moderate fibrosis and cirrhosis [2,3].. The
In clinical practice as well as on research line, there are
technique showed better diagnostic performance than visual
constantly evaluating diagnostic techniques of hepatic
assessment by experienced radiologists for detection of
evaluation in order to find non-invasive alternatives to
chronic liver disease, while for the evaluation of severity of

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replace hepatic biopsy but to accurately assess the degree of whether their weight was between the 85th and 95th
fibrosis. percentile for age and sex, and obese whether their weight
Ultrasonography is usually the first-line investigation in the exceeds 95th percentile, respectiely), all of them with
assessment of patients, considering its low cost, non- modifications to the standard abdominal ultrasound (high
invasiveness, repeatability and easy access; MRI and PET, echogenicity, granular liver aspect, posterior attenuation
and often CT, are restricted to selected cases, due to their suggestive for steatosis); there were 48 patients with various
limited availability and high costs. malignancies under or after chemotherapy, with tumor
Thus, the introduction of new techniques to increase the infiltration of the liver or hepatotoxicity related to cytostatic
sensitivity of US, such as real-time elastography would be a treatment and a number of 20 patients with various etiology
major advantage. of hepatopathy (viral hepatitis, acute toxic hepatitis, drug
The aim of the paper was the study of the liver tissue hepatotoxicity) (as presented in Figure 1).
elasticity, assessed by real-time elastography, in correlation
with biochemical parameters (namely transaminases levels)
in children with different causes of liver injury (obesity,
hepatitis, liver damage in children with malignancies under/
after-chemotherapy, drug-related hepatotoxicity) versus
children with normal biochemical parameters regarding liver
function.
II. MATHERIAL AND METHODS
The present study was carried out at the Ist Pediatric Clinic
Tg.-Mures, Romania, between 2010 September and 2011,
April; it was a prospective study including a control group
Fig. 1. The structure of the three groups (by condition)
composed of 38 children with normal clinical and
paraclinical findings related to the liver function and a lot of Descriptive statistics show averages ± standard deviations
96 children with different causes of hepatopathies, selected (SD) of study groups. In the control group the average
based on clinical signs and symptoms of liver damage elasticity was 1,18±0,28 m/s; in the group of children with
(abdominal discomfort, fatigue, anorexia, nausea, vomiting, different causes of liver diseases, elasticity was 1,39±0,41
jaundice, pruritus, hepatomegaly, ascites), changes in m/s. Alanine transaminase (ALT, IU) was 19,56±8,67 SD in
laboratory findings (liver tests considering the synthetic the control group, and 37,42±31,16 in the group of children
function, hepatocellular necrosis and cholestasis) and/or with liver diseases, while aspartate transaminase (AST, IU)
abnormalities in liver imaging. was 24,88±8.67 SD in the control group, and 39,92±20,12 in
An informed consent was signed by legal tutors of each the group of children with liver inury.
patient at the moment of hospitalization in our clinic (in Comparing liver tissue elasticity values between the groups
accordance with the principles of the Helsinki declaration). higher speeds were found in groups with liver damage, the
Combined B-mode US/ARFI elastography was performed differences being statistically significant at CI of 95%.
using an ultrasound machine Siemens S 2000 with an up-to- We`ve got a statistically significant difference with p =
date soft, using a transducer array operating at 4,1 MHz by 0.0044 (Figure 2).
an experienced radiologist with 11 years of experience in
ultrasonography.
The patients were placed supine with the right arm straight
over head.
SWV (m/s) were measured in the area of interest chosen
by the examiner. Measurements were performed in the right
lobe, especially in the 8th segment, 4 cm under the skin, at
2.5-4.5 cm depth, under the liver capsule (which has been
avoided, being an fibrous tissue rich area). Also, the caudate
lobe of the liver (the 1st segment) was examined in order to
evaluate the elasticity in the right versus the left liver lobe.
There have been made 10 measurements in a selected
region, and median velocity values were obtained through
calculation in Microsoft Excel programm.
For continuous variables, mean values were expressed as Fig. 2. Comparison between the median SVW of the groups
mean ± standard error of mean (SEM) or Standard Deviation
(SD). Regarding alanine transaminase (ALT, IU), as expected, the
Statistical analysis were performed using Graph Pad Prisma levels were higher in group of children with liver diseases,
and Graph Pad InStat Demo programs. Student test, Chi the difference from control was statisticaly extremely
square (χ2), Fisher exact test, ANOVA test were used; significant, with p < 0.0007 (Figure 3).
correlation between average SVW and study variables
(transaminasis) were assessed based on Pearson correlation
coefficient (r).The threshold of significance was p<0.05.
III. RESULTS
In group of patients with liver damage there were 28
overweight and obese children (considered overweight

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Segment 1 (caudate lobe or Spiegel lobe) is a distinct

structure of the liver, receiving blood flow from both the
right and left-sided vascular branches; a special
vascularization which represents the distinctive characteristic
of segment 1 [11,12].
The caudate lobe is less echogenic.
Assessing liver elasticity separate for each segment for the
entire group (all 134 patients in the study), comparing the
SVW values by Mann-Whitney test for liver tissue elasticity
there was found no statistically significant differences
between segment 1 (caudate lobe) and segment 8 (right
lobe), (p=0,1583).
Fig.3. Comparison between the median ALT of the three groups Evaluation of each segment revealed for the control group
As far as it concerns aspartate transaminase (AST, IU), in a median SWV for segment 8 of 1,24±0,31 m/s, while for
the control group it were, also, smaller levels than in the segment 1 SWV was 1,06±0,3 m/s; by applying the Student
group of children with hepatopathies, the difference between T Test between the media of SVW on those two segments
AST mean for the two groups was, as for ALT, statistically (unpaired t test), we obtained a statistically significant
extremely significant, with p < 0.0001 (Figure 4). difference (p < 0,0121, Figure 6).

Fig. 6. Comparison between mean values of SVW on segment 1 and

Fig. 4. Comparison between the median AST of the three groups
segment 8 in the control group.
We searched for correlations between global SVW and other In group of children with hepatopathies, SWV was
determined parameters (AST and ALT) in each group, but 1,30±0,47 m/s in segment 8, and 1,31±0,5 m/s in 1st
we obtained no statisticaly significant correlations between segment, without statistically significant difference when
the assesed parameters, except that between SWV and AST, applying the Student T Test between the media of SVW on
only for the group of children with liver injury (r = 0,54 and those two segments (unpaired t test) (p = 0,8866).
p = 0,01), statistically significant.

Figure 5 - Comparison between the average SWV in segment 1 between

controls and the group with hepatopathies
Fig. 5. The correlation between the values of SVW and AST average in
group of children with liver damage No statistically significant differences were obtained
between control group and the one with hepatopathies when
applying the Student T Test for SWV values in the 8th
The classical descriptive anatomy nomenclature segment (1,24±0,31 m/s versus 1,30±0,47 m/s), with p=
distinguishes four lobes: right, left, caudate and quadrate, 0,4691.
concept which does not reflect the functional anatomy [10]. For the 1st segment, comparison between the average
According to the International Anatomical Nomenclature, SWV of the controls (1.06±0,3 m/s) versus group with
a posterior and anterior segment are attributed to the right hepatopathies (1,31±0,5 m/s), perfomed by Student T test,
lobe, and a medial and lateral segment to the left lobe, each achieved a very significant difference (p=0,0046-Figure 5).
of these segments being divided into an antero-inferior and a
postero-superior segment, so as liver has eight segments,
numbered clockwise from I to VIII [11].

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IV. CONCLUSIONS radiation force impulse imaging versus transient

In children with liver damage, compared to the control elastography. Radiology 2009;252:595–604
group, transaminase levels increased as well as SWV and [3] Lupsor M, Badea R, Stefanescu H, Sparchez Z, Branda
therefore the degree of fibrosis. H, Serban A, Maniu A. Performance of a new
We found that SWV is higher in children with liver-diseases, elastographic method (ARFI technology) compared to
globally, meaning that any tissue injury result in changes of unidimensional transient elastography in the
the liver elasticity up to fibrosis. noninvasive assessment of chronic hepatitis C.
In normal conditions (children with free liver tissue), Preliminary results. J Gastrointestin Liver Dis
SVW was higher for the segment VIII compared to I, 2009;18:303–310
statistically significant, meaning that caudate lobe is [4] Takahashi H, Ono N, Eguchi Y, Eguchi T, Kitajima Y,
―softer‖, difference that does not exist in the group of liver Kawaguchi Y, et al. Evaluation of acoustic radiation
diseases. force impulse elastography for fibrosis staging of
SWV values in group of children with hepatopathies were chronic liver disease: A pilot study. Liver Int
found to increase particularly in the segment I (caudate 2010;30:538–545
lobe), which shows that it is first affected by any liver injury. [5] Palmeri M, Wang M, Dahl J, Frinkley K, Nightingale K.
Faithful evaluating the elasticity, real-time elastography Quantifying hepatic shear modulus in vivo using
has a certain role in the evaluation of hepatic vasculature and acoustic radiation force. Ultrasound Med Biol
tissue damages. Due to this fact, elastographic evaluation of 2008;34:546–558.
liver and particulary in the caudate lobe has further [6] Kim J. E. Lee J.Y., Kim Y.J., Yoon J.H., Kim S.H., Lee
implications for assessment of liver fibrosis and would have J.M., Han JK, et al. ARFI elastography for chronic liver
possible utility in preparation and management in cases of disease: Comparison with ultrasound-based scores of
liver transplantation. experienced radiologists, Child-Pugh scores and liver
Ultrasound elastographic assessment, by new tehnologies function tests. Ultrasound in Medicine and Biology
available, through ARFI quantification respectively, may 2010;36(10):1637-43
enhance the current role of liver ultrasound for patients with [7] Lazebnik R.S. Ultrasound, Mountain View, CA USA
liver disease. Tissue Strain Analytic, Virtual Touch Tissue Imaging
„This paper is partially supported by the Sectoral and Quantification. Siemens Medical Solutions, USA,
Operational Programme Human Resources Development, Inc., 2008
financed from the European Social Fund and by the [8] Roberts E.A. Drug-induced liver disease. In Suchy F.J.,
Romanian Government under the contract number Sokol R.J., Balistreri W.F., (Eds). Liver Disease In
POSDRU/89/1.5/S/60782” Children, Third Edition. Cambridge University Press,
This paper is partially supported by the project NASR Cambridge, New York, 2007;478-512
421/2010: "Correlations between the elasticity of the [9] Bravo AA, Sheth SG, Chopra S. Liver biopsy. N Engl J
caudate lobe and other lobes of the liver in children by real- Med 2001;344:495–500
time elastography, with implications for liver [10] Strunk H., Stuckmann G., Textor J., Willinek W.
transplantation” Limitations and Pitfalls of Couinaud`s Segmentation of
the Liver in Transaxial Imaging. European Radiology
2003;13(11):2472-2482, DOI: 10.1007/s00330-003-
REFERENCES
1885-9
[1] Ophir J, Cespedes I, Ponnekanti H, Yazdi Y, Li X.
[11] Dodds WJ, Erickson SJ, Taylor AJ, Lawson TL, Stewart
Elastography: a quantitative method for imaging the
ET. Caudate lobe of the liver: anatomy, embryology and
elasticity of biological tissues. Ultrason Imaging.
pathology. AJR 1990; 154: 87-93
1991;13:111
[12] Brown BM, Filly RA, Callen PW. Ultrasonographic
[2] Friedrich-Rust M, Wunder K, Kriener S, Sotoudeh F,
anatomy of the caudate lobe. J Ultrasound Med 1982; 1:
Richter S, Bojunga J, et all. Liver fibrosis in viral
189-192
hepatitis: Noninvasive assessment with acoustic

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Fetal Survey via Abdominal Recorded Signals

Dragos TARALUNGA1, Werner WOLF2, Mihaela UNGUREANU1 and Rodica STRUNGARU1
1
Politehnica University of Buharest/Applied Electronics and Information Engineering Department,
Bucharest, Romania, e-mail: [email protected], [email protected] 2Universität der
Bundeswehr München, Institut für Informationstechnik, Germany, e-mail: [email protected]

Abstract – Fetal heart rate (fHR) and the morphological features of the fetal ECG (fECG) can be derived
from (fECG) signals recorded on the maternal abdomen. However, when assessing the fECG through the
abdominal signals (ADS), it’s very low amplitude causes a problem, since the fECG representation in the
ADS is buried in a mixture of other signals with stronger energy. Thus, signal to noise ratio of these
recordings is low, the maternal electrocardiogram (mECG) being the main interference component. The aim
of the present paper is to evaluate the performance of an algorithm for maternal ECG (mECG) subtraction.
The performance of the algorithm considered in this study is evaluated by applying it on both simulated and
real ADS signals.

Index Terms – abdominal recordings, fetal monitoring, fetal electrocardiogram, subtraction algorithm.

I. INTRODUCTION heart rate (fHR) analysis and does not incorporate

Antepartum and intrapartum fetal surveillance constitute characteristics of the fetal electrocardiogram (fECG)
an essential component of the standards for evaluating and waveform, which represent the keystones of cardiac
analyzing the health state of the fetus during pregnancy and evaluation of both children and adults.
labor. The morphological characteristic analysis of the fECG can
Hypoxia is one the most frequently form of fetal distress identify both hypoxic episodes and congenital heart
during pregnancy. The state of hypoxia appears when the disorders described above. Thus, the ST segment is very
oxygen supply to the fetus through the placenta is affected, sensitive to metabolic dysfunction induced by fetal hypoxia:
leading to ischemia or in the worst case to asphyxia. There an increase in T wave, quantified by the ratio of the T wave
are numerous causes for hypoxia from maternal disorders to the QRS amplitude (T/QRS ratio), or a biphasic ST
like: anemia, heart diseases, chronicle lung diseases, to pattern [9], [10], [11]. By combining these morphological
placental disorders, the high stress which is put on the fetus changes of the fECG with fHR analysis, additional clinical
during labor and high consumption of drugs, e.g. cocaine. information is provided to the physicians, leading thus to
The effects of oxygen deprivation are different according minimization of the unnecessary obstetric interventions.
with the terms of pregnancy, thus on early terms it leads to The fECG constitutes the access to both fHR and the
congenital abnormalities, myocardial thinning, late waveform of the electrical activity of the fetal heart.
development of embryo [1] whereas on late terms leads to However, the standard procedure used nowadays for
intrauterine growth restriction and brain damage. The latter recording the fECG is by placing an electrode, invasively, on
can be the cause of psychiatric and neurologic disorders in the head of the fetus, after the rupture of the amniotic sack.
adulthood [2], [3] and of behavioral and cognitive deficits in This recording method has some major drawbacks because it
childhood [4], [5]. However, it is not clear what is the timing is cumbersome, it can put in danger the life of both the
and the duration of a fetal hypoxic exposure that can have as mother and the fetus and it is only applicable during
outcome a specific behavioral, cognitive, and emotional delivery.
sequel in childhood and adulthood. Nevertheless, the early Thus, abdominal recorded signal (ADS) represent an
identification of hypoxic distress is mandatory for alternative, as it is noninvasive, provides clinically
maintaining the health state of the fetus. significant information concerning the health state of the
Another disorder which can appear during pregnancy is fetus through the analysis of the FHR and the morphology of
congenital heart defects which represent the leading cause of the fECG. Moreover, it can also be used for long term
birth defect-related deaths [6]. It affects 35,000 infants, i.e monitoring.
one out every 125 infants born in United States [7] and one Nevertheless, the fundamental problem is that ADS
out 145 infants born in United Kingdom [8]. Congenital represents a multi-component signal containing several other
heart defects represent structural problems, malformations of disturbing signals of high amplitudes besides the low
the heart which are present at birth. Usually they occur amplitude fECG component.
during heart development, due to a mishap, soon after Among these perturbing biosignals, the maternal ECG
conception and often before the mother is aware of the (mECG) is clearly the main source of disturbance. The
pregnancy. The consequence of the defects may range from transabdominal fECG R-peak amplitude ranges from 10 to
simple problems, such as "holes" between chambers of the 100 µV, whereas the amplitude of the QRS complex of the
heart, to very severe malformations, such as complete mECG shows 0.5 to 1 mV [12]. Other disturbing signals
absence of one or more chambers or valves. Moreover, which must be considered are the electronic noise
congenital heart defects can also increase the risk of (introduced by amplifiers etc), the slow baseline wander of
developing certain medical conditions like: congestive heart signals (mainly due to electrode effects), the myoelectric
failure, pulmonary hypertension, arrhythmias, crosstalk from abdominal muscles, and, in particular during
anticoagulation [6]. labor, the uterine contractions. The large amplitudes of these
Nowadays, fetal monitoring is based entirely on the fetal noise sources are hiding the transabdominal fECG and a

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simple high-pass filtering of ADS for fECG extraction For calculating the optimal position of the averaged ECG
cannot be applied due to the overlapping spectra of the fECG template, first the information about the baseline wander is
and of the noise components. introduced in the template using linear interpolation. Then
All these effects reveal evidently that reliable methods for whenever the algorithm detects a mQRS complex, the
removing the mECG are necessary to allow fECG optimal position of the template is determined by adjusting
examination based on ADS recordings. This demand the template position, vertically and horizontally within a
motivates the development of several methods supporting window of 15 samples centered on the considered mQRS
the extraction of the low amplitude fECG from ADS for fHR (15 ms).
computation, such as principal component analysis [13], The minimum error of the fitting between the template
independent component analysis [14] and nonlinear state and the mECG, considering only the mQRS, is taken into
projections algorithms [15]. But the increasing interest of account in order to estimate the optimal position, as the
physicians to consider not only the instantaneous fHR but miss-positioning of the QRS template often leads to a
also the waveform of the fECG introduces new signal remaining maternal QRS, comparable with the fetal QRS
processing requirements, thus (linear) filtering methods in and thus the morphology of the fECG is no longer
general are getting more demanded. For this purpose, our conserved. This way, the current mQRS is replaced by a
paper reports about the evaluation of the performances of an segment including only the random noise from the ADSs,
improved linear method, on simulated and real ADS data. with zero mean.
II. METHOD Based on the interpolated isoelectric line, the denoised
The algorithm described in this paper was developed in ADS is combined with the raw data, preserving the
Matlab version 7.0.1 and consists of two steps: maternal continuity of the signal.
QRS detection and mECG extraction. The flow chart of the ADS + ∑
algorithm is presented in Fig.1
A. Detection of the maternal QRS complex
Low pass filter -
In order to detect the maternal QRS (mQRS), an
additional signal is generating as following: the ADS is 11 Hz fECG
filtered by a bandpass extracting the frequency range of
(5’11) Hz which covers the QRS complex in the ECG High pass filter
mainly. Thus, the P- and T-waves as well as the EHG are 5 Hz
attenuated.
The filters used to generate the additional signal that Derivation
identifies the QRS complexes are described by the following
equations:
y ( n)  2 y ( n  1)  y ( n  2)  x( n)  Squaring
Template Optimal
 2 x( n  6)  x ( n  12) obtained by position of
(1) coherent mECG
Moving average
for the first filter (LP), and: averaging template
window
y ( n)  x ( n  16) 
(2) Fig. 1. Flow chart of the algorithm describing the detection of QRS

1
 y (n  1)  x(n)  x(n  32) complexes in ADS and the mECG extraction with the recovery of the
32 isoelectric line.
for the second filter (HP), as proposed in [9].
Subsequently, the derivate is applied: III. DATA DESCRIPTION
The algorithm was applied on both simulated and real
yn  
1
2  x(n)  x(n  1)  x(n  3)  2  x(n  4) signals.
10
(3) C. Simulated signals
and then the resulting signal is squared in order to emphasize The abdominal signals are simulated using the model
QRS complex. described in [17].
Finally, a moving average window is applied; its window The generation of the morphology of the simulated ECG
length covers a complete QRS complex which lasts about cycles is realized using the three differential equations, (4),
100 ms. This additional signal is aligned with the original which represent the motion equations in 3D around a unit
signal, considering the delay introduced by the previous circle placed in xy-plane. On this circle five distinct points
processing techniques, and further a peak detection are placed at fixed angles, θP, θQ, θR, θS, θT. in order to generate
algorithm combined with a threshold determines its peaks the P, Q, R, S, T waves.
corresponding to the mQRS complexes. x  a  x    y
B. mECG removing y  a  y    x
(4)

2
The mECG component is removed by applying the Event
Synchronous Canceller (ESC) [16]. Each time an mQRS z    a i   i   i  exp(  i 2 )  ( z  z 0 )
iP ,Q , R , S ,T  2  bi
complex is detected in ADS, a template obtained by
averaging of all mQRS segments centered on the R-peaks is
subtracted from the ADS.
Since the uterine activity results in a change of the Thus the waveform is made to move away from the
isoelectric line of the maternal QRS (mQRS) complex, it is isoelectric line, i.e. the unit circle in the xy-plane, near the
necessary to adapt the isoelectric line in the averaged mQRS fixed points which behave like repellors, having a Gaussian
complex. morphology [16]:

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

respiration, introduced as a disturbance in the simulated

  atan  y / x  ,
ADS.
where  = 1- x  y 2 2
, 2

i    i and  is the angular velocity of the time

vector as it moves around the limit circle; ai contains the
amplitude of the waves and bi contains the width of each
wave.
D.Real data
The real data are recorded with the Biopac MP150
acquisition system from a healthy woman; gestational age is
34 weeks and the sampling frequency is 1000Hz.
Ten electrodes are placed on the maternal abdomen as
depicted in Fig.2.

Fig. 5. fECG extraction from simulated ADS: a) simulated ADS signal; b)

extracted fECG, after mECG cancelling by ESC.

F. Results obtained on real data

In Fig. 6 the detection of the mQRS from real abdominal
recorded signals can be observed, whereas in Fig. 7 the
cancelation of the mECG is depicted, without disturbing the
shape of any overlapping fECG.
Fig.2. Electrode configuration on the maternal abdomen

IV. RESULTS AND DISCUSSIONS

E.Results on simulated data
A segment of the simulated data used to evaluate the
performance of the algorithm is depicted in Fig. 3.

Fig. 6. mECG template estimation from real ADS data: a) detection of the
maternal R-peaks; b) Auxiliary signal used for QRS detection; c) extracted
mECG template.

Fig. 3. Simulated ADS signals: a) mECG simulated by the dynamic model;

b) fECG simulated by the dynamic model; c) simulated ADS. Note:
arbitrary units are used for y axis.

In Fig. 4 the detection of the mQRS complexes can be

observed.

Fig. 7. The fECG extraction from real ADS (normal pregnancy, 37wk): a)
real ADS; b) extracted fECG, after mECG cancelling by ESC. Note:
arbitrary units are used for y axis.

The algorithm described in Section II shows very good

results, as demonstrated in Fig. 5 and 7 and its performance
Fig. 4. mECG template estimation from simulated ADS data: a) detection of
the maternal R-peaks; b) Auxiliary signal used for QRS detection; c) is evaluated by calculating the error between the original
extracted mECG template. simulated fECG and the extracted fECG, with:

  fECG  fECG 
The results of the fECG extraction by applying the ESC to 2
the simulated data are depicted in Fig. 5. As depicted in Fig.
 fECG  orig extracted
 0.0379 (5)
5, the mECG is completely removed, even when overlapping
 fECG
2
orig
the fECG; the cleaned ADS signal still shows the maternal

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ACKNOWLEDGMENTS [7] Congenital Heart Defects in Children Fact Sheet,

The work has been funded by the Sectoral Operational American Heart Association, 2008. [Online]. Available:
Programme Human Resources Development 2007-2013 of http://www.americanheart.org/children.
the Romanian Ministry of Labour, Family and Social [8] Congenital Heart Defects, British Heart Foundation.
Protection through the Financial Agreement POSDRU/ [Online], http://www.bhf.org.uk
6/1.5/S/19 and by the National University Research Council [9] I. Amer-Wåhlin, B. Yli, S. Arulkumaran, „Foetal ECG
of Romania (CNCSIS) under the national research grant PN and STAN technology – A review‖. European Clinics in
II ID PCE ID 1723/2009. Obstetrics and Gynaecology, Vol. 1, pp. 61–73,2005
[10] K.G. Rosn, I. Amer-Wahlin, R. Luzietti, H. Norn. ―Fetal
REFERENCES
ECG waveform analysis‖. Best Practice and Research
[1] M. Ream, A. M. Ray, R. Chandra, and D. M.
Clinical Obstetrics and Gynaecology; Vol. 18, pp. 485–
Chikaraishi. ―Early fetal hypoxia leads to growth
514, 2004
restriction and myocardial thinning‖ , Am J Physiol
[11] L.L. Su, Y.S. Chong, A. Biswas,‖Use of Fetal
Regul Integr Comp Physiol, vol. 295, no. 2, pp. R583-
Electrocardiogram for Intrapartum Monitoring‖. Annals
R595, 2008.
Academy of Medicine, Vol. 36, pp. 416–420, 2007.
[2] T.D. Cannon, R Yolken, S Buka, E.F. Torrey, et al
[12] M.Shao, K. E. Barner, M. H. Goodman ―An
―Decreased neurotrophic response to birth hypoxia in
Interference Cancellation Algorithm for Noninvasive
the etiology of schizophrenia‖. Biol Psychiatry Vol. 64,
Extraction of Transabdominal Fetal
No. 9, pp. 797–802, ISSN 0006-3223 2008.
Electroencephalogram‖ IEEE Trans. Biomed. Eng., vol.
[3] C. Mallen, S. Mottram and E. Thomas, ―Birth factors
51, no. 3, 2004
and common mental health problems in young adults. A
[13] V. Zarzoso, AKNandi, E. Bacharakis. ―Maternal and
population-based study in North Staffordshire, Social
fetal ECG separation using blind source separation
Psychiatry and Psychiatric Epidemiology‖, Vol. 43, No.
methods‖. IMA J Mathematics Appl Med & Biol,
4, pp. 325-330, 2008.
Vol.14, No. 3, pp.207-225, 1997.
[4] H. Wienerroither, H Steiner, J. Tomaselli, M.
[14] De Lathauwer L, De Moor B, Vandewalle J. ―Fetal
Lobendanz, L. Thun-Hohenstein. „Intrauterine blood
electrocardiogram extraction by blind source subspace
flow and long-term intellectual, neurologic, and social
separation.‖ IEEE Trans Biomed Eng, Vol.47, No.5, pp.
development‖. Obstet Gynecol Vol. 97, No. 3, pp. 449–
567-572, 2000.
453, 2001.
[15] Richter M, Schreiber T, Kaplan DT. Fetal ECG
[5] J. Li, J.C. Lin, H. Wang, J.W.Peterson, B.C. Furie, et al.
extraction with nonlinear state-space projections. IEEE
„Novel role of vitamin k in preventing oxidative injury
Trans Biomed Eng, Vol. 45, No. 1, pp. 133-137, 1998.
to developing oligodendrocytes and neurons‖. J
[16] M. Ungureanu, W. Wolf, ―Basic aspects concerning the
Neurosci Vol. 23, No. 13, pp. 5816–5826, 2003.
event-synchronous interference canceller,‖ IEEE Trans.
[6] K. J. Jenkins, A. Correa, J. A. Feinstein, L. Botto, et. Al.
Biomed. Eng., vol. 53, no. 11, pp. 2240-2247, Nov.
―Risk Factors and Congenital Cardiovascular Defects:
2006.
Current Knowledge: A Scientific Statement From the
[17] P. E. McSharry Gari D. Clifford, Lionel Tarassenko,
American Heart Association Council on Cardiovascular
and Leonard A. Smith, ―A Dynamical Model for
Disease in the Young:Endorsed by the American
Generating Synthetic Electrocardiogram Signals,‖ IEEE
Academy of Pediatrics ―, Circulation Vol. 115, No. 23,
Trans. Biomed. Eng., vol. 54, no. 3, March 2003.
pp. 2995-3014, 2007.

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Statistic and Fractal Processing of Human

Biological Fluids Phase-Inhomogeneous Images
Yuriy USHENKO, Olga TELENHA, Valentine BALANETSKA, Maksim SIDOR
Chernivtsi National University
[email protected]
Abstract – Performed in this work are complex statistic and fractal analyses of phase properties inherent to
birefringence networks of optically thin layers prepared from human bile. Within the framework of a
statistic approach, the authors have investigated values and ranges for changes of statistic moments of the 1-
st to the 4-th orders that characterize coordinate distributions for phase shifts between orthogonal
components of amplitudes inherent to laser radiation transformed by human bile with various pathologies.
The correlation criteria for differentiation of phase maps describing pathologically changed liquid-crystal
networks are determined. In the framework of the fractal approach, determined are dimensions of self-
similar coordinate phase distributions as well as features of transformation of logarithmic dependences for
power spectra of these distributions for various types of human pathologies.

Index Terms – polarization, phase, fractal, biological fluid, statistic moments, birefringence.

I. INTRODUCTION perform diagnostics of structures inherent to liquid-crystal

Among the methods for optical diagnostics of human networks of human bile with various pathologies by using
biological tissues (BT), the methods of laser polarimetric the method to determine the coordinate distributions of
diagnostics aimed at their optically-anisotropic structure are phase shifts (phase maps) between orthogonal components
widely spread [1 - 31]. The main ―information product‖ of of laser radiation amplitudes with the following statistical,
these methods is availability of coordinate distributions for correlation and fractal analyses of these distributions.
azimuths  x, y  and ellipticity  x, y  of polarization
II. THE OPTICAL MODEL OF HUMAN BILE
(polarization maps) with the following types of analyses: As a base for modeling the optical properties of human
statistical (statistical moments of the 1-st to 4-th orders [5, 6, bile we use the conception of anisotropy observed in BT
10, 14, 19, 25, 26, 30]), correlation (auto- and joint protein networks developed in [1-4, 7, 9, 14, 16, 23-27, 30]:
correlation function [12, 17, 18, 21, 26]), fractal (fractal  human bile can be considered as a two-component
dimensionalities [5, 6, 25]), singular (distributions of amorphous-crystalline structure;
amounts of linearly and circularly polarized states [22, 28]).  optically isotropic - optically homogeneous micellar
As a result, interrelations between the set of these parameters solution;
and distributions of optical axis directions as well as values  optically anisotropic - liquid-crystalline phase,
of the birefringence characterizing the network of optically consisting of three types of liquid crystals: needle crystals of
uniaxial protein (myosin, collagen, elastin, etc.) fibrils in fatty acids, cholesterol monohydrate crystals, bilirubinate
optically anisotropic components of BT layers can be crystals of calcium.
The optical properties of amorphous A and crystalline
determined. Using this base, developed is a set of methods
for early recognition and differentiation of pathological
changes in BT structures related with their degenerative- Ccomponents of biological fluids can be exhaustively
dystrophic and oncological changes [4-6, 12, 19, 20-22, 27, described using the following Jones operators [26]
29, 31]. a a exp  l  0
A  11 12  ; (1)
exp  l 
It is noteworthy that there exists a widespread group of
a21 a22 0
optically anisotropic biological objects for which the
methods of laser polarimetric diagnostics are not so efficient. c11 c12
Optically-thin (the attenuation coefficient   0.1 ) layers of C  
c 21 c 22
various biological fluids (bile, urine, liquor, synovial fluid, . (2)
blood plasma, etc.) can be related to these objects. All these cos 2   sin 2  exp  i  cos  sin  1  exp  i 

layers possess considerably less optical anisotropy of the cos  sin  1  exp  i  sin 2   cos 2  exp  i 
biological component matter as compared with birefringent
BT structures [4]. As a consequence, these objects weakly
Here,  is the absorption coefficient for laser radiation in
 x, y   const ; the biological fluid layer with the geometric thickness l ; 
modulate polarization of laser radiation (  ).
 x, y   0. - direction of the optical axis;   2
On the other hand, the biological fluids are more available  nd - phase shift
for a direct laboratory analysis as compared to traumatic between the orthogonal components E x and E y of the
methods of BT biopsy. From the above reasoning, it seems amplitude of illuminating laser light with the wavelength  ;
topical to search new, additional parameters for laser
n - index of birefringence.
diagnostics of optically anisotropic structures in biological
The Jones matrix of the biological fluid layer, where
fluids.
isotropic and anisotropic creations lie in one plane, can be
This work is aimed at searching the possibilities to

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

expressed as a sum of operators A and C

a11  c11; a12  c12;
M   A C  , (3)
a21  c21; a22  c22.
Let us consider the process of transformation of the
complex amplitude ( E  U ) of a laser wave that passed
through the biological fluid layer ( M  ) located between
two crossed phase filters – quarter-wave plates ( 1 and
 2  ) and polarizers ( P1 and P2 ), planes of Fig. 1. Polycrystalline networks of human bile taken from
transmission for which make +450 and –450 angles with axes healthy patient (a) and patient suffering from insulin-
of the highest velocity. The amplitude U of the transformed independent diabetes (b).
laser beam in this experimental setup can be determined
from the following matrix equation The images of layers prepared from human bile (figure 1)
are indicative of availability of two fractions – optically
U  0.25P2 2 1P1E . (4) isotropic and liquid-crystal network (anisotropic one). As
seen, geometric structure and sizes of separate elements in
Here,
the polycrystalline network of the samples prepared from
  Ex  U 
 E   , U   x  biological fluids are individual for physiological state.
E exp  i    U y exp  i ,
  y 0   
 1 1 1 1 (5)
 P1  , P2   ,
 1 1 1 1
 1 0 i 0
 1   ,  2   .
 0 i 0 1
In the special case of a plane-polarized wave

  1
E E x  E y ;  0  0    , Eq. (4) acquires the form
1
1 1 i 0
U  0.25 
1 1 0 1
cos 2   sin 2  exp i  cos  sin  1  exp i  (6)
 
cos  sin  1  exp i  sin 2   cos 2  exp i 
1 0 1 1 1
  .
0 i 1 1 1
The solution of the matrix equation (6) is the value of
complex amplitude U   that is determined exclusively by
the phase shift  and does not depend on orientation of the
optical axis  for a laser image of biological fluid. Being
based on it, one can write
I  r   UU   I 0 sin 2   2 . (7)
Here, I 0 is the intensity of a probing laser beam, I r  -
intensity of the laser image for the biological fluid layer in
the point r  .
Interrelations (4) to (7) define the algorithm for direct
experimental measuring the coordinate distribution of phase
shifts  r  between orthogonal components of the Fig. 2. Coordinate (a, b) and quantitative (c, d) distributions  of laser
amplitudes U x , U y in the laser image of an optically images for the samples of bile taken from healthy patient‘s (a, c, e) and with
insulin-independent diabetes (b, d, f).
anisotropic biological fluid layer.
Shown in figure 2 are the phase maps (fragments (a), (b),
III. TABLES, FIGURES, EQUATIONS (c), (d)) and histograms (fragments (e), (f)) for distributions
As objects for experimental studying, we chose optically- of random values inherent to the phase shifts  between
thin layers of bile taken from a healthy patient (figure 1a) orthogonal components of the laser radiation amplitude
and patient suffering from insulin-independent diabetes transformed inside layers of bile taken from healthy patient‘s
(figure 1b). (left column) and from patient suffering from insulin-
independent diabetes (right column).
The obtained data show that the value of phase shifts 
for laser radiation transformed inside layers of human bile
lies within the short range of changes 0     . The weak

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phase modulation is related with two factors. First, it is low  fact that autocorrelation functions Kmin x  (figure
geometric thickness (d = 10…15 µm) of the samples. 3, fragments (c, g)) monotonically drop with increasing the
Second, it is weak birefringence ( n ~ 104...102 ) of liquid- step of scanning x in dependences N min x  ;
crystal structures in human bile.  correlation structure of the distribution for the
Our comparative analysis of histograms for distributions extreme sample  m  n   in the phase map describing the
of random values inherent to phase shifts  in laser images
polycrystalline component in bile of a sick patient changes:
of both types human bile revealed availability of two
at the background of monotonic drop there arise oscillations
dominant extreme ranges: 0 ≤  ≤ 0.15 and 0.85 ≤  ≤ 1. In
of values in the dependence K max x  (see figure 4,
our opinion, these features of probabilistic phase
distributions are related with the influence of optically fragment (g));
isotropic (   0 ) and liquid-crystal (    ) components  logarithmic dependences for the power spectra of
in the composition of biological fluid. distributions N min x  for the optically isotropic component
The results show that the differentiation phase maps of in bile of both types possess a stable slope angle (figure 3,
different groups is impossible - change of size and range of fragments (d, f)) within the whole range of geometric sizes
statistic moments of 1 - 4-th order almost coincide. inherent to the laser image registered by the CCD camera
Being aimed at more specific investigation of phase (figure 1);
features for both fractions, we used the following method to  fractal distributions N max x  for phase maps of laser
select information. From the available coordinate set of images describing the optically anisotropic fraction of bile a
  ,... 1n  healthy man (figure 4, fragment (d)) are transformed into the
values  m  n    11  in phase maps (figures 2(a)
  n1 ,...  mn 
statistic ones in the case of insulin-independent diabetes:
approximating curve in the dependence
and 2(b)), we found samples of extreme values  m  n  0
log J N max   log d has no stable slope (Fig. 4, fragment
1
and  m  n   .
(h)).
In what follows, by scanning along the direction
x 1  n we carried out calculation of the amount of
extreme values for phase shifts within the column
m  n 1 pix . Within the limits of each local sample
1pix  n pix k 1,2,...,m ,
we computed the amount ( N ) of
extreme values  k   0 ( N min
k  k  ).
) and  k    ( N max
Thus, we found the dependences
N msn x   ( N msn(1) , N min (2) , ..., N min (m) ) and
N max x   ( N max , N max , ..., N max )
(1) ( 2) ( m)
for the
amount of extreme values of phase shifts within the limits of
laser image for bile.

Figures 3 and 4 show a set of coordinate distributions

 m  n  0,  (fragments (a, e)) for the dependences of the
amount of extreme values Nmin;max x  (fragments (b, f)),
autocorrelation functions Kmin;max x  (fragments (c, g))
and logarithmic dependences log J N min;max   log d 1 for
power spectra of distributions Nmin;max x  (fragments (d, h))
that characterize phase maps for the samples of bile
belonging to a healthy patient (left column) and a patient
suffering from insulin-independent diabetes (right column).
The comparative analysis of the obtained set of Fig. 3. Coordinate m n  (a, e)), quantitative N min x  (b, f)), correlation
experimental data about statistic, correlation and fractal K min x  (c, g)) and fractal log J N min   log d 1 (d, h) parameters of
structures in dependences for the amount of extreme values the extreme sample  m  n  0 for phase maps of the samples of bile
N min,max x  inherent to phase maps describing layers of bile belonging to a healthy patient (a, b, c, d) and a patient with insulin-
of healthy patient and that sick with insulin-independent independent diabetes (e, f, g, h).
diabetes enabled to found:
 tendency to a decreasing (increasing) total amount of From the quantitative viewpoint, the dependences
extreme values  min  0 (  max   ) of the phase shifts in Nmin;max x  illustrate statistic M i1 4 , correlation S  , Q
laser images of layers prepared from bile of a patient with
insulin-independent diabetes (figures 3 and 4, fragments (b, and fractal F  , D parameters determined within the limits
f)); of two patient groups, and they are summarized in Tables 2.
Our analysis of the parameters determined
experimentally has shown that the following parameters are

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diagnostically sensitive in observation of pathologic

processes TABLE 2. STATISTIC MOMENTS M i1 4 , CORRELATION S  , Q
AND FRACTAL F  , D PARAMETERS THAT CHARACTERIZE
THE DISTRIBUTIONS FOR AMOUNTS OF EXTREME VALUES IN
COORDINATE DISTRIBUTIONS  m n  OF LASER IMAGES FOR
HUMAN BILE
 m n  m  n  0  m  n  
Healthy Healthy
M i14
Diabetes (19 Diabetes (19
(21 (21
patients) patients)
patients) patients)
M 1 0.51±0.063 0.54±0.067 0.22±0.025 0.35±0.042

M2 0.13±0.018 0.08±0.011 0.25±0.031 0.14±0.017

M 3 0.26±0.033 0.19±0.022 0.79±0.086 2.18±0.25

M 4 0.48±0.054 0.55±0.068 0.83±0.098 3.11±0.42

Q4 0.14±0.016 0.12±0.015 0.56±0.069 2.21±0.31


S 0.24±0.015 0.21±0.013 0.17±0.021 0.08±0.012

F 2.42±0.12 2.49±0.11 2.58±0.15 Statistic

D 0.21±0.028 0.24±0.027 0.34±0.042 0.18±0.023

 Ascertained and grounded is a set of criteria for phase

diagnostics of inflammatory processes (diabetes,
cholecystitis) as being based on statistic (statistic moments
of the first to fourth orders), correlation (normalized fourth
statistic moment of autocorrelation function, correlation
area) and fractal (fractal dimension and dispersion for the
Fig. 4. Coordinate m  n  (a, e)), quantitative N max x  (b, f)), correlation
distribution of extrema in log – log dependences of power
K max x  (c, g)) and fractal log J N max   log d 1 (d, h) parameters of spectra) analyses of phase distributions in laser images of
the extreme sample  m  n  1 for phase maps of the samples of bile human bile.
belonging to a healthy patient (a, b, c, d) and a patient with insulin-
independent diabetes (e, f, g, h). REFERENCES
[1] W.-F. Cheong, S. A. Prahl, A. J. Welch, ―A Review of
 statistic moments of the third ( M 3 ) and fourth ( M 4 ) the Optical Properties of Biological Tissues,‖ IEEE J.
orders in distributions for the amount of extreme values Quantum. Electron. 26, 2166-2185, 1990.
N max x  of phase shifts  m  n  1 in laser images for bile [2] S. A. Prahl, M. Keijzer, S. L. Jacques, A. J. Welch, ―A
Monte Carlo model of light propagation in tissue,‖ in
of both types – differences between them reach 2.4 and 4.1 SPIE Proceedings of Dosimetry of Laser Radiation in
times; Medicine and Biology, G. J. Müller and D. H. Sliney, eds.

 the kurtosis ( Q4 ) of autocorrelation functions IS 5, 102-111, 1989.
K max x  related to distributions N max x  differ by 1.8 and [3] E. Wolf, ―Unified theory of coherence and polarization
of random electromagnetic beams,‖ Phys. Lett. A. 312,
2.7 times;
263-267, 2003.
 correlation area S  for the autocorrelation [4] Alexander G. Ushenko and Vasilii P. Pishak, ―Laser
dependence K max x  of the distribution for the amount of Polarimetry of Biological Tissue: Principles and
extreme phase shifts in a laser image inherent to joint bile of Applications‖, in Handbook of Coherent-Domain
a patient with osteoarthritis is 2.55 times less than that Optical Methods: Biomedical Diagnostics,
parameter determined for a healthy patient; Environmental and Material Science, Valery V. Tuchin,
 distributions N max x  for the phase maps describing ed. (Boston: Kluwer Academic Publishers, 2004), pp.
93-138.
bile for healthy and sick patients are, respectively, fractal
[5] O. V. Angelsky, A. G. Ushenko, Yu. A. Ushenko, V. P.
and statistic;
Pishak, ―Statistical and Fractal Structure of Biological
 dispersion D of the dependences Tissue Mueller Matrix Images‖, in Optical Correlation
log J N max   log d in the case of pathological changes in
1
Techniques and Applications, Oleg V. Angelsky, ed.
the polycrystalline structure of bile is 1.75 times decreased. (Washington: Society of Photo-Optical Instrumentation
Engineers, 2007), pp. 213-266.
[6] O.V. Angelsky, A.G. Ushenko, Yu.A. Ushenko, V.P.
IV. CONCLUSION Pishak, and A.P. Peresunko, ―Statistical, Correlation,
Thus, one can draw the following conclusions: and Topological Approaches in Diagnostics of the
 Human bile, independently of their physiological Structure and Physiological State of Birefringent
state, contains phase-modulating optically anisotropic Biological Tissues‖, in Handbook of Photonics for
network of biological crystals.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Biomedical Science, Valery V. Tuchin, ed. (USA: CRC [21] O. V. Angelsky, A. G. Ushenko, and Ye. G. Ushenko,
Press, 2010), pp. 21-67. ―Investigation of the correlation structure of biological
[7] Alexander G. Ushenko, ―Polarization structure of laser tissue polarization images during the diagnostics of their
scattering fields,‖ Opt. Eng. 34, 1088-1093 (1995). oncological changes,‖ Phys. Med. Biol. 50, 4811-4822,
[8] A.G. Ushenko, ―Laser diagnostics of biofractals,‖ 2005.
Quantum Electron. 29, 1078–1084, 1999. [22] Oleg V. Angelsky, Alexander G. Ushenko, Yevheniya
[9] O.V. Angel'skii, A.G. Ushenko, A.D. Arkhelyuk, S.B. G. Ushenko, Yuriy Y. Tomka, ―Polarization singularities
Ermolenko, D.N. Burkovets, ―Structure of matrices for of biological tissues images,‖ J. Biomed. Opt. 11, 054030,
the transformation of laser radiation by biofractals,‖ 2006.
Quantum Electron. 29, 1074-1077, 1999. [23] O.G. Ushenko, S.G. Guminetsky, A.V. Motrich,
[10] O.V. Angel'skii, A.G. Ushenko A.D. Arheluk, S.B. ―Optical properties of urine, blood plasma and
Ermolenko, D. N. Burkovets, ―Scattering of Laser pulmonary condensate of the patients with pulmovnary
Radiation by Multifractal Biological Structures,‖ Optics form of tuberculosis,‖ Photoelectronics 16, 133-139,
and Spectroscopy 88, 444-448, 2000. 2007.
[11] A.G. Ushenko, ―Polarization Structure of Biospeckles [24] S.H. Guminetskiy, O.G. Ushenko, I.P. Polyanskiy, A.V.
and the Depolarization of Laser Radiation,‖ Optics and Motrych, F.V. Grynchuk, ―The optical method for
Spectroscopy 89, 597-601, 2000. investigation of the peritonitis progressing process,‖
[12] A.G. Ushenko, ―Stokes-correlometry of biotissues,‖ Proc. SPIE 7008, 700827, 2008.
Laser Phys. 10, 1286-1292, 2000. [25] Alexander Ushenko, Sergej Yermolenko, Alexander
[13] A.G. Ushenko, ―The Vector Structure of Laser Prydij, Stepan Guminetsky, Ion Gruia, Ovidiu Toma,
Biospeckle Fields and Polarization Diagnostics of Konstantin Vladychenko, ―Statistical and fractal
Collagen Skin Structures,‖ Laser Phys. 10, 1143-1149, approaches in laser polarimetry diagnostics of the
2000. cancer prostate tissues,‖ Proc. SPIE 7008, 70082C,
[14] A.G. Ushenko, ―Laser polarimetry of polarization-phase 2008.
statistical moments of the object field of optically [26] A.G. Ushenko, A.I. Fediv, Yu.F. Marchuk, ―Correlation
anisotropic scattering layers,‖ Optics and Spectroscopy 91, and fractal structure of Jones matrices of human bile
313-316, 2001. secret,‖ Proc. SPIE 7368, 73681Q, 2009.
[15] A.G. Ushenko, ―Polarization contrast enhancement of [27] A.G. Ushenko, Yu.Ya. Tomka, V.I. Istratiy, ―Polarization
images of biological tissues under the conditions of selection of two-dimensional phase-inhomogeneous
multiple scattering,‖ Optics and Spectroscopy 91, 937-940, birefringence images of biotissues,‖ Proc. SPIE 7388,
2001. 73881L, 2009.
[16] A.G. Ushenko, ―Laser probing of biological tissues and [28] A.G. Ushenko, A.I. Fediv, Yu.F. Marchuk, ―Singular
the polarization selection of their images,‖ Optics and structure of polarization images of bile secret in diagnostics of
Spectroscopy 91, 932-936, 2001. human physiological state,‖ Proc. SPIE 7368, 73681S,
[17] A.G. Ushenko, ―Correlation processing and wavelet 2009.
analysis of polarization images of biological tissues,‖ [29] S.B. Yermolenko, A.G. Ushenko, P. Ivashko,
Optics and Spectroscopy 91, 773-778, 2002. ―Spectropolarimetry of cancer change of biotissues,‖ Proc.
[18] A.G. Ushenko, ―Polarization correlometry of angular SPIE 7388, 73881D, 2009.
structure in the microrelief pattern or rough surfaces,‖ [30] A.G. Ushenko, I. Z.Misevich, V. Istratiy, I. Bachyns‘ka,
Optics and spectroscopy 92, 227-229, 2002. A. P. Peresunko, Omar Kamal Numan, and T. G.
[19] O.V. Angelsky, A.G. Ushenko, Ye.G. Ushenko, ―2-D Moiysuk, ―Evolution of Statistic Moments of 2D-
Stokes Polarimetry of Biospeckle Tissues Images in Distributions of Biological Liquid Crystal Net Mueller
Pre-Clinic Diagnostics of Their Pre-Cancer States,‖ J. Matrix Elements in the Process of Their Birefringent
Holography Speckle 2, 26-33, 2005. Structure Changes,‖ Advances in Optical Technologies
[20] Oleg V. Angelsky, Alexander G. Ushenko, and 2010, 423145, 2010.
Yevheniya G. Ushenko, ―Complex degree of mutual [31] O. V. Dubolazov, A. G. Ushenko, V. T. Bachynsky, A.
polarization of biological tissue coherent images for the P. Peresunko, and O. Ya. Vanchulyak, ―On the
diagnostics of their physiological state,‖ J. Biomed. Opt. Feasibilities of Using the Wavelet Analysis of Mueller
10, 060502, 2005. Matrix Images of Biological Crystals,‖ Advances in
Optical Technologies 2010, 162832, 2010

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Ultrasound Imaging: Correction of Geometric

Distortions using Warping
Ari LEV-OR and Moshe PORAT
Technion, Haifa 32000, Israel
[email protected] [email protected]
Abstract – Ultrasound images suffer from inherent geometric distortions due to variations in sound speed
within the body. Other distortions include missing surfaces parallel to the direction of the ultrasonic rays,
intense speckle noise, acoustic shadows and resolution inconsistency. These artifacts depend on the
positioning of the transducer relative to the scanned organs, and considerably degrade the quality of the
images obtained. We introduce a new algorithm that combines ultrasound images taken from distant
viewpoints using spatial warping and compounding to obtain a quality-enhanced image. The algorithm is
iterative: in each iteration the B-Mode images are divided into blocks and a matching procedure is performed
between blocks of the reference images. Individual pixels are translated based on inter-block interpolation,
subject to physical and medical constraints. The resultant warped images are used as an input signal to the
next iteration. The algorithm was implemented and tested in-vitro, demonstrating superior results compared
to presently available methods. The results are presented and discussed.

Index Terms – Block Matching, Non-Linear Processing, Spatial Compounding, Ultrasound Imaging, 2D
Warping.

I. INTRODUCTION
Ultrasound is a useful non-invasive tool for soft tissue
imaging due to its low cost along with real time acquisition.
The quality of the reconstructed images however is lower
than in other medical imaging systems such as X-Ray, MRI
or CT. It suffers from differences in spatial and axial
Fig. 1: Ultrasound images (simulation) of a circular cylinder. Left: The
resolution, noise (speckle and other), acoustic shadows, actual speed of sound inside the object is exactly as assumed. Different
missing surfaces and geometric distortions. images are obtained if the speed inside the object is lower than assumed
One of the problems is the deformation caused by the (center) or higher than assumed (right). The transducer is positioned at the
variations in sound speed in the different body tissues. An top in all three images.
ultrasound system assumes that the speed of sound is surfaces are also rectified by compounding two images, and
constant within the human body (1540 m/s) [5], and will be discussed as byproducts of the proposed algorithm.
accordingly reconstructs the echoed pulses into a 2D image. This paper is organized as follows. Definitions and
It is known however that this speed varies [5] and causes the notations are presented in Section II. The new algorithm is
axial dimensions of organs to be out of scale (Figure 1). This described in Section III, and major considerations are
variation in size however, despite its somewhat marginal introduced in Section IV. Simulation results are given in
effect on the resultant image, plays a major role when two or Section V and the paper is concluded with a summary in
more ultrasound images are taken from different angles and Section VI.
compounded to create a higher quality image.
Previous works on image compounding, targeting speckle II. II. DEFINITIONS AND NOTATIONS
reduction and enhancing tissue boundaries, have either The following notations are used throughout this paper.
scanned the region of interest by alternately activating 2.1. Scan Line – an A-Mode ultrasound image. Along this
different parts of the poly-crystal transducer thus scanning in each pixel represents the intensity of the echoed (returned)
different angles [4], or used a mechanical arm to move [7] or pulse.
track [3] the transducer with high accuracy. According to 2.2. Scan Line Collection Image (SLC Image) – a raster
He‘s et al. approach [2], a thin wire phantom is used to display of the scan lines: the horizontal axis corresponds to
calibrate the scanning system before performing the scan on the ultrasonic pulse firing-angle (i.e., angle of scan-line) and
a human subject. the vertical axis represents depth.
In this work we propose a solution to the problem of 2.3. Fan Image - The B-Mode ultrasound image. This is a
geometric distortions based on image processing techniques. straightforward reconstruction of the image given the SLC
According to our proposed algorithm, two scans are obtained image and the angle associated with each scan-line. The term
from two relatively distant viewpoints (Figure 2), resulting ‗Fan‘ indicates that the scan lines are in a fan-like
in significant geometric correction. Local information [6] is arrangement.
used for identifying similar parts in the two images, and an 2.4. Difference between blocks: The obtained images are
iterative process [1] warps the images to optimally match. gray-scale. The intensity of the pixel (x, y) in block k is
This work was supported in part by a grant from the GIF, the German- represented by Ik(x, y), where 0xW-1, and 0yH-1. x, y,
Israeli Foundation for Scientific Research and Development, and by the W, H  Z (integers). W and H denote the width and height of
Ollendorff Minerva Center. Minerva is funded through the BMBF. the block, respectively. The difference between two blocks is
defined by

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P2 P1 out as follows.
4.1. Apply low-pass-filtering to both Fan images to reduce
the sensitivity of the matching process to noise and contour
deformation.
4.2. Divide the first fan image into blocks.
4.3. For each block perform block-matching between the
two images. Two translation vectors are attained: A regular

2D minimum-difference translation, denoted V 2 D , and a
vector of minimum-difference when translation is allowed
only along the scan-line that goes through the block‘s center,

denoted V SL . Consistency in the direction of these two
Fig. 2: The dual-transducer structure. The images obtained from two angles vectors ensures that the deformation is only axial and is due
(P1 and P2) are integrated into a compounded higher quality image. to variations in sound speed.
H 1 W 1 I j  x, y  I k  x, y  
4.4. Calculate a quality factor of the match Q (0Q1): If

Diff jk    (1) V 2 D and V SL point in similar directions, the match is
y 0 x 0 Ej Ek
considered good and Q is close to 1. Q is lower (close to 0)
where Ej is related to the total energy (sum of pixel values) if the directions differ significantly. Denote the angle
of block j: between the two vectors as  (Figure 4), the quality factor is
H 1W 1
E j    I j (x , y ) . (2) defined according to the projection of one vector onto
y 0 x 0
another:
The difference Diff is in the range of [0, 2] due to
normalization according to the size and energy of the blocks.  0 cos( )  0
Q . (3)
Diff=0 means that the blocks are identical, up to a
cos( ) cos( )  0
multiplication factor, as in the case of acoustic shadows.
Maximum difference (Diff=2) is obtained when each white
pixel in the first image corresponds to a black pixel in the Start
other, and vice versa. To avoid singularity, when a block is
all black the result is set to Diff=1.
Equation (1) is also used for calculating the difference
between the two images. 3.1. Acquire two SLC images
III. THE ALGORITHM
Given the above definitions, we can now introduce the
3.2. Convert theSLC images
algorithm for spatial warping and compounding:
3.1. Acquire two SLC images of the same cross-section from into Fan images
two different viewpoints.
3.2. Construct two Fan images based on the two SLC 3.3. Rotate and T ranslate the Fan
images. images to correlate
3.3. Rotate and translate the two Fan images according to the
angle and displacement between the viewpoints.
3.4. Stop if the difference between two consecutive images Yes
is below a resolution threshold. 3.4. Diff < T hreshold?
3.5. Divide both images into blocks. Calculate the spatial
translation required for each block in each Fan image. No
Accordingly, derive the appropriate translation of all the 3.5. Calculate pixel translation
pixels in each SLC image (Section 4). for both images
3.6. Translate the pixels in both SLC images.
3.7. Go to step 3.2.
These steps are summarized in Figure 3. 3.6. T ranslate the pixels in each
The algorithm is iterative. The two images are warped in SLC images
each iteration to reduce the difference between them. The
algorithm may be terminated in one of two ways: 1. After a
predefined number of steps. 2. When the difference between Stop
the images is below a threshold value. The first approach is
straightforward, and adequate. Fig. 3: Flowchart of the algorithm.
IV. IMAGE WARPING The quality factor serves as a weight of the block‘s
The proposed algorithm is block based. Each image is translation when averaging translation of several blocks.
divided into blocks, and a block-matching procedure is 4.5. Calculate the final translation of the block. This
applied. The translation is calculated by averaging the translation must be along a scan-line assuming that the
translation of the block containing the pixel and the distortions due to speed variations are only axial. We define
translation of the neighboring blocks. This process is carried 
the final translation vector V final to have the same direction

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

as VSL , and magnitude of V final  min(VSL ,V2 D  Q) . By image-difference is not related directly to image-quality as
perceived by humans. For example, when using 16 2-pixel
selecting the minimum translation over-warping of the blocks, the image-difference decreases rapidly to a low
image is avoided. value, despite an intense blockiness effect and loss of

4.6. Once V final is calculated for all the blocks, each pixel contour roundness. Larger blocks (322 pixels and above)
is translated according to the weighted average translation of have shown slower decrease but the roundness of the
its neighboring blocks. Two weights are applied when contours was sustained.
averaging: The quality factor Q, and the distance Dn between VI. SUMMARY
the pixel and the block center. An image-processing technique has been applied
successfully to ultrasound images, significantly reducing
Q 0.4
Q=0   their inherent geometric distortions. The proposed algorithm
is primarily designed to compensate for geometric
distortions, however, a highly beneficial byproduct of the
Fig. 4: Two examples of the quality factor Q. Left: >90 , cos()<0 and process is reduction of speckle noise and missing edges,
Q=0. Right: <90 , cos()>0 and Q>0.
since the combined image is an average of two images taken
from distant viewpoints, in which the distortions diverse. It
Thus we get:
is also shown that the manipulation of the images is better
8 
V  G D n   Q n done when using both SLC (scan line collection) and Fan
 n 0
n final
(B-Mode) images.
V Pixel  8
,

G D 
n 0
n

(4)
where the weight function G is monotonically decreasing
with the distance Dn:
 D
1  n 0  Dn  DMax ,
G ( Dn )   DMax
 0 Dn  DMax
(5) (a) (b)
and
D Max  1.5 W 2
H 2 .
(6)
Dn and Dmax are measured in units of the sampling interval
between pixels.
To avoid dependency on a specific block division we use
overlapping block-sets that are displaced relative to the
original division, i.e., the origin of the first (top-left) block is
(dx, dy) instead of (0,0). The pixel translation process is (c)
performed on each block-set, thus eliminating a blockiness
effect in the warped image.
V. RESULTS
The algorithm was tested on the ultrasound images of
Figure 2. The images are 256x256 pixels, each pixel is
represented by 8 bits, i.e., 256 grey levels.

The first few iterations cause the difference between the

images to decrease significantly (Figure 5). However, the
iterative process may introduce an error since pixel Fig.5: The compounded images according to the set-up of Figure 2. (a) The
translation is not necessarily according to an integer number original two images. (b) After one iteration. (c) Minimum difference
and a single pixel may spread its energy in two neighboring obtained after 8 iterations.
pixels. Moreover, there is a mutual-pixel drift due to the Our conclusion is that a dual-transducer system can
feedback nature of the algorithm. The result is that after significantly improve ultrasound imaging compared to the
reaching a minimum, the difference between consecutive traditional approach. The new method may be also useful in
images may increase. correcting distortions caused by differences between lateral
The algorithm was tested with regard to two parameters. and radial resolutions, and may allow a wider ultrasonic
The first parameter was the size of each block, ranging from beam thus achieving better defocusing property.
162 to 562 pixels, in steps of 8 pixels. The second parameter
was the number of block-sets, selected in the range of 1 to 52
(i.e., 5 subdivisions on each axis). According to our results,
the algorithm is robust to the above changes if more than 22
block-sets are used. It should be noted however that the

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ACKNOWLEDGMENT [3] A. Hernandez, O. Basset, P. Chirossel and G. Gimenez,

We thank Dr. Moshe Bronshtein of the Al-Kol ultrasound ―Spatial Compounding in Ultrasonic Imaging using an
clinic in Haifa, Israel, for his contribution to this work. We articulated scan arm‖, Ultrasound in Medicine and
are also grateful to Prof. I. Meizner and the staff of the Biology, Vol. 22, No. 2, pp. 229-238, 1996.
Women-Ultrasound department of the Belinson Hospital [4] Soren K. Jespersen, Jens E. Wilhjelm and Henrik
(Rabin Medical Center), Petah-Tikva, Israel, for their Sillesen, ‖Multi-Angle Compound Imaging‖, Ultrasonic
assistance, and to Prof. Dan Adam of the Biomedical Imaging, Vol. 20, pp. 81-102, 1998.
Engineering department at the Technion for his help. Lastly, [5] ―Biological Effects of Ultrasound: Mechanisms and
we would like to thank Mr. Moti Shenhar, for the Clinical Implications‖, NCRP (National Council on
construction of the ultrasound phantom. Radiation Protection and Measurements) Report No. 74,
NCRP Publications, Bethesda, Maryland, Dec 30 1983.
[6] M. Porat and Y.Y. Zeevi, ―Localized Texture
REFERENCES
Processing in Vision: Analysis and Synthesis in the
[1] Y. Eldar, M. Lindenbaum, M. Porat and Y.Y. Zeevi,
Gaborian Space‖, IEEE Trans. on Biomedical
―The Farthest Point Strategy for Progressive Image
Engineering, vol. BME-36, No. 1, pp. 115-129, 1989.
Sampling‖, IEEE Trans. On Image Processing, Vol. 6,
[7] Gregg E. Trahey, Stephen W. Smith, and Olaf T. Von
No. 9, pp. 1305-1315, 1997.
Ramm, ―Speckle Pattern Correlation with Lateral
[2] P. He, K. Xue, P. Murka, ―3-D imaging of residual
Aperture Translation: Experimental Results and
limbs using ultrasound‖, Journal of Rehabilitation
Implications for Spatial Compounding‖, IEEE
Research and Development, Vol. 34 No. 3, pp. 269-278,
Transactions on Ultrasonics and Frequency Control,
July 1997.
Vol. 33 No.3, pp. 257-264, May 1986.

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Application of a Threshold Methods for

Compression of Vocal Signals
Mahjoubian MASOUD1, G.N. ROZORYNOV1, Fendri Mohamed AYMEN1
1
National Technical University of Ukraine "Kiev Polytechnic Institute",Kiev, Ukraine
[email protected]
Abstract – Types of thresholds used for compression of vocal signals are considered. It is shown that quality of
the restored speech depends straight on the choice of threshold characteristic. The mathematical description
of spectral composition of the signal subjected to threshold is given, its connection with the size of the
threshold is revealed and the nonlinear distortion coefficient is calculated. The graphs of revealed
dependencies on which it is possible to judge on type selection and threshold level are built.

Keywords – compression, threshold, spectral composition, vocal signal, nonlinear distortion coefficient.

I. INTRODUCTION f  x   1 x    x, (1)

The present work is closely connected to the real problem,
1, x  0,
where, 1 x   
arising up at the signal processing in the cellular telephone
 – unit function.
systems, because of the background noises in them. When a 0, x  0,

vocal signal is transferred from a cellular telephone to the The graph of FC at hard thresholding is shown on fig.
base station (or in other direction), it should be compressed 1,a.
in order for an operator could transfer as many signals as the
real carrying capacity of the channel can allow [1].
For trouble-free work of the compression circuit it is
necessary to provide high value of signal/noise relation on
its input. Therefore the removal of background noise is made
before the compression process. This can be done with an
ideal filter which passes only a vocal signal and removes
undesirable noises, for example, car noise or people talks. It
is obvious that practically this task is enough difficult that‘s
why the attempts to utilize different methods of signal
processing, the most successful of which are threshold [2, 3 -
7] are undertaken. Thus, however, there is no data about
threshold type influence and the level of threshold on a
qualitative descriptions of the restored signal.
The purpose of the present work is research of different
threshold methods of decreasing the level of background
noise while compression of vocal signals and choosing the
best one of them on quality of the restored signal criteria.
II. MAIN PART
Threshold methods of noise decrease are based on
diminishing of coefficients values of signal transformation
while its transfer from one representative domain to another
(time-frequency, time-space, and other). It is assumed that
the noise component is represented by small coefficients and b
the threshold method is used for reduction or complete
removal of small coefficients. Then the signal is exposed to Fig.1 Functional characteristics of thresholding: a - hard, b - soft
reverse transformation.
Soft and hard thresholds [2, 3 - 5] are most often used. As In the case of soft threshold use FC is represented:
it is assumed that the algorithm of processing should operate f  x   1 x     x   sign  x  , (2)
in a real-time mode, and the length of input signal can be
large so the input signal is divided into small segments and the graph of such FC is shown on fig. 1,b.
(shots). The algorithm of processing is used on each segment Analysis of the graphs presented on fig.1 shows that the
and the output result is represented as a composition of greatest influence on quality of speech transmission,
separate processed segments. Processing of separate segment especially with background noises, make initial areas of FC.
requires time that all in all leads to the delay of signal in Therefore we will try to modify these areas so that to
communication network. provide the least distortions of the restored signal. The
Let‘s designate the size of the threshold  . Then in case simplest decision for this task is realization of FC of
of hard threshold the functional characteristic (FC) of threshold types, shown on fig. 2.
thresholding will be described by the equation: We will name them FC of linear supersoft thresholding

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

(fig. 2,a) and FC of quadratic supersoft thresholding (fig.

2,b).
,(7)

, (8)

a
(9)
From these calculations it is evident that the signal suffers
most distortions at use of hard thresholding. In addition,
depending on the type of threshold the maximum value of
nonlinear distortion coefficient corresponds to different
values of sin . Only in case of soft and linear supersoft
thresholds these values coincide and equal 0,3.
III. CONCLUSION
1. It was shown that most influence on quality of
transmission of vocal signals, especially with background
noises, renders the type of initial area of functional
b characteristic of thresholding.
Fig.2 Functional characteristics of supersoft thresholding: a - linear, b - 2. 4 types of functional characteristics of thresholding that
quadratic have different initial areas were studied. The mathematical
description of spectral composition of sinusoidal signal
FC at linear and quadratic supersoft thresholding are
thresholding subjected was given, its connection with the
presented, accordingly:
size of threshold was shown and the nonlinear distortion
 x  sign  x 1    ,
 x  , (3) coefficient was calculated. The graphs of shown
f x  
  x, x  .
 dependencies which help to choose the type and the size of a
threshold were built.
 x, x  ,
 (4) REFERENCES
f  x    x2 [1] Шелухин О.И., Лукьянцев Н.Ф. Цифровая обработка
 sign  x  , x  .
 и передача речи / Под. ред. О.И. Шелухина. – М.:
Радио и связь, 2000. – 456 с.
In the formula (4),  is an angular coefficient, [2] Розоринов Г.Н., Колокольцев Ф.В. Компандирование
determining inclination of initial linear area of FC. речевых сигналов для цифровой передачи по
At the compression of vocal signal with losses, with полосноограниченным каналам // Вісник
growth of compression coefficient (size of threshold  ) Державного університету інформаційно-
signal distortions increase accordingly [2, 3]. It shows up комунікаційних технологій. – 2006. – Т.4, №2. – С.
when parasite harmonic components appear in the restored 73 – 79.
vocal signal. [3] Фѐдоров Е.Е. Модели и методы преобразования
The number of distortions of signal after thresholding can речевых сигналов. – Донецк: Норд-Пресс, 2006. –
be defined by the nonlinear distortion coefficient  as a 260 с.
[4] Reccione M.C. The enhanced variable rate coder: Toll
relation of operating value of output signal without its first
quality speech for CDMA // International Journal of
harmonic to the operating value of input signal (in case of
Speech Technology. – 1999. – № 2. – P. 305–315.
sinusoidal signal):
[5] Thiemann J. Acoustic Noise Suppression for Speech
1  2 Signals using Auditory Masking Effects. – Montreal:
 bn Pэф2  21 b12
2 n 2 McGill University. – 2001. – 83 p.
  . (5)
[6] Дьяконов В., Абраменкова И. MATLAB. Обработка
A/ 2 A/ 2
сигналов и изображений: Специальный справочник.
Using (5), will get the followings formulas for the – СПб.: Питер. – 2002. – 608 с.
calculation of vocal signals klirfactors: [7] Малла С. Вейвлеты в обработке сигналов: Пер. с
(6) англ. – М.: Мир, 2005. – 671 с.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

Computed Tomography Aspects of the

Endoscoic Sinus Surgery in Children
Mihail MANIUC, Polina ABABII
SMPhU „N.Testemitanu‖
Abstract - Computed tomography aspects of the endoscopic sinus surgery in children

a correct diagnosis, which in its turn results from diagnostic

I. INTRODUCTION
endoscopic examination and rhinosinusal computed
Performances of endoscopic method in exploring the nasal
tomography [4]. A computed topographic examination in
and sinus cavity reduce the need for radiological
coronary and axial sections allows studying the anatomical
examination in diagnosis of nasal obstruction. On the other
anomalies and variations of the lateral wall of nasal fossa
hand, imaging plays an important role in assessing the
and the objectification of the recurrent or chronic sinusitis.
etiology of sinusitis. If a tumor, a septal deviation, a cornet
In a study by scientist R. Lusk and others, 115 children with
hypertrophy or choanal atresia, i.e., surface examination, can
symptoms of chronic and recurrent sinusitis were examined
be detected by endoscopic investigation, expanding of the
by computed tomography [7, 10]. Therefore, bone
pathologic process can be appreciated only after performing
abnormalities were found in a large proportion of
imaging examination. Functional endoscopic surgical
investigated patients: concha bullosa - 10% infraorbital cells
techniques proposed by W. Messerklinger are based on a
- 10%, nasal septum deviation - 27.8%, paradoxical middle
correct diagnosis, which in its turn results from the
turbinate - 8.5%, uncinate process lateral deviation and
information of endoscopic diagnostics and sinus computed
hypoplasia of the maxillary sinus - 6.9%, enlarged nasal
tomography examination. With the development of
inferior turbinates - 6% [7, 10]. Preoperative CT provides a
endonasal surgery, visualization of the sinus cavities
real map of the paranasal sinuses, providing a good study of
becomes essential for performing intrasinusal surgery.
normal anatomy of the face air cavities, which allows a
Computed tomography examination is considered as the
precise description of dangerous relations, offering the
most informative imaging method for diagnosis of recurrent
possibility of a more beneficial, precise and limited
and chronic paranasal sinusitis. Under our supervision there
therapeutic procedure.
were 120 children with recurrent and chronic sinusitis who
The goal of the research was to evaluate the efficacy of
underwent endoscopic endonasal surgery. The mentioned
the modern investigation method such as computed
method of examination was used for the objectification of
tomography in assessing anatomical architectonics of the
postoperative results.
nose and paranasal sinuses for determining the tactics of
endoscopic surgical treatment in children with recurrent and
II. TOPICALITY chronic pathology of paranasal sinuses.
Recurrent and chronic paranasal sinusitis in children are
quite common pathologic entities in everyday practice.
III. MATERIALS AND METHODS
Paranasal sinus inflammatory diseases in general and
The study included 120 children with recurrent and
recurrent and chronic rhinosinusitis in children in particular
chronic sinusitis, aged 8-17 years, divided into three lots of
are a difficult issue and in childhood and are registered with
40 (X²=0, p>0.05). The overall average age of patients in the
a frequency of 18-30% to 38-42% [1, 2, 3].
study groups was 13.9 years. The gender distribution
The issue of pathogenesis, early diagnosis and endoscopic
analysis showed that 59 (49.2%) of patients were male, and
surgical treatment is being studied in many centers by
61 (50.8%) females. Thus, a statistically significant
rhinologists, but so far remain unclear aspects of it. There
difference given by the parameter X ² = 1.73, P> 0.05 was
are studies that reveal information about the importance of
not noted.
anatomic and physiological peculiarities of nasal cavities and
Depending on the surgical treatment all the patients
paranasal sinuses in the pathogenesis of rhinosinusal
included in the study were divided into three groups. Group I
disorders [1, 3, 4]. In modern literature the pathogenesis of
consisted of 40 patients (21 boys and 19 girls) with recurrent
chronic and recurrent sinusitis is referred to as ―cooperation‖
and chronic paranasal sinusitis, operated by the standard
between infection and predisposing factors. Diagnosis and
method of endoscopic surgery (Messerklinger-Stammberger
treatment of sinusitis in children has changed substantially
technique). Group II consisted of 40 patients (18 boys and
over the past 10 years due to the wide spread and
22 girls), also with recurrent and chronic inflammatory
implementation of functional diagnostic methods (acoustic
disease of the paranasal sinuses treated by the method of
rhinometry, rhinomanometry), diagnostic imaging by
minimally invasive endoscopic sinus surgery. Group III
computed tomography and rhinosinusal endoscopy [4, 5, 6, 7
consisted of 40 patients (20 boys and 20 girls), homogeneous
]. One of the major symptoms presented by patients with
by nosologic structure, patients were operated on by
recurrent and chronic sinus pathology is nasal obstruction
minimally invasive technique completed with surgery on
which is a subjective parameter. The etiology and treatment
endonasal structures.
of obstruction often relies on clinical and rhinoscopy data
CT examination is essential in identifying sinus disorder
and rarely - on objective methods. Functional endoscopic
difficult to diagnose in rhinoscopic, endoscopic or classic
surgery techniques proposed by Messerklinger are based on
radiological examination. Computed tomography is of

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

particular value in diagnosing disorders of ostiomeatal

complex and ethmoid, sphenoid sinus, impossible to
determine using a traditional X-ray examination. Imaging
study was performed in two planes - axial and coronal -
using a Siemens Somatom Emotion Duo CT. The fineness of
bone structures of the nose and paranasal sinuses skeleton
requires fine cups and high resolution. Millimeter thick
images obtained allow the study of teeth that are close to the
alveolar recess of maxillary sinus which is very important in
children in the period of growth. Tomodensiometric
examination is essential for precise analysis of sinus
opacification and integrity of the sinus walls (normal, thin,
densified). CT image is required for viewing the anatomical
elements, which serve landmarks in endoscopic examination Fig.1 Bilateral concha bullosa
and analysis of surgical areas with a high risk of
complications (lamina papyracea of the ethmoid bone, Studying and analysing the CT image we paid particular
lamina cribrosa, persistence of Haller and Onoda cells, attention to middle turbinates variations of presentation
report between the side wall with the internal carotid artery (concha bullosa, paradoxical turbinate), of the processus
and optic nerve, etc.). uncinatus, size of ethmoid bulla and Agger nasi cells,
In the case of recurrent and chronic sinusitis in children, presence of Haller infraorbital cells. In our study the most
the computed topographic examination can detect common anatomic variant was concha bullosa detected in 65
predisposing or maintening factors of inflammatory process patients (54.1%), prevailing in group III - 28 patients (70%)
of sinus mucosa such as different endonasal anatomical (Fig. 1).
abnormalities and variations: septum deviation in different
segments, concha bullosa, paradoxical turbinate,
hypergenesis of uncinate apophysis and various forms of
deviations, excessive pneumatization of ethmoid bulla, etc.
[10]. Results and discussion
The study and analysis of CT images was crucial for
detection and characterization of septal deviation in children
in the study groups, as nasal septum deviation can block the
ostiomeatal complex structures thus favoring the occurrence
of inflammation. Computed tomography can determine the
precise location and nature of the deviation (deformation,
thickening or pneumatization of nasal septum). CT
examination results showed a frequent finding of nasal
septum deviation in patients of the study groups, with a
caseload of 78 (65%) deviations. The deviations had a wide
range of localizations: anterior segment - 37 (30.9%), Fig.2 Paradoxically curved middle turbinate
posterior segment - 15 (12.5%) and septal deviation in the
anteroposterior segment - 26 (21.7%). Diverse anatomical variants of uncinate process were
In accordance with the studies on nose and paranasal detected at CT examination in patients in the study groups:
sinuses physiology and pathophysiology, in emergence and curvature of uncinate process - 21 (17.5%) and excessive
further development of chronic inflammatory process of the pneunmatization of uncinate process - 69 (57.5%) (Table 1).
paranasal sinuses a special place has the anatomical factor, Finally, we can conclude that the frequency of detection of
particularly abnormalities and anatomical variants in the area anomalies and anatomical variations of the nasal passages is
of ostiomeatal complex high in patients with recurrent and chronic inflammatory
Paradoxically curved middle turbinate was determined in process of the paranasal sinuses.
24% cases, which corresponds to literature data showing a
frequency of 5-37% (Fig. 2).
The results of our study have showed a frequency of 23 CONCLUSION
(19.1%) cases of Haller cells, being an anatomical factor CT examination shows an accurate evaluation of
(when they reach to 3 – 6 mm) in the development of ostiomeatal complex structure, which is responsible for the
ethmoidal sinusitis due to narrowing of infundibular space. persistence of recurrent and chronic sinus process, and is
Hiperpneumatization of Agger nasi cells have a major important in performing endoscopic surgery.
clinical importance, compressing the frontal recess and
predisposing to frontal sinus inflammatory process. In our REFERENCES
study it was detected in 17 (15.5%) cases. The CT [1] Bhattacharyya N, Kun Hee Lee. Chronic Recurrent
examination performed on patients in our study determined Rhinosinusitis: Disease Severity and Clinical
pneumatization of ethmoid bulla in 94 cases (78.3%), a Characterization. Laryngoscope, 2005, 115: p.306–310.
figure bigger than in the literature (17-65%) due to bilateral [2] Chao T.K. Uncommon anatomic variations in patients
location of the anomaly. with chronic paranasal sinusitis. Otolaryngology–Head
and Neck Surgery, 2006, 38: p.221-225.

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 International Conference on Nanotechnologies and Biomedical Engineering, Chişinău, Republic of Moldova, 7-8th of July, 2011

[3] Polavaram R, Devaiah A. Anatomic variants and pearls– [7] chronic sinusitis. Radiologic anatomy, 2002, 24: p. 400–
functional endoscopic sinus surgery. Otolaryngologic 405.
Clinics of North America, 2004, 37: p. 221-242. [8] Dinis P.B., Haider H, Gomes A. Rhinomanometry, sinus
[4] Bidilean N. Concordanţe morfo-clinice, radiologice şi CT-scan and allergy testing in the diagnostic assessment
endoscopice în afecţiunile inflamatorii rinosinuzale. of chronic nasal obstruction. Rhinology, 1997, 35: p.
Oto-Rino-Laringo., 1997,Vol. 18,no 3 – 4: p.37-45. 158–160.
[5] Liukkonen K, Virkkula P, Pitkäranta A. Acoustic [9] Numminen J, Ahtinen M, Huhtala H, Rautiainen M.
rhinometry in small children. Rhinology, 2006, Mars, Comparison of rhinometric measurements methods in
44: p.160-163. intranasal pathology. Rhinology, 2003, 41: p. 65-68.
[6] Clemens P.A. Committee report on standartization of Badia L, Lund V, Wei W. Ethnic variation in sinonasal
rhinomanometry. Rhinology, 1986, 22: p. 151- 155. anatomy on CT-scanning. Rhinology, 2005, December 43, p.
210-214

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 International Conference on Nanotechnologies and Biomedical Engineering , Chişinău, Republic of Moldova, 7-8 th of July , 2011

The Interconnection of Polarization Singular

Structure and Mueller-matrix Images of
Biological Tissues in the Tasks of Cancer
Changes Diagnostics
Alexander DUBOLAZOV, Artem KARACHEVTSEV, Vladimir USHENKO, Vadim ISTRATIY
Chernivtsi National University
[email protected]
Abstract – The paper deals with investigating the processes of laser radiation transformation by biological
crystal networks using the singular optics techniques. The obtained results showed a distinct correlation
between the points of "characteristic" values of coordinate distributions of Mueller matrix (M ik = 0,  1 )
elements and polarization singularities (L- and C-points) in laser images of biological crystal networks with
the following possibility of Mueller-matrix selection of polarization singularity. It has been proposed the
technique of Mueller-matrix singular diagnostics of pathological changes in woman reproductive sphere
tissue (myometrium).

Index Terms – Mueller matrix, singularity, polarization, birefringence, biological tissue, statistics.

optical anisotropy inherent to protein crystals. On this basis,

the criteria for early diagnostics of muscle dystrophy, pre-
I. INTRODUCTION
cancer states of connective tissue, collagenoses etc. were
Laser polarimetry (polarization sensitive optical
determined.
coherence tomography, Mueller matrix decomposition
In parallel with traditional statistical investigations,
formalism, coherency matrix analysis, etc.) [1-29] is able to
formed in recent 10 to 15 years is the new optical approach
obtain information about optical anisotropy (linear
to describe a structure of polarization inhomogeneous fields
retardance, optical activity, dichroism, etc.) of biological
in the case of scattered coherent radiation. The main feature
tissues (BT). It has the potential to be an important
of this approach is the analysis of definite (in contrast to
technology for non-invasive diagnostics of organic phase-
continuous 2D distributions) polarization states to determine
inhomogeneous layers. One model approach underlies these
the whole structure of coordinate distributions for azimuths
researches, which generalizes the optical properties of BT [5,
and ellipticities of polarization. The so-called polarization
6, 14, 21, 30]:
singularities are common used as these states [31-37]:
1. all the variety of human BT can be represented by four
- states with linear polarization, when the direction of
main types – connective, muscular, epithelial, and
rotation for the electric field vector is indefinite, the so-
neural tissues;
called L-points;
2. morphological structure of any BT type is regarded as a
- circularly polarized states, when the azimuth of
two-component amorphous-crystalline structure (optical
polarization for the electric field vector is indefinite, the
isotropic and optical anisotropic);
so-called C-points.
3. the crystalline component is characterized by Mueller
matrix M  operators of an optical anisotropy
Investigations of polarization inhomogeneous object fields
for BT with different morphology allowed ascertaining that
1 0 0 0 they possess a developed network of L- and C-points [36].
For example in [37], the authors found interrelations
0 M 22 M 23 M 24
M   (1) between conditions providing formation of polarization
singular points and particularity of the orientation-phase
0 M 32 M 33 M 34
structure of biological crystals present in territorial matrix of
0 M 42 M 43 M 44 human tissue architectonic network. These interrelations
Specifically, the above mentioned model was used for served as a base to make statistical and fractal analyses of
finding and substantiating the interrelations between the distribution densities for the number of singular points in BT
ensemble of statistic moments of the 1st to 4th orders that images. As a result, the authors confirmed the efficiency of
characterize the orientation-phase structure (distribution of this method for investigation of object fields to differentiate
optical axes and phase shifts for directions of protein fibril optical properties of BT with a different morphological
networks) of birefringent BT architectonics and of 2D structure and physiological state.
distributions for azimuths and ellipticities in their laser It is worth to note that the singular approach is mainly
images [5]. It was determined [6, 7, 14, 15, 20, 23, 27, 28] used out of the analysis of the mechanisms providing
that the 3rd and 4th statistic moments for coordinate formation of polarization inhomogeneous laser images of BT
distributions of ellipticities are the most sensitive to the by an extracellular matrix. Thus, development of laser-
change (caused by dystrophic and oncological processes) of polarimetric techniques based on determination of singular

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interrelations "object - field" in order to find new methods of BIOLOGICAL TISSUES AND POLARIZATION SINGULARITIES
DESCRIBED BY THE FOURTH PARAMETER OF THE STOKES
diagnostics of transformation of the BT extracellular matrix
orientation-phase structure related with pre-cancer changes VECTOR V4
in their physiological state is very important.
To solve this problem, we should revert to the analysis of M ik V4 Polarization state
optical properties of biological crystal networks as these
properties are comprehensively described by the Mueller
matrix within the framework of the singular approach.
0 1 C
M 22;33; 44 1 0 +L
-1 0 -L
II. BRIEF THEORY OF THE SINGULAR APPROACH IN
THE ANALYSIS OF BIOLOGICAL TISSUE
0 0 L
BIREFRINGENT NETWORKS M 24; 42;34;43; 23;32 1 1 C
To analytically describe the L- and C-states of -1 1 C
polarization, the most suitable is to use the extreme values of
the fourth Stokes vector parameter. It is a widely applied
mean and appears to be reasonable to represent these
singularities as follows: III. SCHEME AND METHODS OF EXPERIMENTAL
INVESTIGATIONS
 Fig. 1 shows the traditional optical scheme of
V4  sin 2 ; polarimeter for measuring the elements of Mueller matrix of

V4  0  L(   0); (2) the BT histological sections [5, 20].
 
V4  1  C (    ).
 4
Here,  is the value of polarization ellipticity; the  C Fig. 1. Optical scheme of the polarimeter. 1 – He-Ne laser; 2 – collimator; 3
point is assumed to designate a right-circulated polarization – stationary quarter-wave plates; 5, 8 – mechanically movable quarter-wave
plates; 4, 9 – polarizer and analyzer, correspondingly; 6 – object of

state, which can be characterized by the phase shift  investigation; 7 – micro-objective; 10 – CCD camera; 11 – personal
computer.
2
between the orthogonal components of laser beam
amplitude; the  C point is assumed to designate a left- The parallel ( = 104 μm) beam of He-Ne laser ( =
 0.6328 μm, W = 5.0 μW) was used as an illuminator.
circular polarization state (   ). Thus,  C points Polarization illuminator consists of the quarter-wave plates
2 3, 5 and polarizer 4, and it sequentially forms a series of
are the orthogonal states of circularly polarized wave. For
linearly polarized ( I 0 , I 45 , I 90 , I 135 ) with azimuths 0  ,
the L points, the phase shift reaches   0;  .
Using the relations (1) and (2), it is possible to determine 90  , 45  , 135  , and right-hand ( I  ) and left-hand ( I  )
the interrelations between the characteristic values M ik of circularly polarized probing BT laser beams. The BT images
Mueller matrix elements, which correspond to the ―extreme‖ made by the micro-objective 7 ( 4  ) were projected into the
values of BT optical anisotropy, and to the extreme values of plane of a light-sensitive area ( 800 600 pixels) of the
CCD-camera 10.
V4 . Thus, in order to characterize the BT structure we
Polarization images of BT were projected by means of the
obtain the coordinate network generated by a finite number micro-objective 7 (focal distance - 1.5 cm , aperture - 0.2,
of characteristic values of Mueller matrix elements (1) (see magnification – 4x) into the plane of light-sensitive area of
Table 1). the CCD camera (overall amount of pixels – 800x600, light
Thus, measuring the coordinate distributions of the sensitive area size - 4000x3000 m , deviation of

characteristic values ( M ik  0 ,  1 ) of the BT Mueller photosensitive characteristics from the linear one was no
matrix elements enables not only to foresee the scenario more than 15%), which provided the range of measuring the

( M ik  V4 ) of forming the ensemble of polarization structural elements of BT with the resolution
2  2000m . Maximal resolution verification (2 m )
singularities ( V4  0 ,  1 ) of its image, but also to
were performed using the stage micrometer (linear scale),
additionally realize their differentiation, conditioned by the which image was projected into the light sensitive area of
specificity of orientation structure of biological crystals. CCD camera using the micro-objective 7. Minimal
Here,  L point corresponds to a linear polarization resolution ( 2000m ) corresponds to the situation when the
state with   0 ;  L point corresponds to a linear light sensitive area of CCD camera is entirely filled by two
polarization state with    . In this case, as for  C equal sized structural elements (light and dark) of stage
points, we will identify  L points as orthogonal. micrometer. The experimental conditions were chosen in
such a way that it enabled to reduce the space-angular
TABLE I. INTERRELATION BETWEEN THE CHARACTERISTIC aperture filtering when forming the BT images. It was
VALUES OF MUELLER MATRIX M ik ELEMENTS OF ensured by conformance of angular characteristics of the

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indicatrix of light scattering by the BT samples (   16 )

0 – ―-С‖- points ( ) ( M 24, 34 = 0, V4 = 0).
( M 24, 34 = –1, V4 = –1);
and the angular aperture of micro-objective (   20 ).
0

Here,  is the solid angle within which 98% of all the

energy of light-scattered radiation is concentrated.
Polarization analysis of the BT images was performed
using the polarizer 9 and quarter-wave plate 8 according to
the following technique:
 within the section of illuminating laser beam, the
array ( m  n  800 600 ) of values for the Stokes
vector V j 1, 2,3, 4 parameters and elements of Mueller
matrix M ik m  n were determined in accord with
the following algorithms
 V1  I 0  I 90 , V2  I 0  I 90 , V3  I 45  I135, V4  I   I  ,

 (1)

( 2)
 (1)

M i1  0.5 Vi  Vi , M i 2  0.5 Vi  Vi , M i 3  Vi  M i1 , M i 3  Vi  M i1 , i  1,2,3,4.
( 2) ( 3) ( 4)

(3)
 in each array M ik m  n and V4 m  n ,
, 24, 34 m  n 

coordinate distributions of characteristic (singular) Fig.2. Networks of characteristic values M 44
values 0 ,  1 were determined.

At the first stage, the interrelations ( M ik  V4 ) of
IV. MUELLER-MATRIX SINGULAR DIAGNOSTICS
matrix and polarization singularities were investigated on the
AND DIFFERENTIATION OF PATHOLOGICAL
sample of a histological section prepared from healthy skin
CHANGES IN THE TISSUES OF WOMAN
derma.
REPRODUCTIVE SPHERE
Fig. 2 represents coordinate distributions of matrix
elements M 44, 24,34 m  n  corresponding to the skin
Three groups of histological sections of the main tissue of
woman reproductive sphere – myometrium – were used as
derma histological section and the fourth Stokes vector the objects of investigation:
parameter V4 m  n  of its image with the characteristic  biopsy of the healthy tissue of woman
reproductive sphere (type ―A‖ – Fig. 3а);
values ( 0 ,  1 ) plotted on them (within the marked  biopsy of the inflamed tissue (ectonia) (type ―B‖ –
100 pix  100 pix sampling plot). Fig. 3b);
It can be seen from the data obtained that there is direct  biopsy of the tissue in the state of dysplasia (pre-
correlation between the coordinate cancer state) (type ―C‖ – Fig. 3c).
( k , g 1  k  m,1  g  n ) positions of characteristic

values of the matrix element M 44 for skin derma and the
network of L and C points in its laser image
  0   1   C 
M 44 k , g      V4 k , g   

 Fig. 3. Polarization images of woman reproductive sphere tissue –
  1  0  L  myometrium ―А‖ (a), ―B‖ (b) and ―C‖ (c) types in the scheme of coaxial
(Fig. 2a, d). polarizer and analyzer.
Coordinate distributions of characteristic values of matrix
elements M 24, 42 m, n  ,, 43 m, n  and corresponding
  To determine the criteria of Mueller-matrix singular
M 34 diagnostics of myometrium oncological state and
networks of orthogonal  L and  C points (Table 1) differentiate its severity degree, the following technique was
possess the individual structure (Fig. 2b, c). used:
Analytically substantiated and experimentally proven  coordinate networks of characteristic values for

, 24, 34 (m  n)  0 ,  1 were scanned
interrelations between the matrix and polarization matrix elements M 44
singularities were used as the basis for Mueller-matrix
singular diagnostics of oncological changes in the tissues of in the direction x  1, ..., m with the step x  1
woman reproductive sphere. pixel;
of matrix elements M 44, 24,34 (a, b, c) and singularities of  within the obtained sampling
polarization image inherent to the skin derma layer 1 pix  n pix 
k 1, 2, ..., m 
for coordinate distribution of the
histological section V4 (―d‖):
element
M 44 (m  n) , the total amount ( N k  ) of
– ―±С‖-points ( ) ( M 44 – ―+L‖- points (Δ) ( M 44
= 0); = +1); characteristic points ( 0 ,  1 ) that set the complete
– ―+С‖-points ( ) – ―-L‖- points (  ) ( M 44 ensemble of singular points was calculated, and the
( M 24, 34 = +1, V4 = +1); = –1);
– ―±L‖- points (◊)

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
dependences N x  ( N
(1)
, N ( 2) , ..., N ( m) ) were matrix singular diagnostics not only for oncological changes
of myometrium tissue but also for differentiating their
determined; severity degree.
 distributions of the number of singular  L and
 C -points were determined using the following REFERENCES
expressions [1] J.F. de Boer and T.E. Milner, ―Review of polarization
 N x   N C M 34, 43  1  N L M 24, 42  0,
 
 sensitive optical coherence tomography and Stokes
  
 N x   N L M 34, 43  0  N C M 24, 42  1. (4)
vector determination‖, J. Biomed. Opt. 7, 359-371,
 2002.
 statistical moments of the 1st to 4th orders for the [2] J.F. de Boer , T.E. Milner, and J.S.Nelson, Trends in

obtained distributions of N x amount of singularities were
Optics and Photonics (TOPS): Advances in Optical
Imaging and Photon Migration, OSA, Washington,
calculated according to the algorithms 1998.
1 m n [3] M. J. Everett, K. Shoenenberger, B. W. Colston and L.
Z1   N x  ,
m  n i 1 B. Da Silva, ―Birefringence characterization of
biological tissue by use of optical coherence
1 m n
Z2   N x 2 , tomography‖, Opt. Lett. 23, 228-230, 1998.
m  n i 1 [4] Sh. Jiao, W. Yu, G. Stoica, Lihong V. Wang, ―Optical-
1 1 m n fiber based Mueller optical coherence tomography‖,
Z3  3  N x 3 , Opt. Lett. 28, 1206-1208, 2003.
Z 2 m  n i 1
[5] Alexander G. Ushenko and Vasilii P. Pishak, ―Laser
1 1 m n
Z4  4  N x 4 . Polarimetry of Biological Tissue: Principles and
Z 2 m  n i 1 Applications‖, in Handbook of Coherent-Domain
(5)
It follows from the data obtained that: Optical Methods: Biomedical Diagnostics,
Environmental and Material Science, vol. I, Valery V.
 efficiency of laser polarimetry for diagnostics and
Tuchin, Ed. Boston: Kluwer Academic Publishers, pp.
differentiation of early oncological changes of
93-138 (2004).
myometrium tissue is insufficient – the difference
[6] O. V. Angelsky, A. G. Ushenko, Yu. A. Ushenko, V. P.
between the values of statistical moments
Z 1, 2,3, 4 M m  n
of samples ―А‖, ―B‖
44,34, 24
Pishak, ―Statistical and Fractal Structure of Biological
Tissue Mueller Matrix Images‖, in Optical Correlation
and ―C‖ - types is insignificant and does not exceed Techniques and Applications, Oleg V. Angelsky, Ed.
20% - 45%; Washington: Society of Photo-Optical Instrumentation
 technique of polarization-correlation mapping is Engineers, pp. 213-266 (2007).
efficient for differentiation of optical properties of [7] O.V. Angelsky, A.G. Ushenko, Yu.A. Ushenko, V.P.
healthy and oncological changed myometrium tissue Pishak, and A.P. Peresunko, ―Statistical, Correlation,
and Topological Approaches in Diagnostics of the
Z Z
– the skewness ( 3 ) and the kurtosis ( 4 ) of Structure and Physiological State of Birefringent
distribution of the number of singular points of ―А‖- Biological Tissues‖, in Handbook of Photonics for
and ―В‖-types of laser images differ by 1.53 and 2.15 Biomedical Science, Valery V. Tuchin, Ed. USA: CRC
times; Press, pp. 21-67 (2010).
 technique of Mueller-matrix singular diagnostics is [8] Alexander G. Ushenko, ―Polarization structure of laser
efficient for differentiation of optical properties of all scattering fields,‖ Opt. Eng. 34, 1088-1093, 1995.
types of samples – statistical moments of the 3rd and [9] A.G. Ushenko, ―Laser diagnostics of biofractals,‖

4th orders of distributions

N x 
for the samples
Quantum Electronics 29(12), 1078–1084, 1999.
[10] O.V. Angel'skii, A.G. Ushenko, A.D. Arkhelyuk, S.B.
―А‖, ―B‖ and ―C‖ – types differ by 1.7 and 2.5 times, Ermolenko, D.N. Burkovets, ―Structure of matrices for
respectively. the transformation of laser radiation by biofractals,‖
 for distributions
N  x  
of myometrium tissue of
Quantum Electronics 29(12), 1074-1077, 1999.
[11] O.V. Angel'skii, A.G. Ushenko A.D. Arheluk, S.B.
―А‖ and ―B‖ types, the maximal difference (from 2.2 Ermolenko, D. N. Burkovets, ―Scattering of laser
to 4.1 times) is observed between all the statistical radiation by multifractal biological structures,‖ Optics
Z j 1, 2,3, 4 and Spectroscopy 88(3), 444-448, 2000.
moments.
[12] A.G. Ushenko, ―Polarization structure of biospeckles
and the depolarization of laser radiation,‖ Optics and
V. CONCLUSION Spectroscopy 89(4), 597-601, 2000.
It has been ascertained correlation between coordinate [13] A.G. Ushenko, ―Stokes-correlometry of biotissues,‖
locations of characteristic points for 2D elements of the Laser Physics 10(5), 1286-1292, 2000.
Mueller matrix corresponding to an optically thin layer of [14] A.G. Ushenko, ―The vector structure of laser biospeckle
biological tissue and the network of L and C points in its fields and polarization diagnostics of collagen skin
laser image. Shown is the potentiality of Mueller-matrix structures,‖ Laser Physics 10(5), 1143-1149, 2000.
sampling for polarization singularities formed by biological [15] A.G. Ushenko, ―Laser polarimetry of polarization-phase
crystals. It has been demonstrated the efficiency of Mueller- statistical moments of the object field of optically

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anisotropic scattering layers,‖ Optics and Spectroscopy A.G. Ushenko, I. Z.Misevich, V. Istratiy, I. Bachyns‘ka,
91(2), 313-316, 2001. A. P. Peresunko, Omar Kamal Numan, and T. G.
[16] A.G. Ushenko, ―Polarization contrast enhancement of Moiysuk, ―Evolution of statistic moments of 2D-
images of biological tissues under the conditions of distributions of biological liquid crystal net Mueller
multiple scattering,‖ Optics and Spectroscopy 91(6), matrix elements in the process of their birefringent
937-940, 2001. structure changes,‖ Advances in Optical Technologies
[17] A.G. Ushenko, ―Laser probing of biological tissues and 2010, 423145, 2010.
the polarization selection of their images,‖ Optics and [27] Yu.O. Ushenko, I.Z. Misevich, A.P. Angelsky, V.T.
Spectroscopy 91(6), 932-936, 2001. Bachinsky, O.Yu. Telen‘ga, O.I. Olar, ―Polarization-
[18] A.G. Ushenko, ―Correlation processing and wavelet singular structure in laser images of phase-
analysis of polarization images of biological tissues,‖ inhomogeneous layers to diagnose and classify their
Optics and Spectroscopy 91(5), 773-778, 2002. optical properties,‖ Semicond. Physics, Quantum
[19] A.G. Ushenko, ―Polarization correlometry of angular Electronics&Optoelectronics 13(3), 248-258, 2010.
structure in the microrelief pattern or rough surfaces,‖ [28] V.T. Bachinsky, Yu.O. Ushenko, Yu.Ya. Tomka, O.V.
Optics and spectroscopy 92(2), 227-229, 2002. Dubolazov, V.O. Balanets'ka, A.V. Karachevtsev,
[20] O.V. Angelsky, A.G. Ushenko, Ye.G. Ushenko, ―2-D ―Wavelet analysis for polarization maps of networks
Stokes polarimetry of biospeckle tissues images in pre- formed by liquid biological crystals in blood plasma:
clinic diagnostics of their pre-cancer states,‖ Journal of statistical and fractal approaches,‖ Semicond. Physics,
Holography and Speckle 2(1), 26-33, 2005. Quantum Electronics&Optoelectronics 13(3), 189-201,
[21] Oleg V. Angelsky, Alexander G. Ushenko, and 2010.
Yevheniya G. Ushenko, ―Complex degree of mutual [29] S.C. Cowin, ―How is a tissue built?‖, J. Biomed. Eng.
polarization of biological tissue coherent images for the 122, 553-568, 2000.
diagnostics of their physiological state,‖ J. Biomed. Opt. [30] J.F. Nye, Natural focusing and the fine structure of
10(6), 060502, 2005. light, Institute of Physics Publishing, Bristol, 1999.
[22] O.V. Angelsky, A. G. Ushenko, and Ye. G. Ushenko, [31] J.F. Nye, ―Polarization effects in the diffraction of
―Investigation of the correlation structure of biological electromagnetic waves: the role of disclinations‖, Proc.
tissue polarization images during the diagnostics of their R. Soc. A 387, 105, 1983.
oncological changes,‖ Phys. Med. Biol. 50(20), 4811- [32] M.V. Berry and M.R. Dennis, ―Polarization singularities
4822, 2005. in isotropic random vector waves‖, Proc. R. Soc. A 457,
[23] Alexander Ushenko, Sergej Yermolenko, Alexander 141, 2001.
Prydij, Stepan Guminetsky, Ion Gruia, Ovidiu Toma, [33] J.F. Nye, ―Lines of circular polarization in
Konstantin Vladychenko, ―Statistical and fractal electromagnetic wave fields‖, Proc.R.Soc. A 389, 279-
approaches in laser polarimetry diagnostics of the 290, 1983.
cancer prostate tissues,‖ Proc. SPIE 7008, 70082C, [34] Freund, ―Coherency matrix description of optical
2008. polarization singularities‖, J.Opt.A.: Pure and Appl.
[24] A.G. Ushenko, A.I. Fediv, Yu.F. Marchuk, ―Correlation Opt. 6, S229-S234, 2004.
and fractal structure of Jones matrices of human bile [35] O. V. Dubolazov, A. G. Ushenko, V. T. Bachynsky, A.
secret,‖ Proc. SPIE 7368, 73681Q, 2009. P. Peresunko, and O. Ya. Vanchulyak, ―On the
[25] Oleg V. Angelsky, Alexander G. Ushenko, Yevheniya Feasibilities of Using the Wavelet Analysis of Mueller
G. Ushenko, Yuriy Y. Tomka, ―Polarization Matrix Images of Biological Crystals,‖ Advances in
singularities of biological tissues images,‖ J. Biomed. Optical Technologies 2010, 162832, 2010.
Opt. 11(5), 054030, 2006. [36] A.G. Ushenko, A.I. Fediv, Yu.F. Marchuk, ―Singular
[26] S.B. Yermolenko, A.G. Ushenko, P. Ivashko, structure of polarization images of bile secret in
―Spectropolarimetry of cancer change of biotissues,‖ diagnostics of human physiological state,‖ Proc. SPIE
Proc. SPIE 7388, 73881D, 2009. 7368, 73681S, 2009.

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Bioengineering the Mind: from Artificial

Intelligence towards Artificial Consciousness
Radu NEGOESCU
National Institute of Public Health, Bucharest, Romania, [email protected]
Abstract – Whilst the artificial intelligence seems recently to approach its human-close specimen, artificial
consciousness as targeted by bioengineering and information science&technology advances still has some way
to go before becoming an experimental terrain for a bunch of sciences that deals with the problem of
conscience, including philosophy and theology. Depending on our capacity to inseminate a machine
transposition of natural ethics at the same time with increasing machine autonomy, a well guided artificial
consciousness holds the promise to offer a representation of what natural consciousness could be in absence of
distorting influences exerted by biologic (genetic) inheritance on human being as it presents nowadays.

Index Terms – consciousness, conscience, machine consciousness, information technology, cardiovascular

bioengineering.

After M. Draganescu [2] consciousness stands for a type

I. ARTIFICIAL INTELLIGENCE
of integrative information (structural-phenomenological and
Defined by John McCarthy in 1956 as the science and
social) capable of understanding and knowing, knowing that
engineering of making intelligent machines, hopefully in the
knows, and endowed with: feeling of to be, will, intuition
human intelligence sense, the artificial intelligence (AI)
and creative power. Notice that in the philosophical thinking
certainly evolved over the past half century, even if we never
of M. Draganescu structural information is related to (non-
got the humanlike assistants that many thought we would
living) nature and its sciences, while phenomenological
have by now. It offers a valuable technological support in
information is related to the living matter studied by life
critical domains, e.g. computer-diagnosing patients over the
sciences. Integration of structural and phenomenological
internet, but even the most helpful AI system in function
takes place into the real human being as such; dissection by
today must be programmed explicitly to carry out its one
theoretical reasons may enlighten various balances between
specific task. What people wanted and needed was a general-
parts otherwise intimately merged when analysis progresses
purpose intelligence that can be set loose on any problem,
from the molecular and cellular level to organs, systems,
i.e. one that can adapt to a new environment without having
mind and soul.
to be retrained constantly: ―one that can tease the single
Consciousness is naturally human; its versions
significant morsel out of a gluttonous banquet of information
―contaminated‖ by technology or those purely technological
the way we humans have evolved to do over millions of
are referred to by artificial ones.
years‖ [1].
Coming back to terms, in Romanian conscious
Recently yet Hewlett Packard introduced a new class of
(‗constient‘) is also (English-like) pointing to someone who
electronic device overriding the separation between memory
can rationally place his/her Ego vis-à-vis of the world and
and processing, the memristor, into a ―brain-inspired‖
him/herself; the term ―rational‖ sends to the manner in
microprocessor featuring the form factor of a brain, the low
which that positioning is done by a majority of other
power requirements, and the instantaneous internal
individuals. Besides, the Romanian ‗constient‘ refers to
communications - that could be trained and coaxed to behave
someone endowed with a certain level of conscience: "I am
like a brain. Run on this ―brain on a chip‖, the MoNETA
‗constient‘ (aware) of my duties‖, where the attitude versus
(Modular Neural Exploring Traveling Agent) software
duties is already related to moral principles, to an axiology.
written at Boston University's will perceive its surroundings,
Conscience is yet more than what is involved by ―I am
decide which information is useful, integrate that
aware of‖ (that expresses a potential), namely a non-hesitant
information into the emerging structure of its reality, and in
(proved) availability to actualize this potential with the
some applications formulate plans that will ensure its
current behavior. At a higher individual level, conscience
survival - the same drives that motivate humans and entitle
involves looking into the meaning of existence, for him and
the machine as a specimen of true (or real) artificial
for others who do not possess necessary capabilities, by a
intelligence [1].
philosophical and/or religious demarche.
However exercising conscience is mainly done in the
II. CONSCIOUSNESS AND CONSCIENCE social environment. M. Draganescu‘s [2,3] social-human
English uses the term consciousness (or self-awareness) to civilization of the future would be by far towering biological
designate a neural-behavioral state featuring capabilities needs of an aggregate of human individuals whose
of reflection and reaction found as adequate by the rest of the interaction would filter (somehow in the sense of coherent
world, while being vigil. summation in physics) luminous parts present in all of them
French appears to make no much lexical distinction as pieces of truth that are detected, sifted and put together
between consciousness and conscience that are commonly through the collective, social exercise of spirituality. Or, to
referred to by ‗conscience‘ and lets to the context making the cut it short, by the collective conscience.
difference. However, ‗faits de conscience‘ and In this vein, laws of Moses giving early expression to
―connaissance‘ refer unambiguously to consciousness or to a collective conscience codify social behavior of people; social
part of it. sins acting against the group are mainly incriminated, rather

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than individual sins acting against him/her self. While the today could not guarantee the progress of mankind towards a
latter are health-redoubtable (we know how from medicine Conscience Society penetrated by the moral principle of
of lifestyle) ending sometimes in serious somatic illnesses, spiritualized humanism that would dominate all social
the former increase or exacerbate psycho-social stress networks. In his key lecture at the INGIMED II Conference
responsible for more subtle forms of disease or death (e.g. in 2001, M. Draganescu argued why he is skeptical on
sudden cardiac death in apparently healthy people). building a Society of Conscience without participation of
The individual endowed with (sufficient) conscience is artificial consciousness (AC).
unselfish, generous; generosity is seen as the essentials of *
Christianity (as an example of spirituality) gathered in one Summarizing, in terms of cerebral activity, consciousness
single word. At the other end, a social value as bright as stands for neural machinery, mental, reason. Moral principle,
freedom, when practiced at low levels of conscience (or for the vast majority of individuals, is involved by
without conscience of kind) converts to selfishness, greed spirituality, so it is transcendent. Finally, conscience is both
and open contempt vis-à-vis of fellow man. Social behavior material, as tributary to neural machinery, and spiritual, that
of many Romanians since 1989, overtaken at low levels of is transcendent. For some good reason it is said about a man
conscience, if any, by freedom achieved through sacrifice of of conscience that ―he puts his soul into".
others (Revolution heroes), may convincingly illustrate what As M. Draganescu [2] remarks, man of today might not
means non-conscience. be able to create a social-human civilization as his genetic
* apparatus dominates the epigenetic cultural acquisitions.
From these preliminaries, the relationship between Then a solution could be an artificially assisted
consciousness and conscience could schematize as: consciousness by implantation of neurocybernetic
consciousness + moral principle = conscience. ―consciousness prostheses" that by means of significant
Moral principle comes for a vast majority of humans from mental enhancement would offer a better chance to moral
spirituality. rectitude in the average individual; we‘ve just seen that his
"Everyone, writes Mihai Draganescu [3], has an consciousness is largely missing nowadays the influence of
empirical understanding of conscience and realizes that it spirituality.
stands for the highest level of his/her being. He/she then
feels spirituality and spiritual experiences to be the very
III. WAYS TO ARTIFICIAL CONSCIOUSNESS
core of his/her conscience”. In this view, unlike
In terms of technological contribution to a improving or
consciousness, conscience is exclusively human.
recovering human consciousness, neurocybernetic
On this background, a genuine social-human civilization
prostheses are not a novelty in bioengineering or even in
would also be a Society of the Conscience.
clinical engineering, fairly yet with much more modest goals
In general, society is seen by M. Draganescu [3] at the
than "treating‖ low levels of conscience.
crossing of influences coming from science & technology,
Thus, neural engineering aims at replacing a damaged part
environment, genetics and cultural (epigenetic) heritage, and
of the human brain, involved in cognitive functions, with
spirituality (Figure 1). Spirituality is not a relatively
integrated circuits operating on the known principle of the
objective social propeller, like science, but lies in depth of
artificial neural networks. Integrated circuits would not
the intangible human subjectivity, in the conscience.
necessarily be on silicon that after 60 years of supremacy
The question arises whether man‘s level of conscience
will leave their place by 2015 to molecular and quantum
(dependent on spirituality) could overcome at the societal
devices.
level the destructive effects of those parts of his genetic
Other hopes appear related to neuroelectronics that refers
inheritance directed to evil and aggression that prevents the
to coupling organic substrata to electronic systems and
progress of mankind towards a genuine social-human
devices. In this vein Fromhertz et al (quoted by Draganescu,
civilization.
[2]) have combined a silicon chip with the giant nerve cells
of the snail Lymnea Stagnalis and succeeded a two-way
communication, recording and stimulating without
micropipettes, simply by growing neurons on silicon
surfaces - inert except some sensitive areas for collecting and
emitting signals (in fact microelectrodes.
In a broader perspective, Koch and Tononi [4] evaluate
this way the chances of occurrence of artificial
consciousness: “Consciousness is a part of the natural world. It
depends, we believe, only on mathematics and logic and on
imperfectly known laws of physics, chemistry and biology. It does
Fig. 1 (modified after M. Draganescu, [3]) not derive from a magical or transcendent quality. If so, then there
is no reason that consciousness could not be reproduced in a
As for the genetic inheritance, M. Draganescu [3]) is machine, at least in theory”.
quoting the biologist and physician Grigore Traian Popa who Notice that by the term biological (that is living) they add
reviewing in the 40‘s the evils in the society of his times had phenomenological dimension (in Draganescu‘s sense) to the
put that brain should be taken into discussion when structural-informational world dealing with mathematics,
investigating what is going wrong in individuals and society logic, physics and chemistry.
since the brain can instrument both good and evil. In this line of thinking, Koch and Tononi argue how
Keeping the story short, due to its contamination by consciousness does not seem to require many things we
genetic inheritance, human consciousness as it presents currently associate with human being: emotions, memory,

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auto-reflection, language, sensitivity to the ambient and While accepting the possibility mentioned by others to
action in the world. To be conscious, they say, is in last create a conscious quantum computer M. Draganescu [2]
analysis to be a single integrated unit with a large repertoire excludes structural complexity as a source of machine
of states. Integrated information based consciousness theory consciousness; instead, he sees the structural-
(IIT) may suggest a test to measure the degree of phenomenological complexity as a necessary condition for
consciousness of a machine - a sort of Turing test for artificial consciousness.
consciousness (Turing test is a method of detecting a Issued in connection, symbiotic or not, with the human
presence of a human intelligence behind a machine brain, a conscious machine would hold a promise of
presented as an automaton). immortality sui generis, transcending decomposition of our
Talking about the best way to build a conscious machine, biological hardware. Thus, the advocates of singularity see
these authors evoke two complementary strategies: copying us, half in the joke half seriously, first becoming cyborgs -
a mammalian brain or evolving a machine. carriers of implanted chips to emulate perception, memory
The first way seems without perspective: modeling the and intelligence, and finally abandoning our flesh-and-blood
brain of a round worm (Caenorhabditis Elegans) with only selves for uploading our profound ego, digitally formatted,
302 neurons and approximately 6000 chemical synapses has in a computer memory that will forever ensure our
begun in 1986 and more than 2 decades later there was no immortality in the cyber-space. For some, this prospect is
valid model on how this minimal nervous system works. tangible; for example Kurzweil, an enthusiast of singularity,
A more plausible alternative is starting from architecture contemplates changing his lifestyle in the sanogenetic sense
of mammalian brain conveniently abstracted and evolving it "to live quite enough to live forever" (cf. Horgan, [5]).
towards a conscious entity. Attempts to date, the Aibo Letting the joke aside, Cardon, Camus, Campagne et al
robotic dog or the Qrio humanoid proposed by Sony are embarked in 2005 upon an ambitious project meant to
rudimentary tries to operate on a large number of fixed but conceptualize and build a system generating ‗faits de
flexible rules and would not pass perhaps the consciousness conscience‘, in fact an artificial brain aiming at transposing
test proposed by the IIT. Vision systems based on human thinking of something into the computable field, so
hierarchical multistrata maps of "neurons" (artificial neural that an computer-based artificial system would be able to
networks) are admirably managing to classify images from exhibit consciousness features in a viewable manner.
the real world, but presents obvious fragility when “The system will have intentions, emotions and ideas about
modifying background brightness entailed, for example, by a things and events related to itself. The system would have to have a
change of scenery. body that it could direct and which would constrain the system. It
As Koch and Tononi conclude, the big stake of reflection would also have to have a history, and intentions to act and, most
of all, to think. It would have to have knowledge, notably language
on how to build a conscious machine is undoubtedly more knowledge. It would have to have emotions, intentions and finally a
clear understanding of our own consciousness, as a certain consciousness about itself” (Cardon, Camus, Campagne et
necessary support for the next step to take over towards al, [6]).
more conscience - we might add. There is a summum bonum, a most generous statement of
intentions in this field that should deserve, judging
IV. INFORMATION TECHNOLOGY APPROACH conceptual and IT effort deployed, careful consideration
The assumption that computing machines could become even if authors often forget to put due quotation marks when
conscious is based on the analogy seen by many between it is about intentions, emotions and ideas.
brain (wetware) and computer (hard- & soft- ware). It is Two hypotheses judged as reasonable are made for this
expected that before long the computers will reach the transposition:
estimated complexity of the brain. - analogy between the ―geometrical dynamics‖ of the real
A healthy adult brain contains about 100 billion neurons, brain (it is about modeling of human brain when authors
each of them connected by axons (output), dendrites (input) speak geometry) and of the artificial brain. For one, flows of
and synapses with other about 100,000 neurons. It results data refer to complex images, almost continuous; for the
that a typical brain has about 1015 connections between its other, there are dynamical graphs whose deformations
neurons, each supporting at least one discharge per second. (introducing ‗emotions‘) are evaluated topologically;
Many think that in about a decade computers will reach the - reduction of combinatorial complexity of the real brain
computational power of the brain when exceeding 10x1015 by positioning it at symbolic and pre-language level into
operations/second (op/s). The IBM supercomputer Blue computable domain.
Gene /P could execute a year ago up to 3x1015 op/s. A first implementation is reported on equipping the
Argonne National Laboratory (USA, Illinois) is now Sony‘s ERS-7 Aibo robotic dog with a reflective and
upgrading a Blue Gene/P for doing circa 1/2x1015 op/s [5]. reactive ―brain‖ working at several levels (Camus and
However, complexity of the brain once reached, "no one Cardon, [7]).
has the foggiest notion" (E. Kandel, Nobel Laureate, quoted Aibo sensors for touch & distance and a video camera
by Horgan, [5]) how the computer could possibly make the allow to process environment data to give a contextual
qualitative step towards consciousness or beforehand how position (scene representation – 1st level). The camera data
agglomeration of neurons and other soft tissues constituting are processed by an artificial neural network embedded in
the brain gives rise to conscious mind - that intangible entity any of a multi-agents system (several thousands of
that in Horgan‘s words “makes you falling in love, seizing ‗aspectual agents‘ run on a G4, Cardon, [8]) in order to
the irony in a novel, or appreciating the elegance of an build a vision ontology linked a the sensor ontology. The
electronic design”. second level associates the goals of the robot with its
environmental knowledge in order to give priority to some
objects or actions in the scene. The third level works on the

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multi-agent system morphology to detect on line particular, as spirit. A human is an incarnate spirit but his/her spiritual
stable geometrical forms (Campagne, [9]) in order to life is defining for a person. In the same manner we use
recognize and classify geometrical forms as ‗emotions‘ apparatuses and instruments to probe the inner of inanimate
generated by the robot during its evolution in the scene things, to reach the deepness of a person we need personal
accompanied by recognition of objects and subsequent interrelations that in the ideal form represent love. The
actions. The fourth level creates a relationship between the intimate knowing of a person cannot be entrusted to objects
‗cognition‘ and the (re)action (‗behavior‘). For a cognition (that is artifacts, though they can help) but to another person
degree, there is a succession of actions on different only‖ (Ciobotea, [10]).
actuators: the more the cognition degree is higher, the more If so, best understanding of brain is that given to
the list of actions is specified. The fifth level is a continual another brain (e.g. scientific brain seen as a collectivity of
bidirectional interaction and adaptation between the brains interacting via communication technology - CT). One
environment and the robot behavior. For each action, there is can remark the role played in such instance by artifacts (like
feedback, a relationship between sensors and actuators. The CT): that of modest but useful adjunct of the real brain
‗attention‘ of the robot (in fact its knowledge base) evolves approaching (ideally with empathy and generosity) another.
with the number of performed actions. Cognition and action Finally, to Cardon‘s last questioning ―what we must to do
are treated in parallel by the multi-agent system. about a system generating artificial consciousness facts for
The project is developed on an Oz/Mozart shell. Oz is itself, having the sensation to generate artificial thoughts for
reported as a multi-paradigm language with scripting, object, its pleasure and using all the control-command systems and
logic and constraints programming. It allows using all de knowledge systems as rather gentle tools (our
paradigms such as the concurrency for developing a multi- highlight), without any human intervention? ― (Cardon, [8]),
agent system with asynchronous communication or the the answer could not be else than pouring out some axiology
constraints programming to create different action plans. into the puzzle next to the machine ontology before
While progresses in developing the novel Aibo‘s ―brain‖ detaching the dog (be it the Aibo one) from any human
along the above coordinates will perhaps continue by care of intervention. Problem remains how.
Cardon‘s younger colleagues, himself appears as the main And now our question. An AC system endowed with
beneficiary of insight got as team leader upon the (true) intentions, emotion and good actuators could be fully
human brain itself. Even if we do not share his rather autonomous that is entirely disconnected from human
pessimistic view put as: “Since the permanence of the physical control or guidance? Apparently not, because once its power
real apprehensible by senses is very strong, the preoccupation to source interrupted everything would stop. Or maybe, similar
think by man is quite limited, in his civilizations”. to actual humans, ―It‖ would become conscious (among
Dealing with artificial consciousness one has to keep in others) of such an weakness and consequently would (auto)
mind distinction among different level of analysis. The level assure a sub rosa backup power to continue its rapid
of reality refers to what is, the human brain, fragmentally development of knowledge, experience and capabilities even
and in general poorly understood. The level of our reflection against the will of its creator?
upon what is, uses words and logics taken from maths or In the same vein, Hanson [11] put: “If we do not humanize
experimental sciences. The level of simulation uses IT our intelligent machines, then they may eventually be dangerous.
artifacts to mimic brain functioning in its known aspects: To be safe when they “awaken” (by which I mean gain creative,
autonomy, adaptiveness, partly reason/partly emotion – free, adaptive general intelligence), then machines must attain deep
driven a.s.o. Simulation occurs since there are hopes that understanding and compassion towards people. […] Only if they
arranging such IT artifacts in relations deemed to be right the have humanlike character, can there be cooperation and peace
ensemble would begin to exhibit ―consciousness facts‖ with such machines. It is not too early to prepare for this
eventuality”.
replicating symbolically some features of what we
(bioengineers, neuroscientists, philosophers) think to be V. BIOENGINEERING AND CONSCIOUSNESS TOPICS
consciousness. Made up to cross the difficult border between medical
Why not remaining at the reflection level? For what education and the polytechnic one, biomedical engineering is
making such a complicate and tedious simulation? placed in the privileged position to advance knowledge in
Because, while reflection dissect (analyze) marvelously the field of human consciousness, in connection with the
single elements, simulation puts together various elements in conundrum whether or not computing machines may
their very interactive dynamics better than our reflection become conscious.
inherently static can do. Already seen before, bioengineering is central to
Associated risk with simulation is confusion of levels experiments that investigate direct human-machine
(planes); forgetting to use appropriate quotation marks, one interfaces, a topic of neural engineering.
may think that simulation might actually become, as an Thus, if the human brain has principle difficulties in
example, thinking itself but not an inspiring manner to understanding it own functioning, signal processing
enrich reflection upon. according to information theory rules allied with clinical
It is interesting to notice that theology, that is in part research on normal subjects may help to climb the staircase
science and part faith, while accepting the benefic role of to the brain starting from organs apparently less intelligent
medicine in treating some bodily illnesses, gets very but prone to be more easily understood.
precocious when is about knowing and influencing (and Cardiovascular bioengineering is today able to distinguish
eventually treating) the superior level of human being, the various consciousness states by analyzing heart-related
person (and personality) intimately associated with the brain. records by means of available knowledge on the control of
In the theological perspective, the person is considered visceral functions by the brain (Figure 2).
―the highest form of existence and defined before anything Increasing the cortical control on visceral regulation that

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conventionally is called autonomic represents one main its nuances among concentrated attention, moderate or strong emotion. RR-
LF clearly distinguishes between focused attention and emotion. These
aspect of corticalization of our species, in which Stefan
states of consciousness can not be discriminated with the same clarity using
Milcu [12] saw the neurophysiologic mechanism of human cerebral electrical activity noninvasively recorded on the scalp.
being‘s evolution including consciousness and conscience. Consciousness states and moods deeply influence the physiological
Developed by exercising information, the cortex has machinery [14]. Since sympathetic ventricular overdrive is arrhythmogenic,
such studies may offer a track for risk detection and prevention of sudden
already spread its "antennae" to the lower floor of the brain,
cardiac death in apparently healthy people (not known as cardiac patients)
the brainstem regulating the vegetative life, and further on under sustained psycho-social stress [15].
by the cranial nerves to the peripheral organs. According to
M. Draganescu [13]: "It would be possible that mental While conscious people without conscience are
processes get manifest by such extensions throughout the unfortunately too frequent today, humanity cannot afford a
body”. It stands for a philosophical inference confirmed at machine reply of its brain developing exponentially
least at the heart‘s level. capabilities and power outside of any moral.
Question remains upon the finality of such influence or On the contrary, if we succeed to seed at the right time a
control exerted by cortex upon ―lower-minded‖ organs. ‗moral principle‘ into the machine we could enjoy a
Auto-assuring the best functioning conditions given the prototype of pure or ideal consciousness, escaping from
multiple circular feedback loops relating brain and biological impulsions and restrictions, that might guide or
―subjacent‖ physiological machinery? If so, best functioning emulate humanity‘s struggle towards a true Society of the
refers to which criteria: physical effectiveness, mental Conscience.
performance, emotional refinement or higher propensity to REFERENCES
moral (read spiritual) values? If the latter proves as true, [1] Versace M., Chandler B., MoNETA: A mind made
entering the regulatory loops by gentle means, natural (as from memristors, IEEE Spectrum Robotics/Artif. Intell.,
breathing pattern control) or artificial (as noninvasive, December 2010.
remote influencing the heart rhythm) could hold promise for [2] Draganescu M., Neural engineering and
human being improvement without appealing to artificial neuroelectronics facing artificial consciousness, Key
consciousness. note to the INGIMED II Conference, Bucharest, 2001.
VI. CONCLUSION [3] Draganescu M., Societatea Constiintei, Raport de
Bioengineering and information science&technology cercetare, Academia Romana, Bucuresti, 2003.
certainly advance towards artificial consciousness. [4] Koch C., Tononi G., Can machines be conscious? IEEE
How benefic for humanity is yet not clear. It depends on Spectrum: special report on singularity, June 2008..
our capacity to inseminate a machine transposition of natural [5] Horgan J., The consciousness conundrum, IEEE
ethics, at the same time with increasing machine autonomy. Spectrum: special report on singularity, June 2008
Complete autonomy should superpose to a free will (libre [6] Cardon A., Camus M., Campagne J-C., System
arbitre) having behind a machine axiology built at the same generating consciousness facts, 2005,
time. Neglecting or postponing the latter might associate http://abrainproject.googlepages.com
catastrophic escaping from any human control. [7] Camus M., Cardon A., Towards emotional decision-
making, Innovative Concepts for Autonomic and Agent-
Based Systems, LNAI 3825, Springer, 2007.
[8] Cardon A., Artificial consciousness: the hard problem,
ISC Lyon, June 2008.
[9] Campagne J.-C., Systèmes multi-agents et morphologie,
Thèse de doctorat en informatique de l'Université de
Paris 6, septembre 2005.
[10] Ciobotea IPS D., A vindeca şi a ajuta în tradiţia Bisericii
Răsăritene, Lucrarile Simpozionului de
oncologie, Clinica pentru biologie tumorală (Klinik für
Tumorbiologie), Universitatea din Freiburg in Breisgau,
iunie 2003.
[11] Hanson G., Why we should build humanlike robots,
IEEE Spectrum Robotics, April 2011.
[12] Milcu St., Minte si materie, Seminarul de
bioinginerie ISPB, Bucuresti, 1994.
[13] Draganescu M., Semn si semnal. Key note la
Fig. 2 - Repercussion at heart of consciousness states investigated in 23 Sesiunea Academiei Romane, iulie 1986.
healthy young people, 19-21 years, studied in relaxation sitting (baseline), [14] Negoescu R., Bioengineering spots heart repercussions
under concentrated attention induced by an arithmetic test without of mental processes: sudden cardiac death corde
constraint of time (labeled as attention), and under emotion or strong
emotion induced by time constraint (emotion/high emotion). RR - the heart indemno is preventable, Proceedings of the Romanian
period; RR-LF/QT-LF - the fractions of low frequency (0.04-0.15 Hz) in the Academy, Series A: Maths, Phys, Tech Sci, Inform Scie,
spectra of variability of heart period or of QT interval in the Volume 4 , Number 1, pp. 65-73, Bucharest, 2003.
electrocardiogram; IV QT-LF – the fraction of low frequency in the [15] Negoescu R., Dinca-Panaitescu S. Processing high-
spectrum of variability of the QT interval from which heart rate influences
were extracted using cross spectral techniques – is an emerging indicator of resolution ECG facsimiles to detect ventricular
sympathetic control of ventricles (idioventricular). P indicates significant sympathetic overdrive & to prevent sudden death corde
differences between group averages. The idioventricular sympathetic indemno, A review, ECIT, Iasi, 2008.
control as expressed by IV QT-LF respond significantly to stress whatever

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Cross-Sector-Communication and Continuity of

Care: Using Standards for an Integrative Health
Environment
Rolf ENGELBRECHT1, Claudia HILDEBRAND2, Hans DEMSKI2
1
ProRec Germany, Glaslweg 33 D 85737 Ismaning
2
IBMI -Institute for Biological and Medical Imaging, MEDIS - Medical Information Systems,
Helmholtz Zentrum München, German Research Center for Environmental Health
Ingolstädter Landstr. 1, D 85764 Neuherberg, Germany
Abstract – European healthcare is changing The increased movement of the citizen asks for administrative
changes, but also for patient records that can be accessed ubiquitously in real time and also across boarders. New
technologies offer new approaches and possibilities. This paper outlines the changes of developments in the health
sector brought upon by ICT. It demonstrates present initiatives towards European eHealth cross-border solutions
regarding different levels of interoperability such as semantics, technical requirements, organisational and
security related requirements. The project ByMedConnect is given as an example for implementing standardised
solutions for overcoming limiting factors and ensuring an interoperable solution supporting continuity of care.
Challenges on a future user-friendly European eHealth solution are discussed.

Index Terms – eHealth, electronic healthcare record, EHR, interoperability, standard, cross-border healthcare,
CCR, Continuity of Care Record, EHRcom, ISO EN 13606, ProRec, EuroRec,

I. INTRODUCTION II. HEALTH INFORMATION SYSTEMS

Electronic support of health care known as eHealth is able Health information systems are developed for different
to improve the access to clinical data, knowledge and purposes using a variety of technologies. They might be
information and to enhance the quality of services and supporting administration or even decision support. The
working conditions offered. eHealth supports mobility. It scope of functions provided and the way they are
allows patients to access appropriate health resources based implemented depend on the health care area. Primary care in
on equal opportunity and informed choice. Information and mostly all countries is visit oriented with treatment time
communication technologies (ICT) support networking usually restricted to few minutes. This minimises the amount
between human beings, institutions and health information of data which are documented per visit.
systems -also across borders. Smart and safe communication In secondary and tertiary care larger systems were
of data, information and knowledge will remain main developed; these support logistics and patient management.
development issues in the next decade as networks are They are episode oriented and at their core are ADT
crossing regional and national boundaries. There are several (Admission-Discharge-Transfer) and financial management.
national initiatives in Europe which are not harmonised so The systems serve as an administrative basis for
far. departmental and service systems such as laboratory and
In 2008 the European Commission issued a radiology.
recommendation on cross-border interoperability of the While presently healthcare systems and medical services
electronic healthcare record (EHR) [1]. It states that in order evolve around the patient-doctor relationship, in the near
to achieve interoperability ―Member States are invited to future this correlation will be just one part of a more holistic
undertake actions at five levels, namely the overall political, approach. eHealth needs to be seen being a framework of
the organisational, the technical, the semantic and the level compliance with privacy issues, healthcare centres, home-
of education and awareness raising‖. monitoring, and results being used for research. Social
At the same time a large scale project, called epSOS services are in many countries getting linked to health
(European Patients Smart Open Services) [2] involving 12 services.
Member States (and many Health Ministries) aiming to Today health data communication is usually limited to one
support the implementation of cross-border healthcare was institution or to regional doctor networks. Most countries
initiated. lack communication between the different health care
Many other National and European projects have helped institutions, e.g. hospitals and primary care. Some of the
advancing interoperability in different sectors of eHealth, reasons are technical problems and missing standards and/or
e.g. TrustHealth [3] and SEISMED [4] in security, the insufficient application of existing standards.
DIABCARD [5], NETCA@RDS [6] and ARTEMIS [7] Missing common terminology is another hindrance in
developed technical and semantic solutions for communication, even more so when communication
communication, TOSCA [8] showed feasible solutions for concerns institutions or physicians in different countries.
tele-health, Bit4Health [9] demonstrated ways towards an The DIABCARD project [5], which aimed at improving
eHealth architecture. communication in diabetes care, was one of the first projects
to demonstrate an interoperable solution. Its dataset was
based on the standardised European Emergency Data Set

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[10] and on a ―Diabetes dataset‖ developed by European get information on eHealth standards to help them decide –
physicians and agreed by EASD (European Association for backed by an online Standards‘ Repository - whether a
Studying Diabetes). Chip card technology was used for specific standard would be of help to them or not. The
communicating data between physicians and other health project was exemplified on security standards in eHealth.
professionals. A dedicated card connecting interface module A main step towards interoperability of healthcare related
ensured the independence of the solution from specific cards data and the development of eHealth platforms were
and card readers. DIABCARD was implemented in Austria, decision 189, 190, 191 on the European Health Insurance
Greece, Italy, Spain, France and Germany. The follow-up Card (EHIC) [6], which is used to proof the citizen‘s
project ByMedCard - Health across Borders adapted and entitlement to health treatment in any EU Member State. As
implemented the DIABCARD concept for citizens travelling an additional measure the European Commission issued
between Germany and Hungary. Mandate 403 (M/403) [12] to the three European Standards
Increased mobility of the citizens asks for administrative Organizations (CEN, CENELEC, and ETSI) in order to
changes, but also for patient records that can be accessed provide a consistent set of standards to address the needs of
ubiquitously in real time and also across boarders. Thorough European eHealth provision.
and adequate administrative changes are required. Amongst others digital identity is a major issue. This can
EpSOS [2] aims to develop a practical eHealth framework be defined as a collection of digital information on one
and an ICT infrastructure that will ensure secure access to subject. It is needed to link different electronic data to one
patient health information, particularly with respect to basic person, e.g. a person‘s health insurance number to his lab
patient summaries and ePrescriptions between different data in order to store these in the person‘s health record.
European healthcare systems. NETC@RDS [6] has been Digital identity serves different purposes: identification,
working towards the establishment of new improved health authentication, and assurance. It consists of a set of
care administration services for mobile citizens across the attributes, e.g. characteristic habits, preferences or traits plus
EU. an identifier which can be real or anonymous.
Management of digital identities (eID) is a very complex
III. STANDARDISATION
area. eIDs need to be allocated not only to human beings but
Healthcare information is presently still very fragmented
to all principals and even to specific items. eID of replicable
with proprietary medical information systems using
things and robots which are used for automated operation of
individual interfaces, data protection solutions and even
patients have to be envisioned in the near future. Several
terminology. In contrast mobility requires interoperability
projects and activities work towards to overcoming barriers
which has to enable the exchange of clinical data between
in the digital identity sector and to finding ways on eID
computer based applications, even for cross-border
management.
communication.
Modern technology supports mobility: the internet enables IV. SUPPORTING CONTINUITY OF CARE
fast and –almost- ubiquitous access and is to be seen as a The Continuity of Care Record (CCR) [13] developed by
main platform for the future. Trusted portable devices like a ASTM is a well structured basic data set of the most relevant
mobile phone, a smart card or other devices such as USB facts about a patient‘s health status, covering one or more
sticks can complement it for reliable identification and episodes or visits. These may be documented by a GP, a
authentication of users. Safe communication between sender specialist physician, a hospital physician or a nurse during
and receiver relies on confidentiality, authenticity, data treatment in order to enable other health professionals caring
integrity and accountability. for a patient to readily access a summary of relevant and
The information needed to treat the patient as well as actual information. It includes identifying data, information
security functions will have to be available in the preferred about the patient‘s health status (e.g. anamnesis, allergies,
language of the health professional. Under strict security risks, problems, medications, operations) and basic data
conditions, authorised healthcare personnel will be able to about insurance, care documentation and care plans. The
read and write information locally or remote. This requires CCR is represented in XML, a structured electronic format.
interoperability on different levels: The CCR is meant to address the information needs for
 Semantics ensuring common definition and continuity of care from one health professional to another.
As it contains only selected, relevant portions of a patient‘s
understanding of the content;
health record it provides a perfect data source for treatment
 Technical enabling the use of different environments across borders.
in order to integrate the different applications; The physician originating the CCR transmits it to the co-
 Organisational requiring the understanding of treating practitioner. This approach already proofed
legislation, regulation and other policies as well as applicable in the DIABCARD system where a smart card
was used as communication tool. The XML structure
governance models;
contains also links which point to selected documents of the
 Security making sure of a trustful environment. patient‘s EHR. The documents are located on a specific
A number of ISO and CEN standards have been published server and can be accessed by authorised physicians using
to advance these goals. They range from requirements on the Health Care Professional Protocol (HCPP) [14] via
protocols, devices and architectures to service internet.
infrastructures. Unfortunately, they are often neither known The ASTM standard CCR has been introduced in the USA
nor used. The BioHealth project (Security and Identity in more than 100 health care systems. Microsoft's Health
Management Standards in eHealth including Biometrics) Vault and Google‘s concept for healthcare support have
[12] has been analysing reasons for this and has at the same implemented this standard. Another variant is CCD, the
time tried successfully to provide ways to enable SMEs to

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CCR is translated into an electronic document conforming it tools are developed that enable the clinicians themselves to
to the HL7 CDA [15] concept. Solutions for patient centred define these universal models in an international
administration of the CCR by use of mobile phones are collaborative approach [19]. Archetypes created can then be
available. published in a repository for sharing and reusing them within
inter-institutional and inter-sectoral communication. The use
of archetypes is an important step towards semantic
interoperable EHRs that are portable (via institutional /
regional boundaries), precise (e.g. terminology binding),
accessible (individual queries + decision support) and
durable (life-long record).
Archetype based data exchange has the potential to fill the
gap of lacking communication capabilities between
heterogeneous systems. The standard for EHR
communication has recently been published for international
use at ISO, e.g. a Japanese version is ready for
implementation. The standardisation activities are supported
by the EUROREC Institute [20] and the OpenEHR
Foundation [21].

V. INTEGRATION OF LEGACY SYSTEMS

Fig 1: Secure communication network between physicians in hospital and A multiplicity of different routine applications is used in
primary care using professional cards (Arztausweis) and the DIABCARD hospitals, by family doctors and in medical specialist
smart card. practices. These software solutions are often specialized for
In the ByMedConnect [16] project the pragmatic and the surroundings and to the tasks they support. Users are
limited approach of the CCR is complemented by the more versed in them and have a lot of experience in handling the
comprehensive standard ISO 13606 – Electronic Health included procedures.
Record Communication [17]. It consists of various parts and A replacement of the programs in use is not feasible. But
proposes an advanced architecture to deal with the major disadvantage is in most cases that data of patients,
heterogeneous systems existing in the medical domain. It which would be helpful for further attendances, is stored at
defines a reference model for the EHR that specifies the different places in different forms.
common building blocks, and introduces Archetypes [18] as To gain interoperability between health care institutes, it
a formal model of real clinical concepts that lay the basis for is necessary to transmit data in a standardized format. EN
interoperable semantically sound data exchange. Currently 13606 provides structures for this task, but doesn‘t define
how information can be extracted out of already existing

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Fig 2: Export of data in ISO 13606 compatible format out of the Russian version of the disease management software DIABCARDcom
 International Conference on Nanotechnologies and Biomedical Engineering , Chişinău, Republic of Moldova, 7-8 th of July , 2011

systems. ByMedConnect meets this challenge by the The success of eHealth will depend on the acceptance by
development of a transformation module. all users. This means that a comprehensive European
The module is placed at the existing software environment eHealth strategy needs to be developed. eHealth offers large
of the health care institute. Thereby it is connected to business opportunities and it has the potential to drive
interfaces of the routine applications. On demand, it extracts, innovation. This necessitates the development of new
the necessary data out of the legacy systems into XML, or products and high investment costs. A clear political
into an XML convertible form (CSV, JSON). A commitment towards the financing is required.
correspondent XML schema (XSD) describes the data eHealth requires accessibility of new technologies and e-
exported. Approaches to use this schema for binding literacy. The European population is aging. This means, on
information on parts of tharchetypes have been published the one hand, large opportunities towards the support of the
before [7, 8]. Scripts can be generated out of the mapping elderly, but, on the other hand, challenges like creating
automatically, this allows the module to do the correct awareness and technology education in the elderly have to be
transformation without any further interaction by the user. met. In a European cross-border scenario legal barriers such
as the contradiction of national legal requirements, and of
national laws impacting identity have to be overcome
VI. CONCLUSION
without neglecting social barriers such as the culture of
In future healthcare will be different. The benefits of
distrust or the fear of loss of anonymity. eHealth relies on
eHealth are apparent. For many years the Member States and
the trust in the system by all stakeholders. This keeps data
the European Commission have been supporting projects
protection, privacy, security and also ethical issues high on
enhancing the quality of care by ICT. The present
the agenda.
technological developments -building on the results and
achievements of those early initiatives- are pointing towards ACKNOWLEDGEMENT
patient-centred health care supported by anytime-anywhere The authors are in debt to the European Commission and
access to health information and enabling instantaneous the freestate Bavaria for funding several successful research
connections to clinical support. Presently eHealth is at a projects especially DIABCARD and ByMedCard. The
crucial point; many initiatives towards European eHealth project ByMedConnect is currently funded by the Bavarian
solutions have been initiated and are ongoing as has been Minister for environment and healh.
shown in the p
REFERENCES
[1] Commission Recommendation of 2 July 2008 on cross-
border interoperability of electronic health record
systems (notified under document number C(2008)
3282)
[2] epSOS- European Patients Smart Open Services;
http://www.epsos.eu (last accessed 24-09-09)
[3] Blobel, Bernd (2000) The European TrustHealth Project
experiences with implementing a security infrastructure.
International Journal of Medical Informatics 60 (2), S.
193-201.
[4] SEISMED - Secure Environment for Information
Systems in Medicine;
http://ehto.org/aim/volume2/seismed.html (last accessed
24-09-09)
[5] DIABCARD
[6] NETCA@RDS -A step towards the electronic European
Health Insurance Card; http://netcards-project.com (last
accessed 24-09-09)
[7] ARTEMIS- Building interoperability into medical
information systems;
http://istresults.cordis.europa.eu/index.cfm/section/news
/Tpl/article/BrowsingType/Features/ID/79928 (last
accessed 24-09-09)
[8] TOSCA- Tele-Ophthalmological Services - Citizen-
centred Applications; http://www.ist-
world.org/ProjectDetails.aspx?ProjectId=525f09f393a6
4657a6c645111f3fc278 (last accessed 24-09-09)
Software [9] Blobel, Bernd (2005) Die Implementierung von
bIT4health im Spiegel der europäischen Initiativen
Healthcare Institution sowie der fortgeschrittenen Programme anderer Länder.
Figure 2. Integration of legacy systems
In: Steyer, Günter und Tolxdorff, Thomas, (eds.) bit for
bit - Halbzeit auf dem Weg zur Telematikinfrastruktur:
receding chapters. These solutions still need to be proved TELEMED 2005 - Telematik im Gesundheitswesen.
applicable, feasible, usable, acceptable and useful.

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Akad. Verl.-Ges., Berlin, S. 88-95. ISBN 3-89838-064- [16] ISO13606-Part 1:2008,

5 http://www.iso.org/iso/catalogue_detail.htm?
[10] European Emergency Data Set – NETLINK csnumber=40784 (last accessed 24-09-09)
Requirements for Interoperability; http://www.sesam- [17] ByMedConnect - Improving communication by linking
vitale.fr/netlink/netlink_requirements_for_interoperabili domains thus fostering integrated healthcare in Bavaria;
tyv21.pdf (last accessed 24-09-09) http://www.bymedconnect.de (last accessed 14-06-
[11] BioHealth - Security and Identity Management 2010)
Standards in eHealth including Biometrics; [18] ISO 13606-Part 2:2008,
http://www.bio-health.eu (last accessed 24-09-09) http://www.iso.org/iso/iso_catalogue/catalogue_tc/catal
[12] M/403 EN; ogue_detail.htm?csnumber=50119 (last accessed 24-09-
http://ec.europa.eu/enterprise/standards_policy/action_pl 09)
an/doc/mandate_m403en.pdf (last accessed 24-09-09) [19] openEHR Clinical Knowledge Manager;
[13] Continuity of Care Record (CCR) Standard - Resource http://www.openehr.org/knowledge (last accessed 24-
Site; http://www.ccrstandard.com (last accessed 24-09- 09-09)
09) [20] EuroRec Institute; http://www.eurorec.org (last
[14] ByMedCard - Health-Care-Professionals-Protocol accessed 14-06-2010)
(HCPP); [21] openEHR Foundation; http://www.openehr.org (last
http://www.stmugv.bayern.de/krankenhaus/telemedizin/ accessed 14-06-2010)
projekte_detail.htm?ID=AAxpv0ps7BE2AiIRuFTDJA Address for Correspondence
%3D%3D (last accessed 24-09-09) Rolf Engelbrecht
[15] HL7book – CDA Resource Page; ProRec Germany,
http://hl7book.net/index.php?title=CDA (last accessed Glaslweg 33
24-09-09) D 85737 Ismaning

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New Parameter for Describing and Analysis of

Optical-anisotropic Properties of Biological
Liquid Crystals Nets
Yuriy A. USHENKO
Chernivtsi National University
[email protected]

Abstract – This paper is aimed to investigate the potentiality of describing and differentiating optical-
anisotropic properties of biological liquid crystal nets by statistic analysis of coordinate distributions of a new
analytical parameter – complex degree of mutual anisotropy.
Index Terms – polarization, birefringence, anisotropy, laser image, statistics.

I. INTRODUCTION U x r1 U x r2   U y r1 U y r2 

Traditionally [1, 8-24] the processes of forming the 1  ,
2

polarizationally-heterogeneous fields U r were considered U x r1 U y r2   U y r1 U x r2 


in every point ( r ) as a result of the amplitude ( U x , U y ) – 2  , (3)

2
phase (  ) modulation of laser radiation by the biological U x r1 U y r2   U y r1 U x r2 
crystals network 3  i .
2
The analysis of coordinate distributions of the CDMP
 U x r   d11 r  d12 r   U0x  polarization-heterogeneous laser images of biological liquid
   
U r   d r  d r  U 0 exp  i 0   crystals net - protein fibrils network forming the biological
 y  21 22  y  (1)
tissue (BT) extracellular matrix, - became an important
 d11 r U 0 x  d12 r U 0 y exp  i 0  
  . diagnostic application of the above mentioned theoretical
 d 21 r U 0 x  d 22 r U 0 y exp  i 0 
 approach. The ranges of changes of the 1st-4th distribution
order statistic moments of coordinate distributions of the
Here 0 – the phase shift between the orthogonal CDMP of the corresponding laser images, important for
components U 0 x and U 0 y of the illuminating laser beam diagnostics of the human connective tissue oncologic state
were determined in [8, 22]. On the other hand, such analysis
amplitude; d ik – the Jones matrix elements [1, 8]. lead to disregarding the BT extracellular matrix
For the complex analysis of polarizationally birefringence, which is a principal physical mechanism of
heterogeneous laser radiation fields a new approach was their polarizationally-heterogeneous images formation. That
suggested in [2-6, 22], based on the generalization of is why it appears to be important to search for new
coherence matrix by the polarization coherence matrix for diagnostic parameters directly characterizing the degree of
 
two points r1 , r2 . In [7, 22] for characterizing the similarity of optical axes and birefringence orientations of
various points of BT liquid crystal net [12, 15, 18, 19].
consistency between the polarization states of the stationary Further, similarly to [7] we shall call such a parameter the
 
laser object field in the points r1 , r2 with the intensities complex degree of mutual anisotropy (CDMA).
I r1  , I r2  a new parameter – complex degree of mutual Taking into account (1) – (4) we obtain the expression of

polarization (CDMP) V r1 ,r2  – is introduced. It has the

   
CDMA W r1 , r2 of two points r1 , r2 of the biological
liquid crystal The operation of complex conjugation is
following analytical form: designated by the asterisk (  ).
 12   22   32
V r1 , r2   4 II. RESULTS
I r1 I r2 
, (2)
Experimental investigations were carried out in the
classical polarimeter the main parts and elements of which
where the coefficients  i are determined as the difference of are presented in Fig. 1 [8]. The value of CDMA
the values of visibility of interference images formed by
W r1 , r2  r1  r  of the two points ( r1 , r1  r ) shifted by
electromagnetic waves from the points r1 , r2
the interval r of the network of protein liquid crystals is
calculated using the algorithm (5). Coordinate distribution
 
W x, y of the BT layer extracellular matrix is determined

W r1 , r2  

 d11r1   id 12 r1 d11 r2   id12 r2   d 21r1   id 22 r1 d 21r2   id 22 r2  
  2

I r1 I r2 
(4)

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. with different geometric thicknesses (15 and 40 m ).

In order to form a single and multiple scattering regimes
we have used a histological sections of biological tissues
with different geometric thicknesses (15 and 40 m ).
Fig. 1. Optical scheme of polarimeter for measuring coordinate CDMA In the figures 3 and 4 the comparative results of
distributions Here 1 – He-Ne laser ( = 0.6328 m); 2 – collimator; 3, 5 and calculations of the average ( M 1 ), the dispersion ( M 2 ), the
8 – quarter-wave plates; 4 and 9 polarizes; 6 – BT histological section; 7 –
projection microobjective; 10 – CCD –camera; 11 – PC. skewness ( M 3 ) and the kurtosis ( M 4 ) of CDMA W x, y 
Histological sections of sound connective tissue (k=20 (Fig. 3) distributions of two groups of connective tissue and
samples) and oncologically changed (k=19 samples) one  
of CDMP V x, y (Fig. 4) of their laser images are
(dysplasia – pre-cancer state) of uterus neck were taken as
presented. In order to estimate the statistic reliability of
the objects of investigation.
calculations the amount of samples within each group (norm
The series of coordinate distributions ( 600 pix  800 pix
or oncology) were chosen that confidence interval
– fragments (а), (d); 50 pix  50 pix – fragments (b), (e)) and p  0.01 . The area of illuminating laser beam was chosen
the histograms (fragments (c), (f)) of CDMA values
M 1 , M 2 , M 3 and M 4 did not depend
W x, y  of physiologically normal (fragments (а), (b), (c))
~ that magnitudes of
on displacement in the plane of the histological section
and pathologically changed (fragments (d), (e), (f)) sample. For our experiment the diameter of laser beam was
connective tissue samples are presented in Fig. 2.
5mm , and the size of histological section was 15 15mm .
The statistic moments were calculated in accordance with
the following technique [21, 22]:
1 N 1 N
M1   W  x, y  , M 2 
N i 1
 (W x, y   M 1 )i2 ,
N i 1 (5)
1 1 N 1 1 N
M3   W x, y i , M 4  4 W x, y i ,
3 4
3
M 2 N i 1 M 2 N i 1
where N - is the number of elements in discrete
sampling.
From the obtained data about the coordinate distributions
of CDMA of optically thin layers of connective tissue one
can see that:
The average and dispersion of distributions W x, y of  
both types of samples differ insufficiently. For 2D
 
distributions V x, y of laser images there is practically no
difference between M 1 and M 2 .
The skewness values M 3 of distributions W x, y  of
Fig. 2. Coordinate distributions ( 600 pix  800 pix – fragments (a), (d);
the investigated samples differ by 2.1 times; the kurtosis
50 pix  50 pix
 
– fragments (b), (e)) and histograms (fragments (c), (f))
values – by 3.2 times. For CDMP distributions V x, y the
W x, y  of physiologically normal ((а), (b), (c)) and
~
of values rd th
pathologically changed ((d), (e), (f)) histological section of connective
values of the 3 and 4 statistic moments vary for M 3 – by
tissue. 1.3 times; for M 4 – by 1.8 times.
For chaotically oriented network of liquid crystals of the
sound tissue extracellular matrix (Fig. 2(а), (b)) the values of
 
W x, y histograms represent rather equiprobable
distributions (Fig. 2(c)). Early oncologic changes of
connective tissue are accompanied with the formation of the
protein liquid crystals net growth direction. It is optically
shown (Fig. 2(d), (e)) in some localization of the CDMA
random values distribution (Fig. 2(f)) in the domain of
W  0,4  0,6 extrema.
In order to obtain objective criteria of diagnostic
efficiency, the comparative investigation of CDMP
   
( V x, y ) and CDMA W x, y techniques was performed
in the conditions of single and multiple scattering of laser
radiation by the layers of uterus neck connective tissue.
In order to form a single and multiple scattering regimes
we have used a histological sections of biological tissues

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Fig. 3. The histograms of statistical moments of CDMA W x, y  for Methods: Biomedical Diagnostics, Environmental and
physiologically normal (white bars) and pathologically changed (black bars) Material Science, Valery V. Tuchin, ed. (Kluwer
connective tissue. Academic Publishers, 2004), pp. 93-138.
[9] Alexander G. Ushenko, ―Polarization structure of laser
scattering fields,‖ Optical Engineering, 34(4), 1088-
1093, 1995.
[10] Ushenko A.G., ―Laser diagnostics of biofractals,‖
Quantum Electronics 29, 1078–1084, 1999.
[11] Angel'skii O.V., Ushenko A.G., Arkhelyuk A.D.,
Ermolenko S.B., Burkovets D.N., ―Structure of matrices
for the transformation of laser radiation by biofractals,‖
Quantum Electronics 29, 1074-1077, 1999.
[12] Angel'skii O.V., Ushenko A.G., Arheluk A.D.,
Ermolenko S.B., Burkovets D.N., ―Scattering of Laser
Radiation by Multifractal Biological Structures,‖ Optics
and Spectroscopy 88, 444-448, 2000.
[13] Ushenko A.G., ―Polarization Structure of Biospeckles
and the Depolarization of Laser Radiation,‖ Optics and
Spectroscopy 89(4), 597-601, 2000.
Fig. 4. The histograms of statistical moments of CDMP V x, y  for [14] Ushenko A.G., ―Stokes-correlometry of biotissues,‖
physiologically normal (white bars) and pathologically changed (black bars) Laser Physics 10(5), 1286-1292, 2000.
connective tissue. [15] Ushenko A.G., ―The Vector Structure of Laser
Biospeckle Fields and Polarization Diagnostics of
III. CONCLUSION
Collagen Skin Structures,‖ Laser Physics 10(5), 1143-
To characterize the degree of consistency of parameters of
1149, 2000.
the optically uniaxial birefringent protein liquid crystal nets
[16] Ushenko A.G., ―Laser polarimetry of polarization-phase
of BT a new parameter – complex degree of mutual
statistical moments of the object field of optically
anisotropy is suggested. The technique of polarization
anisotropic scattering layers,‖ Optics and Spectroscopy
measuring the coordinate distributions of the complex
91(2), 313-316, 2001.
degree of mutual anisotropy of BT is developed. It is shown
[17] Ushenko A.G., ―Polarization contrast enhancement of
that statistic approach to the analysis of distributions
 
images of biological tissues under the conditions of
W x, y of BT of various optical thicknesses appears to be multiple scattering,‖ Optics and Spectroscopy 91(6),
more sensitive and efficient in differentiation of their 937-940, 2001.
physiological state in comparison with investigations of [18] Ushenko A.G., ―Laser probing of biological tissues and
complex degree of mutual polarization of the corresponding the polarization selection of their images,‖ Optics and
laser images. Spectroscopy 91(6), 932-936, 2001.
REFERENCES [19] Ushenko A.G., ―Correlation processing and wavelet
[1] Born M., Wolf E., Principles of Optics. Cambridge analysis of polarization images of biological tissues,‖
Univ. Press, 1999. Optics and Spectroscopy 91(5), 773-778, 2002.
[2] Gori F., Santarsiero M., Vicalvi S., Borghi R. and [20] Ushenko A.G., ―Polarization correlometry of angular
Guattari G., ―Beam coherence-polarization matrix,‖ structure in the microrelief pattern or rough surfaces,‖
Pure Appl. Opt. 7, 941-951, 1998. Optics and spectroscopy 92(2), 227-229, 2002.
[3] Gori F., ―Matrix treatment for partially polarized, [21] Angelsky O.V., Ushenko A.G., Ushenko Ye.G., ―2-D
partially coherent beams,‖ Opt. Lett. 23, 241-243, 1998. Stokes Polarimetry of Biospeckle Tissues Images in
[4] Wolf E., ―Unified theory of coherence and polarization Pre-Clinic Diagnostics of Their Pre-Cancer States,‖
of random electromagnetic beams,‖ Phys. Lett. A. 312, Journal of Holography and Speckle 2(1), 26-33, 2005.
263-267, 2003. [22] Angelsky O.V., Ushenko A.G., and Ushenko Ye.G.,
[5] Mujat M. and Dogariu A., ―Polarimetric and spectral ―Complex degree of mutual polarization of biological
changes in random electromagnetic fields,‖ Opt. Lett. tissue coherent images for the diagnostics of their
28, 2153-2155, 2003. physiological state,‖ J. Biomed. Opt. 10(6), 060502,
[6] Ellis J., Dogariu A., Ponomarenko S. and Wolf E., 2005.
―Interferometric measurement of the degree of [23] Angelsky O.V., Ushenko A.G., and Ushenko Ye.G.,
polarization and control of the contrast of intensity ―Investigation of the correlation structure of biological
fluctuations,‖ Opt. Lett. 29, 1536-1558, 2003. tissue polarization images during the diagnostics of their
[7] Ellis J. and Dogariu A., ―Complex degree of mutual oncological changes,‖ Phys. Med. Biol. 50, 4811-4822,
polarization,‖ Opt.Lett. 29, 5365-5338, 2004. 2005.
[8] Alexander G. Ushenko and Vasilii P. Pishak. Laser [24] Angelsky O.V., Ushenko A.G., Ushenko Ye.G., Tomka
Polarimetry of Biological Tissue: Principles and Yu.Ya., ―Polarization singularities of biological tissues
Applications, in Handbook of Coherent-Domain Optical images,‖ J. Biomed. Opt. 11(5), 054030, 2006.

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Better Information, etter Decisions, better Care–

Introducing a Web-based Inventory System for
Medical Devices in Moldova
Claudio ZAUGG 1,2
1
Swiss Tropical and Public Health Institute
2
Moldova-Swiss Perinatology Project
[email protected]
Abstract – As in most health care systems, health technologies made a significant contribution to
improvements in quality of care in the Republic of Moldova in the last decades. However, there are currently
no instruments in place to efficiently plan, manage and coordinate investments in health technology. The
present work describes the assessment, evaluation and introduction of a web-based application with the
objective to strengthen the Health Technology Management (HTM) in the country. The open source tool
―openMEDIS‖ was configured, adapted and successfully introduced in six pilot hospitals. The new
management instrument has received good attention by the decision-makers at national and at regional level.
As a next step, openMEDIS will be scaled-up to all maternities in the country to facilitate evidence-based
planning in Perinatology.

Index Terms – Health Technology Management, Health Information Systems, Open Source Software

the Regionalization of Pediatric Emergency (REPEMOL

I. INTRODUCTION
Project). Besides the development of clinical standards,
Clinical equipment is one of the major contributors to the
rapid progress of healthcare [1]. The global market today capacity building, quality management, etc., both projects
counts more than 10‘000 distinct device groups and 500‘000 have also taken care of the procurement of respective
products from over 13‘000 registered manufacturers medical equipment. In this light, the introduction of an
worldwide [2], [3]. Innovation is the growth motor of the electronic information system in order to sustainably
industry: There are studies suggesting 50% of all diagnostic improve planning and management of the new technologies
and treatment methods we use today did not exist 10 years was a recognized as a priority by the Swiss Government.
ago [4]. This constant increase in the variety and complexity II. METODS
of available health technologies require good management The process started in 2009 with a qualitative needs
instruments to allocate the available resources efficiently. assessment looking into the Health Technology Management
The review of the World Bank‘s global $1.5 billion (HTM) landscape of Moldova – the managerial and technical
investment in medical devices showed that there are cases environment in which an information system for medical
where 30 % of the more sophisticated equipment stock was equipment will function in the future. The advances in HTM
unused and the rest had 25 to 35 % downtime because of driven by the two projects were coordinated by the HTM-
weak capacity to maintain equipment. A root cause turned Working Group which involved 20-30 stakeholders mainly
out to be ineffective management including planning, from hospital directorates, the Technical University of
acquisition and subsequent operations [5]. Moldova (TUM) and Ministry of Health (MoH).
The foundation for good management practice and good Based on the needs, a software application including a
policies is good data. Decision-makers in the Moldovan nomenclature system was to be identified and – if necessary
health care system have yet not been able to draw from a – adaptations and translations to be implemented. Along
respective information base in order to plan and streamline with the SW tool, targeted training modules on both the use
investments in medical equipment efficiently. Given the of the software application and on the importance in a
large number of international actors and programs with broader HTM context needed to be developed.
different procurement- and supply channels the need for Before the system was ready to be scaled-up it had to be
coordination becomes even more apparent. tested in two to three facilities (ideally in places where
The WHO collaborative agreement with Moldova [6] technical workshops were established in order to assure a
prioritizes capacities to monitor and evaluate the sustainable benefit for the hospitals). The data collection was
performance of the health system strengthened and systems mainly done through biomedical engineering students during
to facilitate coordination. Considering the large share of their internship or their first assignment in hospitals. In this
investments in medical monitoring its performance deserves process, but also in the adaptation and further development
a special attention. of the tool, the Technical University of Moldova (TUM) has
In the last years, the Swiss Government has been played an important role.
supporting Moldovan‘s health care system in the area of
Perinatology (Moldova-Swiss Perinatology Project) and in

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III. RESULTS planning in the past years, the paper-based lists found at
At the time of the evaluation, HTM in Moldova was some departments were often outdated, incomplete or faulty.
not very developed: planning and procurement were largely Another challenge was the experience of the data
influenced by donors and vertical intervention programs. collectors who had difficulties in finding the correct
The corrective and preventative maintenance of equipment nomenclature term for a specific devices or who have not
was done by private companies. Technical workshops to recognized them in the wards. Later on, a consultant was
service and maintain equipment were normally not present in employed to supervise the data collection process and to
public health facilities. Often, a head nurse or a director of a assure good data quality. After repeatedly addressing and
department without formal technical background was in discussing the problems and fine-tuning of the application in
charge of equipment management. Given such
the formal HTM working group meetings, the three
circumstances, key requirements to a software tool to
inventories were initially collected over a period of six
manage the equipment inventory were identified to be the
months to one year.
following:
 Be easy to use (simple graphical user interface).
 Offer possibility for remote data review, analysis,
backup and technical support.
 Include nomenclature according to ISO [7].
 Facilitate translation of user interface and
equipment tables into local language.
 Allow step-wise approach: Begin with a simple
system which can be extended as other areas of
HTM start to develop (e.g. maintenance)
 Do not impose high license cost to the public
health care budget once the system is scaled-up.
An evaluation of existing tools has shown that most
products on the market are either made for high-expenditure
health care systems or they are country specific tailor-made
solutions. The above mentioned criteria and the literature
suggested that web-based open source software would be
most suitable. The application which could meet the
requirements best was ―openMEDIS‖ [8] - a software
originally developed by the Swiss TPH that had also been
validated through implementation in similar settings.
―openMEDIS‖ was programmed using a PHP interface
and a mySQL database. The software provides functions
needed for systematic collection and exchange of health
technology data. Information such as a manufacturer
database, an integrated, reduced UMDNS nomenclature
(with 325 generic terms), or equipment images shall Fig. I. openMEDIS data entry page in a firefox Web-Browser
facilitate data collection. The tool‘s main focus is on the The stock of the three tertiary and secondary level pilot
management and planning of the equipments and therefore facilities counted 2120 devices all together with a total net
also captures data on suppliers, service agents, warranty book value of more than 33 Mio. MDL at the time of
contracts and financial matters.
writing. The results also show that the tree facilities together
The department of Biomedical Engineering at the
managed to assign a nomenclature term to 1775 out of 2120
Technical University of Moldova has provided significant
terms (83.7 %). In other words, more than 80% of the
support in e.g. the translation of the user interface and
nomenclature lists or writing of a user‘s manual in local equipment found in the hospital could be denominated using
language. the 325 translated UMDNS terms.
Along with the software, six thematic training modules on As the piloting was successful, the installation of the
Health Technology Management and information systems, software was expanded to three further institutions which
nomenclature use, data management and -analysis, etc. were were involved in the HTM imitative. The local inventory
created. consultant has trained the new users independently using the
The training of the users in three pilot centers was done in training material and the user‘s guide.
a two-day workshop whereby the first day was focusing on As for the hosting of openMEDIS, the project has
theoretical background and the second day involved a managed to transfer and install the application to the web-
practical exercise in a real-life environment. space of the Society of Biomedical Engineers of Moldova
The data collection itself was rather challenging. Even the (SIBM) who is actively involved in the development and
minimal datasets that the system required were difficult to promotion of the management instrument.
obtain. For example, at the hospital level, information about First analysis of the equipment stock in the three pilot
purchase date, expiration of warranty or supplier data was facilities resulted in the summary indicators listed Table 1.
often not present. As a result of absence of systematic The analysis shows that all three facilities own roughly

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the same number of equipment from more than 100 different Thus, decision-makers at facility, regional or national
manufacturers. It can also be seen that Facility #1 (a tertiary level have the opportunity to run queries and to extract the
level referral hospital) has by far the most valuable stock information they are interested in.Another feature of
(21'239'946 MDL) as more sophisticated is in operation openMEDIS is the option to define ―essential equipment‖
there. and customize it for each facility type- and size. Depending
TABLE I. KEY INDICATORS FOR PILOT HOSPITALS on the clinical discipline, MoH or WHO guidelines and
Indicator Facility 1 Facility 2 Facility 3 provide such lists which later serve as a standard to which
Number of assets 680 585 855 the actual inventory is compared with. Concretely, the
Total purchase price (lei) 32'102'060 18'522'648 13'716'653 Moldova-Swiss Perinatology Project is incorporating the
Total remaining value (lei) 21'239'946 9'966'155 1'881'258
Ministry Health‘s standard equipment list for Obstetrics and
Neonatology [9], expanding inventory practices to all
Number of manufacturers 102 119 100
facilities in the country with perinatal services and using
Number of suppliers 21 37 27 openMEDIS as evidence-based planning tool.
Departments with equipment 18 35 29 The open source license of the application allowed
Unique nomenclatures 576 430 769 creating modules and features freely. Properties and
Non-specific nomenclatures 104 155 86 characteristics can be removed or new ones can be added. A
Other summary graphs are also obtainable from the good example is a corrective- and preventative maintenance
system at real time; One of these being a ―histogram‖ module linked to the inventory which is being developed by
showing the age distribution of the inventory. As Figure II the Technical University of Chisinau.
illustrates, there is still a significant amount of equipment in IV. CONCLUSION
place which was purchased before independence in year The situation analysis has shown that an essential
1991. On the other hand, there was little investment made in information system for medical devices should urgently be
the following years until year 2000. implemented in Moldova. The open source application
―openMEDIS‖ has met the needs for an easy to use, flexible
and inexpensive system best.
During the implementation it was shown that
―openMEDIS‖ as a tool to collect data on the medical
equipment stock was a good choice. After training and a few
cycles of quality awareness workshops, the equipment of six
hospitals was entered into the web-based application without
major problems. The pilot activities were also key in
revealing shortcomings in the current documentation system
of medical devices.
One of the biggest challenges was the availability of
human resources. Until recently, the profession of
biomedical- or clinical engineers was not existent in
Fig. II. OpenMEDIS output - graph showing the distribution of the
Moldova and respective working places at the hospitals are
equipment stock (partial data for 6 facilties) only at the stage of development. People responsible for the
heath technologies at the 1st level and 2nd level facilities were
Another graph shows the ―health‖ of the equipment. In head-nurses or deputy chiefs with limited interest and skills
this case (aggregated data from 6 hospitals) 20 % of the for electronic information systems. On the other hand, the
devices are currently not functioning properly or need repair new workforce of Bioengineers was yet lacking practical
(Figure III). experience.
Now that data is available in a standardized and structured Nevertheless, the initiative was widely supported because
format, the possibilities for analysis and aggregation are the power of the openMEDIS tool lies in its ease of use and
nearly unlimited. An intelligent filter in openMEDIS allows the fact that it addresses the issues at management level at
a combination of search criteria. first. This creates acceptance by the decision-makers.
Initiatives towards a (possibly commercial) more
sophisticated and hospital-based Computerized Maintenance
Management System (CMMS), where the focus is rather in
the organization of the maintenance should be deferred.
As the project‘s efforts to establish further maintenance
workshops move along, either a CMMS can be evaluated or
further modules (for maintenance, calibration, billing) can
also be programmed in openMEDIS.
In particular the web-based- and open source architecture
has proven to be suitable to the Moldovan setting. Firstly,
because it can be up-scaled with no extra license fees and
secondly because it can be hosted, managed and supported
remotely.
Fig. III. OpenMEDIS output - graph showning the overall status of the The tool is also appreciated by hospital managers and by
assets
the Ministry of Health. The Ministry is in the process of

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building-up an Agency for HTM and formulating respective GMDN Agency, ―Medical Technology Brief,‖ 2007.
policies and guidelines. It is also in-line with the World [Online]. Available:
Bank funded ―e-Governance‖ initiative and the Government www.eucomed.org/~/media/pdf/tl/2008/portal/aboutind
of Moldova‘s proclamation to put an ICT toolkit in place to ustry/medtechbrief2007.ashx. [Accessed: 02-Mar-2009].
achieve better governance in public health [10]. [2] Medical Device Register, The Medical Device Register.
Grey House Publishing, 2008.
ACKNOWLEDGMENTS
[3] J. Sanders, Where is Technology Taking Healthcare?
The author whishes to express thanks Prof. Sontea who
Where is Healthcare Taking Technology? CADTH
was the leader of the HTM working group, Tatiana
Symposium, 2007.
Buzdugan, who is the local HTM coordinator and Cristina
[4] World Bank, ―Proceedings: International Forum for
Matei, the inventory consultant for the PERINAT and
Promoting Safe and Affordable Medical Technology in
REPEMOL projects. All of them have significantly
Developing Countries,‖ 2003.
contributed to the successful implementation. Also many
[5] R. of M. WHO/Europe, ―Biennial Collaborative
thanks to the Swiss Development Cooperation (SDC) who
Agreement 2010–2011.‖ [Online]. Available:
financially supported HTM in the frame of the two projects.
http://www.euro.who.int/en/where-we-work/member-
REFERENCES states/republic-of-moldova/publications2/bca.
[1] B. Wang, ―A Framework for Health Equipment [Accessed: 29-Apr-2011].
Management in Developing Countries,‖ Hospital [6] ISO 15225, ―Nomenclature -- Specification for a
Engineering & Facilities Management, pp. 1-3, 2003. nomenclature system for medical devices for the
purpose of regulatory data exchange.‖ International
Organisation for Standartization, 2000.
[7] ―openMEDIS - an essential Medical Device
Information System.‖ [Online]. Available:
http://sourceforge.net/projects/openmedis/. [Accessed:
04-Feb-2010].
[8] MoH Moldova, “SERVICIUL PERINATAL
REGIONALIZAT:NIVELURI SI CONTINUT” Ghidul
BNational de Perinatologie. Ministerul Sanatatii si
Protectiei Sociale al Republicii Moldova, 2006.
[9] Government of the Republic of Moldova, ―Activity
Program 2011-2014.‖ 2011.

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Formation of Economic-managerial Knowledge

System within Training of Healthcare Workers
Olga KUDELINA
Siberian State Medical University, Tomsk, Russia
[email protected]
Abstract – Medical personnel are the most important part of resource maintenance of healthcare system, they
make the defying influence on structure developments’ implementation in healthcare reforming. High number of
medical staff characterizes personnel structure of Russia. However, there is imbalance at comparison of rate in
regions of federation, in urban and rural areas that cannot allow delivering qualified medical care widely. That is
why specialists who have economic-managerial skill and able to organize and plan healthcare system development,
are necessary. Medical universities during lifelong education must give attention to forming of managerial and
economic knowledge of healthcare in theirs programs. The programs that have been developed in Siberian State
Medical University are intended to a wide range of healthcare specialists: physicians, head physicians, managers
and nurses.

Index Terms –healthcare system, medical universities, personnel potential, programs of physicians’ training,
staffing.

Main causes of unfavorable dynamics of development of home nursing, and rehabilitation.

healthcare and public health are caused by absence of In these conditions, the organization of economists-
strategic planning and personnel administration, managers training is a necessary component of strengthening
imperfection of financing and legal regulation. Shortage of and development healthcare sector.
the medical personnel in many countries is the deterrent Existence of medical institutions that are various not only
factor of the provision of high-quality medical care [1]. on the organization, but also by the form properties, leads to
Problems of staffing demand the complex approach to their requirement for competent specialists, both for public
decision, and also analytical developments and scientific healthcare, and for economy and management sphere.
support. Graduates of faculty of economy and management in
In previous years Ministry of health and social healthcare of the Siberian State Medical university (SSMU)
development of the Russian Federation gives great value to became such experts.
planning of health manpower, professional and career
development, creation of acceptable working conditions,
especially in primary health care. The structure of staffing in
Russia is characterized by the expressed imbalance at
comparison of indicators in subjects of federation (fig. 1),
thus frequency ratio of such disparities reaches 1,5-3 times
[2,3].
The rate of density of physicians in Tomsk oblast
throughout the last decade increased and has made 66,9 per
10 thousand population in 2009, exceeding average all-
Russian indicators (fig. 1). However, average density of
nurses and midwives steadily decreases: from 105,6 in 2003
to 102,7 per 10 thousand population in 2009 [4].
Thus, despite of increase of quantity of medical workers
in countryside, level of medical staff‘s provision in rural
hospitals differs from city‘s health care facilities in times [5].
Average age of a physician in Tomsk is 48,3±2,31 years, in
oblast areas 54,8±3,14 years, and of nurses - in Tomsk -
54,3±2,95 years, in areas - 58,2±4,12 years.
The ratio of nurses to physicians in our country is much
lower, than in the majority of the developed countries of the
world: 1 doctor on 2 nurses whereas world experience shows
that an optimum ratio is not less than 3-5 nurses on 1 doctor
[1]. The rate of medical workers‘ multiple job holding in
Tomsk oblast on the average is 1,3 lower, than the all-
Russian (1,5), a ratio of nurses to physicians - 2,1.
Deficiency of medical staff in area reaches 13,4 %, nurses -
22,1 %. This imbalance limits possibilities of development
of system of medical care, especially services of aftercare, Fig. 1. Dynamics of medical staff provision in 2003-2009 years

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The specialty 080502.65 - economy and management at existing state educational standard on a specialty are
the enterprise (in healthcare) has been opened in 2003. For a provided.
small interval of the activity faculty of economy and Considering necessity of the exact and systematic
management in healthcare has carried out 12 graduations, economic account and a substantiation of activity of the
having prepared more than 200 experts. Thus for the medical organizations in conditions of healthcare
majority of them the new specialty was the second, and modernization and at realization of the pilot project, the
training and reception of qualification "economist-manager" requirement for professional economists-managers is rather
was necessary for reception of the systematized economic- high. By approximate calculations only in territory of Tomsk
administrative knowledge and desire of the further career oblast, it makes more than 100 experts in a year as
growth in healthcare field. It is no secret that training process economists and the accountants who do not have an
passes with high return, under condition of the expressed overview about technology of rendering of medical care and
motivation of trainees who already have some operational the organization of medical process work in healthcare
experience in health care facilities and other medical system.
organizations. Prominent aspect is the development of system of lifelong
The faculty of economy and management in healthcare medical education, which means constant updating of
conducts training on the basis of secondary education on knowledge, skills of the physician. Obtaining of new
internal (5 years) and the correspondence form (6 years), on economic-administrative knowledge opens additional
the basis of the higher or unterminated higher education on possibilities for continuous professional training and
internally-correspondence (3 years) and correspondence (4 improvement both in the field of the basic specialty, and in
years). Now on a specialty about 300 foreheads are being other allied fields. Primarily, all this can be offered by
trained, including on a budgetary basis on a full-time course medical high schools.
of study. Educational process is realized on all modes of Educational strategy of medical universities should reflect
study as well on a paid basis, and the approach for payment real requirements of the branch. Forecasting of oblast‘s
educational services the differentiated. healthcare modernization‘s requirements area has laid down
Graduates of faculty are prepared for the professional in a basis of designing of various interdisciplinary
work that provides rational management of economy at the educational programs in SSMU.
enterprise of social sphere taking into account branch The department of organization of healthcare and public
specificity, and for work on scientific and pedagogical posts, health takes an active part in education and retraining of
in bodies of the state and local management. personnel. Training of healthcare organizers within the limits
In territory of Siberia, only SSMU has obtained the of internship is conducted. Subjects of postgraduate training
corresponding license and the certificate on the registration, are expanded; new programs with attraction of foreign
giving the right to realization of educational programs of the experts are developed. The department has the settled
higher vocational training, including economy and collaboration on medical informatics with German partners
management at the enterprise (in healthcare) by the results of within the within the bounds of work of e-Health section of
complex check (License A №227772 from 19.02.07, cert. the Koch-Mechnikov Forum (Berlin) headed by professor H.
№0616 from 04.05.07). Hann. For example, in theme «Information technology in
The curriculum on a specialty 080502 - economy and healthcare» materials of lectures kindly given by the
management at the enterprise (in healthcare) in 2006 has professor of R. Engelbreht (Germany, Munich) and manuals
been confirmed by the Information-methodical center on on medical informatics of Institute of medical informatics of
certification of the educational organizations (Shakhty city) University of Braunschweig are used. Within the limits of
and includes all traditional blocks of general and special the international cooperation with the Koch-Mechnikov
disciplines. Forum, there is an academic exchange that allows inviting
The cycle of general professional disciplines reflects all German experts for lecturing and carrying out of seminars.
palette of knowledge and the skills that are necessary for Simultaneously with it, employees of the department can
support of economic, accounting, administrative and exchange experience with German colleagues, improve the
communicative activity of any enterprises. In the block of qualification during participation at conferences and
special disciplines, the subjects reflecting specificity of seminars in the leading medical organizations of Germany.
management of healthcare and medical institutions are More than 150 people are passing thematic and general
presented. For example, medical care quality management, improvement on the department annually; from them 30-40
technology of the outpatient and stationary help, legal % are head physicians of various establishments and oblast
regulation in healthcare, management of medical expenses, healthcare organizations. Therefore, training of economy and
forecasting of healthcare development, etc. Many disciplines management in healthcare is an obligatory component of
are unique; they are developed only for preparation of educational curriculum.
experts in the field of economy and management of Now for accreditation an educational program of
healthcare. In addition, the disciplines of specialization, preparation of bachelors in a direction «Industrial
which allow students to define in a concrete direction of the management» is presented, work on the program
future professional work, are presented: strategic planning at «Innovative activity», which should be started in 2011-12, is
the enterprise, financial management, organization and finished.
economy of general physician practice. The economists-managers prepared at our faculty receive
On study disciplines working programs and corresponding not only full volume of economic knowledge, but also study
methodical support are developed. the organization of healthcare and public health, plunging
For practical skills acquisition and fastening of theoretical thus into environment of medical traditions of one of the
knowledge all kinds of practice in conformity with the oldest medical universities of Siberia. Besides, it has been

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noticed that our graduates in private healthcare (drugstores, European approaches to the decision of problems of
including rural, stomatology clinics, medical associations, healthcare staffing, undoubtedly, will allow to accelerate
etc.), and in administrative structures of city and regional integration of high schools within of Bologna Accords, and
healthcare where new innovative approaches are most finally to improve public health and economic efficiency of
actively used at economic activities conducting. management of the entire system of healthcare as a whole.
New educational standards not only meet the level of REFERENCES
modern medical and biologic knowledge and guarantee [1] Handbook on Monitoring and Evaluation of Human
quality of given medical care, but also are economically Resources for Health with special applications for LOW
proved. Thus, at a stage of high school training of the future - and middle-income countries, Geneva, WHO, 2009,
expert the correspondence of educational standards with 188 p.
standards of rendering of medical care is necessary. [2] Svetlichnaya T.G. The actual problems of the
In the nearest future, it is necessary to pass to personnel professional personnel supply for regional public health,
selection planning in each subject of the Russian Federation Problems of social hygiene, healthcare and history of
based on the Federal register of medical workers and medicine, no. 3, 2008, pp. 38-41.
developed standard documents, including documents, [3] Mikhailova Yu V., Son J. M., Sokhov S.T., Danilova
concerning a target enrolment of students. Therefore, N.V., Shestakov M.G., Sasina N.S., Takhtarova Yu. N.
development of the innovative program of professional Development of the health care personnel potential:
training in territory of Tomsk oblast is priority for SSMU state-of-the state and prospects. Healthcare of the
and the department of healthcare of the oblast. Russian Federation, no. 1, 2008, pp. 52-54.
The medical high school should become an active [4] Healthcare of the Tomsk region in 2010. The statistical
participant of healthcare developments and initiator of collection. Tomsk: OSIH «Bureau of medical statistics»,
innovative projects in the branch. 2011, 67 p.
It is necessary to restore and expand the lost traditions of [5] Oreshin A.A., Kudelina O.V., Khlynin S.M. Prospects
interaction of medical high schools of the post-Soviet for development of medical care in the Tomsk Region.
territory. Exchange of experience, joint development and Healthcare of the Russian Federation, no. 6, 2009, pp.
adaptation of the educational programs based on the all- 48-50.

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Towards an Images Dataset Processing trough

Supervised and Unsupervised Learning
Nicoleta ROGOVSCHI Nistor GROZAVU
LIPADE, Paris-Descartes University, France
[email protected]
LIPN, Paris 13 University, France
[email protected]

Abstract – Internet offers to its users an ever-increasing number of information. Among those, the
multimodal data (images, text, video, sound) are widely requested by users, and there is a strong need for
effective ways to process and to manage it, respectively. Most of existed algorithms/frameworks are doing
only images annotations and the search is doing by these annotations, or combined with some clustering
results, but most of them do not allow a quick browsing of these images. Even if the search is very quickly,
but if the number of images is very large, the system must give the possibility to the user to browse this data.
In this paper we investigate the use of the supervised learning to classify an images dataset and the
unsupervised learning to browse the images. In our proposed schema, we used both PCA and LDA to
transform the feature space and then to classify the dataset. We used this technique for all five datasets
available on the challenge web site of The German Traffic Sign Recognition Benchmark: HOG1, HOG2,
HOG3, HueHIst and Haar [7]. Finnaly we used a voting approach to find the consensus for all five partitions.
Also, an application to the images browsing is shown using the topological unsupervised learning.

Index Terms – content-based image retrieval, topological learning, clustering, self-organizing maps.

methods, and feature transformation techniques as Principal

Component Analysis (PCA) and Linear Discriminant
I. INTRODUCTION
Analysis (LDA).
Producing visual data/content in digital form, even the
We observed that we can increase the classification result
visualization of the numerical data is becoming more and if the feature space is transform using a principal component
more common and affordable. Images datasets are becoming analysis technique.
more common and widely used as visual information is The traditional text-based approaches to image retrieval
produced at a rapidly growing rate. have proven out to be inadequate for many purposes. In
Creating images and storing them became an easily and some occasions, image databases have associated captions or
very used process for general use. Consequently, the digital other text describing the image content and these annotations
visual libraries are growing and there is a strong need of can be used to greatly assist image search. Manually
adequate solutions to process this data and to extract relevant annotating large databases takes, however, a lot of effort and
information from it. raises the possibility of different interpretations of the image
The German Traffic Sign Recognition Benchmark content. As a result, content-based image retrieval (CBIR)
competition task [7] is a multi-class classification problem. has received considerable research and commercial interest
The dataset consists of 39209 images where 26640 are for in the recent years. One of the challenges is to automate the
training and 1569 images are for the test. process of image retrieval and to make it separately from
Five pre-calculated features sets were available for the text annotation [5].
Challenge: three sets of HOG features, Haar-like features One of the most interests and used technique for data
and Hue Histograms having the size: reduction and visualization in machine learning are the Self-
- HOG1: 1568 features; Organizing Maps (SOM) proposed by Kohonen in 1998.
- HOG2: 1568 features; This approach was used for image retrieval system called
- HOG3: 2916 features; PicSOM [5] which use the tree structured SOM (TS-SOM)
- HueHist: 256 features; [4].
- Haar: 11584 features; In this work we propose a novel technique which proposes
The first phase to do when deal with large dataset is to to use the lwo-SOM [1] to attempt a 3D visualization and
transform the features space and to detect the irrelevant browsing of the dataset.
variables. The rest of this paper is organized as follows: We show in
The second step is to apply a classification approach on section 2 the used feature transformation and dimensionality
the new dataset to learn a model and to affect the test data. reduction approach. The supervised learning and the fusion
Finally, the last phase is the fusion of all the results technique used in the proposed method (section 5) are
(classification of the all) in order to obtain a global presented in sections 3 and 4. In section 5.A we describe the
classification result combining all five pre-calculated proposed unsupervised learning for images clustering and
features. browsing, and we show the results using this technique on
We tested several supervised learning approaches to the Wikipedia images. Finally we offer some concluding
obtain high classification accuracy as: neural networks based comments of the proposed method and the further research.

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II. FEATURES TRANSFORMATION AND this 'scree'. We therefore needed to identify the point of
DIMENSIONALITY REDUCTION maximum deceleration in the curve.
Principal component analysis (PCA) is a popular data Figure 1 shows an example of a curve generated using a
processing and dimension reduction technique. As an un- data vector.
supervised learning method, PCA has numerous applications
such as handwritten classification, human face recognition,
etc.
There is a strong link between the self-organizing maps
(SOM) and PCA, as they have the same goal, i.e. to reduce
the dimension and to visualize the dataset. This is why; we
will use the both SOM and PCA as a pre-processing step for
our model.

The PCA algorithm is presented as following:

Let the data X be a nxm matrix, where n and m are the
number of observations and the number of variables,
respectively.
The PCA estimation problem can be equivalently
formulated as the following optimization problem, in which
the sum of estimation errors from all variables is minimized:
Figure 1: The Scree Test Acceleration Factor

We thus executed the following steps presented in the

Algorithm 1.
Algorithm 1: The Scree Test Acceleration Factor
Input: a vector  j size d
x̂i are the i-th measured and estimated For i = 1 to d Sort the weights in descending order  [ j ] .
where xi and
ẑ Thus we obtaina new order
observation, and i represents the the estimated principal  [ j] =( .[ j],1,  .[ j],2 ,..., .[ j],i ,..., .[ j ],d ) ; where i indicates
component corresponding to the observation xi.  theindex order. 
In order to detect the number of eigenvalues values, we
use the Cattell's Scree Test which is a graphical method first End for
proposed by [8].  For j = 1 to d (on the sorted vector)
The basic idea of the Scree test is to generate, for a
principal components analysis (PCA), a curve associated Compute the first difference df i =  .[ j],i   .[ j],i1 and we
with eigenvalues, allowing random behavior to be identified obtain the vector  [df1j]

(a simple line plot). Cattell suggests finding the place where 

End for
the smooth decrease of eigenvalues appears to level off to
the right of the plot. To the right of this point, presumably, For p = 1 to d (on the  [df1
j]
vector)
one finds only "factorial scree". Non graphical solutions to 
Compute the second difference (acceleration)
the Cattell scree test are also proposed: an acceleration factor acc i = df i  df i1 obtaining the vector  [dfj ]2
and the optimal coordinates index. The acceleration factor 
indicates where the elbow of the scree plot appears. It End for 
corresponds to the acceleration of the curve, i.e. the second
For l = 1 to d (on the  [dfj ]2 vector)
derivative. Frequently this scree is appearing where theslope

of the hill changes drastically to generate the scree. It is why Find the scree: max i abs(acc i )  abs(acc i1)
many researches choose the criterion eigenvalue where the
slope changes quickly to determine the number  of End
 for
components for a PCA. It is what Cattell named the elbow. 
OUTPUT:
So, they look for the place where the positive acceleration of 
the curve is at his maximum. Cattell's scree test and Bartlett's Retain all the features displayed before the scree (we used
chi-square test for the number of factors to be retained from the initial index values of features before sorting).
a factor analysis are shown to be based on the same
A.Complexity of the Scree Test procedure
rationale, with the former reflecting subject sampling
The Scree Test acceleration procedure has four steps until
variability, and the latter reflecting variable sampling
finding the scree in the vector. We will analyze all these
variability. In the Cattell scree method, we can interpret the
eigenvalues as the degree of relevance of each factor axis. steps:
The concept of covariance or correlation matrix is not • Ascending sort: to made the sort of the weight vector
appearing and is not necessary. Therefore, this method is not we are using the Merge sort procedure which has an
specific to PCA or a factorial analysis. The number of logarithmic complexity: O(d log d) ;
variables retained is equal to the number of values preceding • First difference: the complexity for the first difference

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df i is the O(d) ; Algorithm 2 : Proposed method

• Second difference: for the second difference the
Input: images vectors vector xi … xn
complexity is the same as previously: O(d) ;
  • Find the scree: to find the scree in a vector, the For i = 1 to n (for all datasets)
complexity will be O(d) . PCA with U 1100 eigenvectors on the train data
As there is no nested loop,
 the total computational time
For j=1 to m (on the development dataset) :

for the Scree Test acceleration algorithm is the sum of the
complexity of the four steps, and respectively it will be
O(d logd 3d) .
Apply LDA on the U and obtain the model M;
End For
III. CLASSIFICATION
As classification model we test the supervised Self- Plot the test data on the same features space using the U and
 Organizing Maps and the Linear Discriminant Analysis, and obtaining Ut;
we note that the use of the PCA improves the classification Affect the Ut to the model M;
results. So, for all the dataset the LDA were used.
Given a dataset X size nxm, where X = x1, x2, ..., xn End For
represents the set of object with m features.
Output: Label of the test data;
Let, B R nxp be the transformation matrix that maps
We repeat the algorithm for all five datasets by computing
these features to p-dimensional features, i.e.
the accuracy index for all of them.
z j R p (j=1,...,m), and z j  BT x j .
At the end we use a fusion technique to fusion the
classification results using a voting approach.
VI. EXPERIMENTAL RESULTS
Using the proposed method to all datasets, we obtain a
classification accuracy index equals to 95.47 %, but we
found that using only the HOG2 and HOG3 datasets, the
accuracy index grow up to 96.53%.
Note that we classified the dataset using the LDA
algorithm on the result of a PCA with 1100 eigenvectors.
A.Visualization
is the within-class covariance matrix, and
Even the topological learning methods doesn't improve
the results for this challenge compared to the PCA and LDA,
it allows the visualization of the classification results.
So, in this section we show an example of an extended
is the between-class covariance matrix. SOM algorithm to classify and to browse a images dataset
Indeed to use the initial dataset as input for the LDA proposed by Rogovschi and Grozavu [9].
method, we use the eigenvalues vectors issues from the 1)Images topological map browsing
The topological learning allows building a multi-level
PCA.
map which could be benefit to browse an images dataset by
IV. FUSION levels.
There are two types of combining classification Firstly, we visualize the map with the best matching units
(clustering) results: the fusion and the collaboration. (the most representative images) and then, we can choose the
The goal of the fusion based techniques is to find a next level to visualize (or to skip some levels) until we are
consensus for all the results using a fusion approach, as is satisfied of the result. This process is doing in a 3D
the voting procedure. Contrarily, the collaborative (hierarchical) visualization by displaying the maps with the
classification is based on the changing the information corresponding captured images step by step like shown in
during the learning process. the figure 1.
For this challenge, we tested the both types of methods, Our purpose is to automate the browsing task using not
and we conclude that for these datasets, the better one is the only the annotated text, but also the similar images founded
fusion method. during the unsupervised learning.
As fusion method technique we use the voting principle. The idea is to present an images map to the user in order
to detect not only the searched image, but also the similar
images from the map (neighbored cells using the Euclidean
V. PROPOSED METHOD distance). Furthermore, a cell from the map (the best
We introduce in this section the proposed methodology matching unit) can be used to represent many others similar
using the principal component analysis within the Cattel pictures, and will accurately suggest the kinds of pictures
ScreeTest and Linear Discriminant Analysis for the that will be found by exploring the respective cluster.
classification. The method is used for all five datasets and The figure 1 shows the map with the best matching units
the classification results (the labels vectors) are used to find
(first level), and the next 3 levels of the maps. For each map
the consensus by applying a voting technique.
the neighborhoods displayed images are correlated between

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them, and one can detect also some cells which are empty, on the challenge of The German Traffic Sign Recognition
because there are cells which captured only 1, 2, or 3 Benchmark obtaining good results.
images. So displaying the map level which is greater then For the unsupervised learning, we presented a novel
the size of the captured images vector for a cell, the solution for manage and process visual datasets. We used the
respective cell will display an empty (white) image to show lwo-SOM [1] which allows us to do a better classification of
that where are no more correlated images to the last one. the data and to obtain more correlated images on the map.
As future work, the fusion of both methods (to classify
and to browse the images dataset) will be an interested
challenge.
REFERENCES
[1] N. Grozavu, Y. Bennani, M. Lebbah. From variable
weighting to cluster characterization in topographic
unsupervised learning. IJCNN, Atlanta, USA, 2009.
[2] C. Julien, and L. Saitta. Image databases browsing by
unsupervised learning. ISMIS, 2008.
[3] T. Kohonen, Self-Organizing Maps. Springer Berlin,
2001.
[4] P. Koikkalainen. Progress with the tree-structured self-
organizing map. In Proc. 11th Europ. Conf. Artificial
Intell., 1994.
[5] M. Koskela. Interactive image retrieval using self-
organizing maps. Dissertation Repport, 2003.
[6] F. Perronin and C. Dance. Fisher kernels on visual
vocabularies for image categorization. page 1-8, 2007.
[7] Johannes Stallkamp, Marc Schlipsing, Jan Salmen, and
Christian Igel. The German Traffic Sign Recognition
Benchmark: A multi-class classification competition. In
submitted to International Joint Conference on Neural
Networks, 2011.
[8] R. Cattell. The scree test for the number of factors.
Multivariate Behavioral Research, 1:245–276, 1966.
Figure 2. Images DataSet browsing using lwo-SOM technique. [9] Rogovschi N., GROZAVU N. (2010), « A content-
based image retrieval system based on unsupervised
VII. CONCLUSION
topological learning», in Proc. ICMIA'10 : IEEE
In this paper we adapted the supervised and unsupervised
International Conference on Data Mining and Intelligent
learning to deals with an images dataset. For the supervised
Information Technology Applications, November 30 -
learning we used the PCA and LDA algorithms coupled
December 2, 2010, Seoul, Korea.
within a fusion approach. This new methodology was tested

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Use of Telemedicine in Pilot Centers within the

Perinatal System
P. STRATULAT*, Tatiana CARAUȘ*, M. BLUNIER**, Ala CURTEANU*
*- Mother and Child Research Institute from the Republic of Moldova
**- Swiss Tropical and Public Health Institute
Abstract – In the last decade of the twentieth century in many countries rapidly has developed telemedicine.
Telemedicine is not a separate discipline within the health system, but a "transfer of information at distance regarding
patient's medical care." In the Republic of Moldova telemedicine implementation into perinatal system started in 2009
in four pilot centers: MCRI (level III), CP Hospital no. 1 Chisinau, CP Balti and CP Cahul (level II). Thus the creation
and development of this interdisciplinary network of teleconsultation and telediagnostic has followed the
improvement of health care services quality and decrease of their costs, increasement of quality of patients life in
perinatal system, orienting themselves to consultation of serious neonatal and obstetric cases from level II Perinatal
centers. Although it’s on its beginning, telemedicine network in the frame of perinatal sytem has already achieved
success. Cooperation between specialists from levels II and III of perinatal care has strengthened, interactive work
and multidisciplinary cooperation between obstetricians-gynecologists and radiologists, imagists have strenghtened
also.

VAP and SiPap parameters, monitors within the

I. INTRODUCTION
consultations with II level pilot centers.
In the last decade of the XXth century the Telemedicine
has rapidly developed in many countries. Telemedicine is
not a separate discipline within the health system but a
„transfer at distance of the information regarding medical
care for a patient‖. Telemedicine represents a potential to
improve medical care worldwide through the diversification
of medical services which will be offered to communities
and individuals who do not have the access to these services,
both from urban and rural areas. In addition, Telemedicine
can help to attract and retain in rural areas health
professionals in the medical field via continuous education
and collaboration with other professionals in the field from
other centers (tertiary, educational [1,2,3].
II. MATERIAL AND METHOD:
In the Republic of Moldova the implementation of the
Telemedicine into perinatal system started in 2009 in four
pilot centers: MCRI (level III), PC Hospital nr. 1 from mun.
Chisinau, PC Balti and PC Cahul (level II). Thus, the
creation and development of this interdisciplinary network
of telediagnostic and teleconsultations aimed to improve
quality of health care and to lower their costs, to increase the
quality of patient‘s life from perinatal system being oriented
to the consultation of neonatal and obstetrical cases from II
level perinatal centers. This component of the Project offers
a possibility to consult, make diagnosis and carry out
medical trainings at distance for all medical staff within the
perinatal system between III level institutions and II level
pilot centers with the help of lecturers from the Medical
University ‖Nicolae Testemițanu‖; unclear or difficult cases Fig.1. The Telemedicine system within the perinatal system of the Republic
of Moldova
must be consulted with specialized clinics from abroad.
Thus, the pilot institutions, where 40% out of total number The Telemedicine‘s implementation was approved by the
of deliveries take place and where severe newborns and MoH Order nr.285 from 18.08.2009 ―On implementation of
premature babies are concentrated, have been identified Telemedical consultative system in perinatal pilot centers‖
during the first stage. The number of working places from in 4 pilot centers: MCRI (level III), PC Hospital nr. 1 from
wards and NICU from pilot institutions has been identified. mun. Chisinau, PC Balti and PC Cahul (fig.1). According to
16 computers with web cameras, color printers, scanners and this Order, the list of specialists who will activate as
digital cameras have been procured to document data for consultants from the Departments of Obstetrics, Gynecology
clinical cases as much complete as possible, later 3 more and Neonatology from the Medical University ‖N.
notebooks were procured for presentation of newborns, of Testemițanu‖ was created. Also, through the telemedicine

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system the MCRI, level III perinatal center within the examinations data exposed in the questionnaire of Perinatal
regionalized system, carries out consultation of severe Health group, as well as of Rx examination data or other
neonatal and obstetric cases from level II perinatal centers. investigations placed at the iPath platform. Diagnosis is
Unclear and difficult cases from MCRI are consulted with made in real time by doctors-consultants who decide which
the specialized clinics outside the republic. During the must be the tactics of investigations, treatment or where the
second phase the obstetric and neonatal cases needed to be patient must be transported to receive the appropriate
placed at the iPath platform were identified. treatment as soon as possible. During the past year,
This platform for Telemedicine was designed for the specialists from the second level pilot centers have benefited
Republic of Moldova to facilitate the exchange of from consultations of images (radiography and USG).
information and communication between professionals Weekly the teleconferences of neonatologists from the
working in health sector providing the following pilot institutions are held in the morning: every week on
functionality: creation of discussion groups on various health Tuesday and Friday doctors from all departments of the
topics being a link of continuous education to perinatal MCRI take part in these conferences, the cases are presented
system. National working group together with consultants briefly in a narrative form, the results of investigations are
from Switzerland have identified and created four working reported, then it is made the contact with NICU from pilot
groups that are placed at local international platform iPath: PCs (Hospital No.1, Balti and Cahul) which present severe
 Test group and complicated cases that took place over a week and have
 Perinatal Health been placed at iPath, there is a possibility to show the baby
 Regional Group (Moldavian-Romania-Ukrainian) via video at notebook. A positive factor is the participation
 Health Technologies Management of doctors from pilot centers in these clinical conferences,
Initial areas of users‘ interest are Telemedicine in perinatal those who are present have the opportunity to ask questions,
system and Health Technology Management; within each of to express their opinion on the diagnosis and treatment of
the discussion group the members can: present and discuss patient, thereby increasing the quality. Next is the
cases (medical) in order to exchange information and description of the pilot centers‘ experience in use of iPath
opinions, organize consultations at distance via which the platform. During this period of time, until 01.03.2011, 163
specific cases are presented to colleagues to provide a of users became registered at iPath platform, out of them:
second opinion. obstetricians-gynecologists 79 (49%); neonatologists – 48
On this platform the following specialists are registered: (20%); doctors-imagists – 3(2%); other professionals – 33
obstetricians/gynecologists, neonatologists, radiologists, (29%). In 2010 over 300 of emergent Telemedicine calls
pathomorphologists, traumatologists and other professionals. took place, all from 3 II level PCs from the country (PC
Currently, the Telemedicine system in perinatal system Hospital nr.1 from Chisinau, PC Balti and PC Cahul).
offers us: In the frame of the Working Groups 376 cases totally were
1) Teleconsultations in specialization of obstetrics and registered on the platform:
neonatology (during 24 hours) 1. Group Perinatal Health – 330 (305 clinical cases +
2) Teleradiology - on-line consultation of radiological 25 information).
images during 24 hours; 2. Test group – 40.
3) Teleeducation - training for specialists at distance. 3. Regional Group (Moldavian-Romanian-Ukrainian)
in Perinatal Health –
III. RESULTS: 4. Health Technologies Management – 41
(instructions, guidelines for users, regulations,
forms which are elaborated in clinical departments
to ensure the equipment‘s maintenance).
Out of 376 of cases placed on the platform the specified are
the following: obstetric cases – 79(21%); gynecological –
1(0,26%), neonatal – 270 (72%), pediatric (sugar) –
1(0,26%) and other information (guidelines, protocols,
traduced articles ) - 25 (7,0%).
There were comments placed for 223 cases (63, 7%),
Fig.2. On-line consultation at distance via iPath network by III level those confirming the diagnosis - 92%, treatment – 90%, and
specialist, consultation of neonatal case from PC Balti medication– 91%. Thanks to teleconsultations offered to
The Telemedicine System within perinatal service is the patients from II level pilot centers, especially from the Balti
first unit in the country where the teleconsultations, Perinatal Centre and Cahul Perinatal Center, the
investigations of patients at every level of the country are transportation of patients to level III has decreased by 30%,
practiced effectively and can easily be followed and thus reducing the costs for newborns transportation to III
interpreted on-line by specialists from III level, where level and travelling of specialists within AVIASAN service.
consultations at distance via audio-video connection are In Phase III (2011) the Telemedicine service will be
provided. After the birth of a severe baby in one of II level extended to other II level perinatal centers, which will be
Perinatal Centers, the specialist from the territory during the equipped with audio-visual equipment and Internet
first 2 hours comes into contact with one of the consultants connection.
from the level III (MCRI), the consultation is provided on IV. CONCLUSIONS:
the basis of audio-video communication, as well as via 1. Although it is on its first stage, the Telemedicine network
tracking of health indicators (Ps, TA, FR, SaO2), laboratory within perinatal system has already achieved the success.

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 International Conference on Nanotechnologies and Biomedical Engineering , Chişinău, Republic of Moldova, 7-8 th of July , 2011

2. The cooperation between specialists from II and III level support of parents of high risk newborn infants.
of perinatal care, multidisciplinary collaboration and [2] Chan DS, Callahan CW, Sheets SJ, Moreno CN,
interactive work of obstetricians-gynecologists, radiologists Malone FJ. An Internet-based store-and-forward video
and imagists have been strengthened. home telehealth system for improving asthma outcomes
3. The educational part has improved – the level of in children. American Journal of Health-System
knowledge has increased (precision of diagnosis, treatment) Pharmacy 2003;60:1976-81.
and, as a result, practices and quality of care were also [3] Jaatinen PT, Forsstrom J, Loula P. Teleconsultations:
improved. who uses them and how?. Journal of Telemedicine and
4. Motivated by a continuous desire to increase Telecare 2002;8:319-24
effectiveness/costs, we succeeded that the teleradiology [4] Introduction to telemedicine / Ed. by R. Wootton, J.
became a significant part of everyday practice. Craig. – London: The Royal Society of Medical Press,
5. Telemedicine ensured saving of time and financial 1999. – 208 p.
resources provided for necessary transportation (has [5] Coiera E. Guide to medical informatics, the Internet and
minimized the number of travelling of Aviasan specialists telemedicine. – Chapman and Hall Medical, 1997. – 376
for consultation of case). p.
[6] Spooner SA, Gotlieb EM. Telemedicine: pediatric
REFERENCES:
applications. Pediatrics 2004; 113Șe639-43.
[1] Kenneth Tan, Nai Ming Lai. Telemedicine for the

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SonaRes - Computer-Aided Approach for

Advanced Ultrasound Medical Diagnostics
Liudmila BURTSEVA, Svetlana COJOCARU, Constantin GAINDRIC,
Olga POPCOVA, Iulian SECRIERU
Instiitute of Mathematics and Computer Science of the Academy of Sciences of Moldova
[email protected]
Abstract – Ultrasound image is the primary (input) information for every ultrasound examination. Despite
the difficulties of ultrasound image interpretation, this source of information is still significant for diagnosis
decision making. This paper describes the experience of SonaRes diagnostic decision support system (DDSS)
for ultrasound examination development. Considering two-layer structure of the information contained in
ultrasound images, two main approaches in DDSS creation may be distinguished: Image-based systems and
Knowledge-based systems. In the SonaRes the advantages of both are combined. In the process of any DDSS
development there are three points of major importance, influencing essential the success: i) knowledge
acquisition and formalization; ii) image processing and search for similar ones, and iii) interaction with user
[1]. SonaRes – represents one of the possible solutions to these problems aimed at increasing the DDSS
functionality, user attitude and, as a result, adequacy of generated conclusions.

Index Terms – computer-aided approach, knowledge, ultrasound image, decision support, medical
diagnostics.

specialists. Besides the difficulties of ultrasound image

I. INTRODUCTION
interpretation, because of the speckle, tissue related textures
Diagnosis is a process consisting of separate steps. These
and artifacts, this source of information is still significant for
steps begin with establishing the certain facts in the process
diagnosis decision making.
of examination and lead to the inference that the obtained
Computer-aided diagnosis schemes has been subject to
facts correspond to some conclusion or begin with some
various research since 1980, when a number of medicine
preliminary diagnosis achieving the conformity of the set of
domains began to use computer assistance [2]. During these
objective facts of the patient state to confirm the presumptive
years, huge databases of medical images were created and
diagnosis or reject it, if the facts do not correspond to or
became a powerful source for decision making. Taking into
contradict the assumption.
consideration these tendencies, two main approaches to
In general case DDSS medicine are not intended to
create DDSS systems can be distinguished:
replace the physician, their role being to give clinician
 Image-based systems;
recommendation on his request or draws automatically his
attention to the special cases (cases of alerts).  Knowledge-based systems.
Obviously, DDSS are targeted on a specific area, which A joint realization of decision making and image retrieval
in DDSS development leads to new explicit domain-specific
may be more or less broad, and the domain of their
knowledge and better results in many applications.
applicability is defined by a pathology (a group of
Moreover, research in medical image analysis tries to find
pathologies) or a diagnostics method, which in its turn is
links between image features and knowledge in order to
oriented to certain pathologies (group of pathologies or
organs). The subject of our work is development of decision fulfill quantification tasks and to answer prognostic
support systems for diagnostics based on ultrasound questions.
examination. There are three points of major importance, influencing
essential the success of DDSS, are the following:
II. DECISION SUPPORT SYSTEMS IN ULTRASOUND  Knowledge acquisition and formalization;
DIAGNOSTICS  Image processing (with extraction of knowledge
The ultrasound examination of patients, being non- from the images, if possible) and search for similar
invasive and not expensive, is a basic technique of medical ones;
imaging.  Interaction with user.
Ultrasound image is the primary (input) information for The way these issues are resolved determines the
every ultrasound examination. The main characteristic of
functionality, user attitude and, as a result, adequacy of
these images is two-layer structure of the information
generated conclusions.
contained in it. The first layer is the image itself (graphical
In what follows, we will discuss these points, basing on
features), and the second layer is its textual description in
solutions realized in the SonaRes – a Diagnostic decision
medical terms (medical features).
support system for ultrasound examination of the abdominal
However, utilization of this technique does not always
region.
come up to expectations, encountering some difficulties
associated with the dependence on operator, which affects III. KNOWLEDGE ACQUISITION IN ULTRASOUND
the quality of the obtained images, and the way the results DIAGNOSTICS DOMAIN
are differently described and interpreted by several There are 5 main stages in the development of knowledge-

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based systems [3]: knowledge base generator, accessible to expert with

1. Problem identification; intuitively clear graphical interface – ExpShell [5]. In this
2. Knowledge acquisition; case the expert himself had to supervise the process of
3. Knowledge structurization; knowledge base filling from the beginning up to the end, but
4. Knowledge formalization; the "knowledge engineer" only defines the method of data
5. Prototype development. storage and representation.
The phase of knowledge acquisition and formalization is ExpShell allowed expert to describe the subject domain in
considered as the key one for the development of medical a free form. The expert has possibility to work simple and
computer-assisted systems (decision support, adaptive clear only in two routines: 1. filling the list of facts, used in
training, learning, etc.). gallbladder ultrasound investigation domain; 2. selecting
During the second stage of the development of already introduced facts and establishing in graphical
knowledge-based systems – knowledge acquisition – the interface the existent relationships between the facts –
expert competence and knowledge should be transferred to connections of type →, & and ¬. As the result a decisional
"knowledge engineer", aiming the "knowledge engineer" to graph that describes a diagnostic feature / pathology /
obtain the fullest subject domain representation. The process anomaly of gallbladder is obtained. Using this ExpShell,
of knowledge acquisition in ultrasound investigation domain expert knowledge considered the most important (58 facts
on an example of separately taken organ (gallbladder) is and 30 decisional graphs) was acquired.
described in details in [4]. The analysis of the acquired knowledge has shown that its
The necessary knowledge about ultrasound investigation further use for decision-making process is very difficult
of gallbladder was acquired from the experts-physicians: because of its weak structurization. Since there was no clear
 Gallbladder localization information (including distinction between the facts and rules, the additional
methodology of visualization in typical location, verification of acquired knowledge was required (often the
objective conditions of non-visualization or difficult same diagnostic feature, participating in different
visualization in typical location, causes of non- pathologies, was described by different sets of facts).
visualization in typical location); Therefore, the tactics of knowledge structurization was
changed.
 Information about the gallbladder pathologic states
Since the quality of acquired knowledge is the
(chronic cholecystitis, compressed gallbladder,
determinant factor in successful realization of any
scleroatrophic gallbladder etc.);
knowledge-based system, the decision was to turn to the
 Principal characteristics of gallbladder description traditional method of knowledge acquisition (with
(dimensions/volume, shape, tonicity, gallbladder participation of "knowledge engineer") [6].
contour etc.);
 Gallbladder anomalies and pathologies information, V. KNOWLEDGE REPRESENTATION SCHEMES
every anomaly or pathology being determined by At the forth stage of the development of knowledge-based
changes in principal characteristics of gallbladder systems – knowledge formalization – the representation form
description (dimensions anomalies, shape (language) for acquired and structured knowledge should be
anomalies etc.). selected. The formalized representation of problem domain
concepts is created basing on of the chosen knowledge
IV. ASPECTS OF KNOWLEDGE STRUCTURIZATION representation form.
IN UNSUPERVISED EXPERT‘S WORK The fundamental goal of knowledge representation is to
At the third stage of the development of knowledge-based represent knowledge in a manner to facilitate drawing
systems – knowledge structurization – the structure of the conclusions (inference) by the computer-assisted systems.
subject domain acquired knowledge (the list of the basic We distinguish two approaches – single and hybrid
concepts and their attributes, the relationships between them, knowledge representation schemes.
the structure of the input/output information, decision- There is no single or hybrid scheme to satisfy end-users
making strategy, etc.) should be defined. The aim is to preferences and/or all the requirements of knowledge-based
obtain the informal knowledge description of the subject systems developers. So, taking into account only the system
domain as a graph, a table, a diagram or a formatted text. requirements on the knowledge acquisition stage, one can
In the beginning, the loss in knowledge acquisition say that semantic nets, decision trees, frames and description
dialogue was considered the most essential drawback at the logics are more suitable to represent medical knowledge [7].
interaction expert-"knowledge engineer", when the volume For SonaRes system we have chosen the decision tree as a
of information, possessed by the expert, differs from the model of acquired knowledge representation. Basing on the
remembered and communicated one, that is much more than principles of the decision tree scheme, the knowledge base
information, listened by "knowledge engineer", and finally, of gallbladder ultrasound examination domain has been
essentially differs from knowledge volume, formalized and established.
stored in knowledge base. Moreover, the information
received from the expert can be apprehended incorrectly by VI. KNOWLEDGE STRUCTURIZATION AND
the "knowledge engineer" that will cause mistakes in FORMALIZATION DURING EXPERT-"KNOWLEDGE
knowledge base. So, the time-consuming procedures of the ENGINEER" INTERACTION
explanation and additional control are necessary, leading the The information obtained from the experts-physicians was
time, spent for interaction between the expert and the structured, formalized and introduced by the "knowledge
"knowledge engineer", to influence terms of knowledge base engineer" in knowledge base (a pyramid of meta-concepts,
creation. Therefore, was created an expert environment – and a set of rules created on its basis), marking out 9 main
characteristics for gallbladder ultrasound investigation,

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representing principal nodes. Other nodes are connected to  The interface should be adaptive. It should change,
principal ones by hierarchical links, forming a tree structure depending on time available to the end-user to make
of "attribute" and "value" nodes. The knowledge pyramid a decision. In addition, the interface should conform
has 335 nodes with at most 9 deep levels. to the basic forms of end-user diagnostic thinking.
Using obtained knowledge pyramid, 54 decision rules for  The interface should not restrict unnecessarily the
gallbladder pathologies and anomalies determination were end-user's actions.
created. The analysis of 54 rules obtained for gallbladder  The interface should be oriented on the restricted
shows, that in addition to the normal state and anomalies, we screen space and on limited decision making time.
also embraced all basic groups of pathologies. Moreover, The end-users often have to use the system in an
creation of the rules with a simple structure gives possibility
emergency or in a network mode.
to describe diagnostic of some simple structures and solitary
The dialogue is the most common form of communication
lesions, as well as of any complex pathology, which consists
and information transfer. Therefore, the organization of the
of several separate pathologies: for instance, acute user interface as an ordered set of questions is justified.
gangrenous lithiasic cholecystitis associated with solitary
The essence of the proposed new representation approach
adenomatous polyp and focal cholesterosis. Description of
is the separation of knowledge into one, used in the inference,
the complex pathologies can be obtained by combining the
existing rules. The obtained knowledge base describes and other, used only in the interface [7].
At the first step of the creation of the alternative
completely the ultrasound investigation process of
representation of the knowledge base there were determined
gallbladder.
Common work of the "knowledge engineer" and experts those facts of the decision tree, which are involved in the
has shown that in ultrasound investigation domain the inference.
reasoning with metaconcepts (facts) and knowledge For each fact a question concerning the existence or non-
representation as a pyramid completely corresponds to the existence of this fact was formulated. For instance, for the
experts‘ mentality and thinking. However, the division of fact F1=<gallbladder volume, normal> there was formulated
metaconcepts up to the level of objects, concepts and their the question Q1="Is the volume of gallbladder a normal
attributes, and construction of further reasoning on their base one?", for the fact F2=<gallbladder volume, enlarged> – the
is not always clear to the experts, especially, if we demand question Q2="Is the volume of gallbladder enlarged?", and
this at the initial stage of knowledge acquisition. for F3=<gallbladder volume, reduced> – Q3="Is the volume
of gallbladder reduced?".
VII. KNOWLEDGE MANAGEMENT TECHNIQUES
As a result, 203 questions were formulated. Answering to
The development of the user‘s interface for the medical
some of these questions, the user can describe the case from
computer-assisted systems basing on the decision tree can
gallbladder ultrasound investigation domain. All of 54
lead to various problems and inconveniences. The main lack
is the fact that the user‘s interface does not correspond to the pathologies and anomalies of this domain were described in
daily work and habits of the end-user – physician. Moreover, terms of these questions.
the discrepancy of the user‘s interface of the medical At the second step we have stored all existing
computer-assisted systems and with the form of physician‘s relationships between the facts. So, we have elaborated an
diagnostic thinking may become the reason of different interconnection system between all formulated questions.
mistakes or may lead the user to reject its utilization in his There are two types of relationships between facts in the
medical practice. decision tree. The first one indicates the position of a given
fact in the knowledge base hierarchy. The second type of
To organize an effective dialogue with end-users and to
relationships indicates the existence of interdependence
eliminate the mentioned deficiencies an alternative
between the facts.
representation scheme of the knowledge base was created in
These relations do not depend on the form of visualization
the SonaRes system.
of the facts or the whole user interface, but represent the basis
The source of information for the alternative
representation scheme is the knowledge base, described as a of the system's knowledge base and inference.
Separation of the existing relationships between the
decision tree. It was necessary to propose such a
representation of the acquired knowledge in order to have questions in two groups – those, used in inference, and those,
the opportunities to realize an adaptive user interface with used only in the interface, allows us to create a high-quality
the following features: adaptive interface based on the individual characteristics and
habits of the end-user. It is achieved because the user can
 The interface should be simple and understandable.
define himself the subject and the form of dialogue (by
The dialogue with the end-users should take place in
changing the visualization relationships between the
its usual rhythm and form, and should not require questions), without any fear to influence the inference.
the changes in his reasoning.
Additionally, the questions grouping will allow to diversify
 The interface should correspond to the end-user's
the form of dialogue.
daily work and preferences. The end-users should This approach allows realization of different versions of
have possibility to influence the dialogue form. the user interface with restricted screen space and limited
 The interface should be "transparent". The solution time for the decision making (for instance, medical
proposed by the inference of medical computer- computer-assisted systems used in emergency cases).
assisted system should be easily to verify.
 The dialogue with the end-user should not have a
linear structure. The end-user always should have
the opportunity to return to the appointed step back.

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VIII. CHALLENGES AND SOLUTIONS IN images seems to be the application of both medical features
UTILIZATION OF ULTRASOUND IMAGES. IMAGES (obtained from a knowledge base) and visual features
RETRIEVAL (obtained from images). Retrieving based on medical
As mentioned above, ultrasound images have a dual features allows confirmation of the diagnosis assumption by
nature considering information they hold. A part of this obtaining a gallery of images containing the supposed
information is related to visual representation and can be pathology or fact.
managed by computer graphics techniques. But the most Retrieving based on visual features allows user to select the
specific feature of this type of images is their medical most appropriate image from obtained list of similar ones.
content. To manage this type of information the content- The combined retrieval, using medical and visual features,
based image retrieval technology is usually used. makes possible to search a visual representation for textual
SonaRes system collects a set of "model" (representative) description of medical feature and conversely to find the
annotated ultrasound images. The acquiring of the "model" textual explanation for visual feature.
ultrasound images represents a continuing process, where the
ACKNOWLEDGMENT
experts-physicians play a leading role, providing the ground
truth. Experts associate these images to the corresponding The research for this paper has been partial supported by
rules. On static images the regions of interest (ROIs) are the common project of the Academy of Sciences of Moldova
marked out. These ROIs are associated to particular and the National Authority for Scientific Research of
characteristics of the organ – facts (nodes of the knowledge Romania, grant 10.820.08.06/RoA.
pyramid).
The "model" ultrasound images are stored in SonaRes REFERENCES
image database. These are gray-scaled images, mainly, of [1] S. Cojocaru, C. Gaindric, Decision support system in
*.jpg and *.bmp storage formats. It is supposed that the ultrasound investigations, Proceedings of XIII
future additions can also be represented in non-DICOM International conference KDS-2007, vol. 1, ITHEA,
formats. Sofia, Bulgaria, 2007, pp. 241-246.
To provide the ROIs marking, association between ROIs [2] K. Doi, ―Computer-aided diagnosis in medical imaging:
and nodes as well as between images and rules, the special historical review, current status and future potential,‖
tools for work were developed. These tools help experts to Comput Med Imaging Graph 31(4-5), 2007, pp.198-
realize of the following actions: 211.
 ROIs management – allowing marking out the ROIs [3] Т.А. Гаврилова, К.Р. Червинская, Извлечение и
(as a contour of connected points) as well as other структурирование знаний для экспертных систем,
operations: addition, deleting and viewing ROIs; 1992.
 visualization of all ROIs corresponding to the [4] Iu. Secrieru, O. Popcova, S. Puiu, D. Sologub,
selected node on different images; ―Knowledge Structure Modeling in Ultrasound
 visualization of all ROIs (corresponding to different Investigation Domain―, Proceedings of the 5th
nodes) on the chosen image. European Conference on Intelligent Systems and
In SonaRes system the role of annotated images in Technologies (ECIT 2008), Iasi, Romania, July 10-12,
decision making process is to be a correct helpful 2008, CD.
illustration, if the physician is not sure how to interpret an [5] Iu. Secrieru, D. Sologub, Expert shell aimed at creation
ultrasound image. Since the results of SonaRes images of the knowledge base for ultrasonic research intelligent
retrieval serve mainly as help for the user, the corresponding system. Revista de inventica nr. 48, vol. IХ (ХV-2005),
tool was placed in the part of SonaRes web-interface. pp. 7-12.
The retrieving process starts with pattern image uploading [6] L. Burtseva, S. Cojocaru, C. Gaindric, E. Jantuan, O.
and optionally setting an own ROI (as a restriction to avoid Popcova, I. Secrieru, D. Sologub, SONARES – A
time-consuming and to increase retrieval accuracy). After decision support system in ultrasound investigations,
the process is finished, the web-gallery of similar images is Computer Science Journal of Moldova, vol.15, nr. 2
shown. (44), 2007, pp.153-177.
The images preview thumbnails are clickable. If one of [7] Iu. Secrieru, Structured knowledge management
these images is selected by the user – a new window is techniques for the development of interactive and
opened, showing the full size view of the image, matched adaptive decision support system, Computer Science
ROI and its annotation. Journal of Moldova, vol. 17, nr. 1 (49), 2009, pp.58-73.
The most fruitful method for retrieving similar ultrasound

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Information System Analysis of Heart Rate

Variability
Anatolie IAVORSCHI, Valerii PAHOMI, Valeriu PIRTAC, Dmitrii ANGHILOGLU, Serghei RAILEAN,
Andrei BRAGARENCO, Vitalie SCRIPNIC
Technical University of Moldova
[email protected]
Abstract – In this work is presented the software for heart rate variability analysis using methods of ECG and
FPG signal registration and processing.

Index Terms – electrocardiogram, photopletismography, heartbeat, cardio interval.

the PC's USB port, start/stop recording signal in real-time,

I. INTRODUCTION
copying data files from SD-card memory device, printing the
Implementation of continuous non-invasive methods of
results and closing the program.
monitoring the health of the surveyed people on the base of
File Manager allows you to work with the patient data
acquisition and analysis of the ECG or PPG with the aid of
files: save signal in a file, opening a file, delete a file and
the computerized technical means enables rapid
sorting files.
identification of different heart spontaneous affections or
monitoring functional status of the autonomic nervous
system by heart rate variability analysis.
Worldwide mortality from cardiovascular disease ranks first
among human diseases. One of the routine examinations of
any patient is to determine the frequency of cardiac
contractions [1-3]. Analysis of variability in time of heart
contraction frequency – cardiointervalography is used both
for diagnosis of a diseases and examination of health people
in order to assess the state of stress and level of adaptation in
extreme conditions [4-6].
II. STRUCTURE OF THE INFORMATION SYSTEM FOR
THE ANALYSIS OF THE HEART RATE VARIABILITY
Developed information system allows analysis of heart
rate based on electrocardiogram or photopletismographic
signal (Fig. 1) during signal recording more than five
minutes [7-9].
Fig. 2 Block diagram of software for analyzing HRV

Fig. 1 ECG and PPG signal

Structure of the information system HRV consists of three

Fig. 3 Graphic interface of the software for the HRV
core compartments (Fig. 2): Main Menu, File Manager and
HRV Result Analysis. III. TESTING THE INFORMATION SYSTEM IN THE
The third section allows viewing HRV outcome analysis: LABORATORY CONDITIONS
real-time signal indicating extracted cardio intervals, the In the first stage of informational system work is
result of the string of the analysis of cardio intervals in time necessary registration and visualization of the
domain and temporal indicators calculation, the result of the photopletismographic or electrocardiogram signal in real
string analysis of the cardio intervals in the frequency time as well as the extraction of the cardio intervals on the
domain and calculation of spectral components. base of the memorized signal (Fig. 4).
Graphical interface of informational system for heart rate After recording the signal with at least of 5 minutes
variability analysis is represented in Fig. 3. duration and extraction of the string of cardio intervals can
The main menu contains a set of buttons with the help of be performed the analysis of the cardio intervals in time
which can be conducted the operation of the software: on/off domain and getting Rhythmogram (Fig.5)

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Fourier fast transformation (FFT) in order to calculate the

distribution of the spectral power corresponding to the
spectral components: Ulf, VLF, LF, and HF (Fig. 7).
Analysis of the spectral power density of the heart rate
oscillations provides information on the power distribution
in dependence upon the frequency of oscillations. To this
fast Fourier transformation refers.
Fig. 4 PPG signal recorded in real time and indication of the cardio
intervals. TABLE I. TEMPORAL INDICATORS
, Histograms, Scattergram and temporal indicators: HR, HR Heart rate frequency (pulse) [beats / min]
RRmin, RRmax, SDNN, CV, RMSSD, pNN50, Mo, Amo, RRmin The minimum value of cardio intervals [ms]
DRR, SI (Fig.6). RRmax The maximum value of cardio intervals [ms]
SDNN Mean square deviation [ms]
Quadratic mean difference characteristic
RMSSD
[ms]
The percentage of RR intervals which,(RRi
pNN50 – RRi-1)>50 ms, reported on the total
number of the intervals [%]
CV Coefficient of variation [%]
The difference between the minimum and
dRR
maximum value of the cardio intervals [ms]
Mo Mode [ms]
Amo Mode amplitude
SI Stress index

Fig. 5 Getting rhythmogram on the base of the string of cardio intervals

Rhythmogramma – displays interval duration dependence

RR on the time recording interval RR. On the Axe abscissa
is represented the time registration (seconds, minutes), but
on the axis of ordinates is represented the RR measured
interval duration (milliseconds).

Fig. 7 HRV result analysis VRC in dependence upon the frequncy. Spectral
components

Table II contains the name of the spectral components and

the frequency diapason corresponding to each component.

TABLE II. SPECTRAL COMPONENTS

Spectral power in domain of 0,15-0,4 Hz
HF
the high frequency (2-6,6 sec)
Spectral power in domain of 0,04-0,15 Hz
LF
Fig. 6 Getting histogram, scattergram and temporal indicators
the low frequency (7-25 sec)
Spectral power in domain of 0,015-0,04 Hz
Histogram – represents the maximum number of RR VLF
the very low frequency (25-66 sec)
intervals in a determined time interval. On the abscissa axis Spectral power in domain of 0,003-0,015 Hz
is represented time interval (seconds) but on the ordinates ULF
the ultra low frequency (66-333 sec)
axis - density of the RR time intervals (%).
Scattergram - a two-dimensional representation of cardiac When the used method for investigating HRV is
rhythm. On the abscissa axis is represented the size of RRi photopletismography at the same time can be performed an
(seconds), but on the ordinates axis is represented the RRi+1 analysis of the photopletismographic signal by calculating
interval (seconds). Table I contains the name of temporal the main parameters of the rapid component of the pulsating
indicators and measurement units. wave FPG (Fig. 8).
Analysis of the string cardio intervals in the frequency Table III contains the full name of the main parameters of
domain involves obtaining a continuous cardio interval by the fast wave pulsating component FPG.
applying cubic spline interpolation and then applying

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IV. CONCLUSIONS
V. BIBLIOGRAPHY
Developed system allows recording and processing the
[1] SAUL JP, ALBRECHT P, BERGER RD, COHEN
electrocardiographic or photopletismographic signal in real-
RJ.Analysis of long term heart rate variability: methods,
time, extraction of the cardio intervals on the base of the
1/f scaling and implications.Computers in Cardiology
recorded signal at a long period of time (up to 24 hours),
1987.IEEE Computer Society press, Washington 1988:
saving and performing heart rate variability analysis by
419-22.
analysis in time and in the frequency of the cardio intervals
[2] MALIK M, FARRELL T, CRIPPS T, CAMM AJ.Heart
string obtained.
rate variability in relation to prognosis after myocardial
infarction: selection of optimal processing
techniques.Eur Heart J 1989: 10:1060-74.
[3] MALIK M, XIA R, ODEMUYIWA OET AL.Influence
of the recognition artefact in the automatic analysis of
long-term electrocardiograms on time-domain
measurement of heart rate variability.Med Biol Eng
Comput 1993; 31: 539-44.
[4] МАШИН В.А. Нестационарность и длительность
временного ряда сердечного ритма при диагностике
функциональных состояний. Биофизика, 2007, Т. 52,
No 2, с. 344–354
[5] R.BRYCHTA,R.SHIAVI,D.ROBERTSON. A
SIVPLIFED Two-Component Model of Blood
Pressure Fluctuation.
Am.J.Physiol.,2007,February,292(2),H1193-H1293.
[6] http://www.ecg.ru/standarts/hrv/contents.htm
Fig. 8 Key parameters of the fast wave pulsating component FPG
[7] Методические рекомендации. Исследование
TABLE III. KEY PARAMETERS OF THE FAST COMPONENT FPG вариабельность сердечного ритма с использованием
WPA Wave pulsating amplitude пакета программ «КардиоКит». Санкт-Петербург
ADW Amplitude of the decrotic wave 2003
IH Incesure height [8] http://circ.ahajournals.org/cgi/content/full/93/5/1043
IDW Index of the decrotic wave [9] http://www.hrv.ru/standart/contents.html
DAP Duration of the anachrotic phase of the
pulsating wave
DDP Duration of the decrotic phase of the
pulsating wave
DDP Duration of the descent phase
DPW Duration of the pulsating wave
TRW Time reflection of the pulsating wave
FCC The frequency of the cardiac
contractions
IUW Index of the upward wave
ET Ejection time
DSP Duration of systolic phase of heart rate
DDP Duration of diastolic phase of heart rate

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The Analysis of the Legal Framework in the

eHealth Field in Moldova, in the Context of
European Integration
Alexandru ROŞIORU
National Health Management Center, Technical University of Moldova
[email protected]
Abstract –The analysis of the legal framework in the eHealth field in Moldova, was made in the
context of European integration. This study is aimed to identify the legislative and normative gaps in the field
of implemetning eHealth in Moldova; intiation of changes in normative existing documents and making new
papers, policies documents, plans, standards. This study reviewed all medical information systems,
implemented in Moldova, to Identity legal gaps exist. Also in this study was structured lead analysis and the
legal basis in the field of eHealth from European Union.

Index Terms – eHealth, Legal framework in the eHealth field, Health Information Systems,
Regulatory framework.

 Efficient use of extremely limited financial

I. INTRODUCTION, AIMS AND OBJECTIVES resources;
―Solving the legal problems is primarily in  Integration of eHealth services in health care
developing any eHealth systems‖ system to ensure appropriate use of informational
The medical information systems are developing rapidly technologies;
in the world. This is due to qualitative and quantitative  Legislation to create and exploit the
changes in the request for medical services, the amount of eHealth systems in accordance to legislation,
information in the public health care field and developement national and international standards;
of informational skills of the society.
 Protection and security of personal data in
In this way, eHealth has a great potential to become a
primary factor in developing and improving medical
the patient’s interest;
services.  Accesibility and transparency of
The process of inforamational society developement in information regarding public health and medical
Moldova is based on the National Strategy of Informational services;
Society Edification ―Electronic Moldova‖, approved by the  Increasing the role of patients decision
Government‘s Decision no. 225 from March 9 [1], of making and use of information aimed at health and
medical developement field in Moldova. medical services;
eHealth means the use of Internet technologies and
 Social orientation of eHealth care system in
electronic communications by providing and administrating
medical services and public health care.
Moldova.
Specific objectives for eHealth startegy in Moldova are
eHealth facilitates the prices administration, lowering
based on equally treated subsystems, that will contribute to
medical errors and offering improved medical services for
succesful development of medical informational space in
the patients.
Moldova:
eHealth will have a major effect on:
- Developing normative and legislative
 The directing of health care system;
framework for the use of informational
 Curative and preventive assistance; technologies in medicine and its adjustment to
 Increasing working efficiency in extreme the European.
situations; - Implementation of the Integrated Medical
 Developing medical science; Information System Concept (IMIS) to control
 Training and retraining of the staff; medical and administrative information flows.
- Achieving economic and management benefits
The principles on the basis of strategy development from implementin eHealth services.
in eHealth field are: - Developing telemedical services to improving the
 Use of excelence examples and EU quality and accesibility of medical services and
requirements for developing e-health services system; bring closer medical services to the patient‘s place
 The responsability of local and central of residence.
administration bodies in the succesful development - Training in using informational technologies and
process of eHealth; improving the access of medical staff to

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information and education, to increase the programs at national level.

efficiency and quality of medical services. The variety of eHealth services technologies, successfully
- Facilitating the access to information for patiens implemented, include all levels of medical assistance, from
and citizens on public health and personal health to public health to robotic surgery, from providing effective
economic services and accessible to communities from dense
increase their participation in the decisions making
populated areas to providing qualitative medical services in
process. poor areas.
In recent years there has been a significant increase in use Developing legal framework for eHealth technologies use
of ICT in health system. There were developed and involves an analysis of current legislation, regulation in
implemented administrative information for primary health care and telecommunications to identify legislative
medicine, health insurances, Automated Informational and administrative barriers in implementing the referred
System "state Nomenclature of drugs‖, management in services. In the study will be outlined the normative and
transfusion, monitoring and evaluation of the national legal changes necessary for creating eHealth services in
Program of control and prevention of tuberculosis, etc. Moldova.
According to the Ministry of Health‘s data, although there In the analysis of international experience will be
is universal access to ICT, only 143 medical institutions reviewed the legislation and practice of European
have broadband Internet access, fixed and mobile, and only Community in the field of eHealth services regulation,
seven institutions use ICT for data and information traffic protection of personal data, access to medical confidential
between the medical instituutions. Despite the fact that the information, etc.
number of medical staff using ICT is rising, currently only This study is aimed to identify the legislative and
12% of the doctors use Internet and 18% - use the computer normative gaps in the field of implemetning eHealth in
in their proffesional activity. Moldova; intiation of changes in normative existing
Currently in Moldova‘s health system are implemented documents and making new papers, policies documents,
telemedical pilot-projects in perinatal, neurology and plans, standards.
ophthalmology fields. Telemedical videoconferences and This study involves several components research:
educational support based on Web, are used in proffesional - Analysis of existing legal framework in using
training in remote. Through videoconfrences doctors and informational technologies and communications in
students have regular access to international classes in Moldova‘s health care system;
different specialized medical fields. - Analysis of legislative actuality of Integrated
The importance of ICT to enhance the quality and Information Health System Concept and of other
accessibility to medical services is increasing every year. All documents at the basis of informational and
EU countries have adopted national strategies within the communication system in health sector;
mutual effort of European Communities, mentioned in a - Outlining legislative issues within the practices
number of documents supranational policies in the field, framework of SIA implementation in health sector in
developed by the European Board in the years 2000-2009. Moldova.
To the end of 2011, EU countries are required to assess the - Documenting positive practices of EU countries
situation and to adopt national legislation on access to regarding the harmonization of legislation in eHealth;
telemedical services, including accreditation, accountability, - Recommendations/proposals regarding development,
procedures for reimbursement of services, confidentiality changes or improvement of legislative documents aimed
and data security. to ralley the acquis communautaire, including its
The documents referred are aimed to optimizing the use of adjustment in accordance with other national legislative
health systems resources, through mentioned by insertion of papers recently approved.
eHealth services. Through eHealth technologies is improved -
communication between providers of medical services and
increases the patient‘s access to health information. II. CONCLUSIONS AND RECOMMENDATIONS
Through the Communiqué COM(2008) 0689 from REGARDING LEGAL FRAMEWORK FOR
4.11.2008 „Telemedicine for patients benefits, health system IMPLEMENTING E-HEALTH SERVICES IN
and society‖, European Board outlines the importance of MOLDOVA.
telemedicine, and for positive implementation of telemedical The concept of eHealth changes essentially practices and
services suggest to EU countries great facilities, related to rules in health sector in terms of relationships between
building confidence and acceptance of telemedical services, doctors and patients, between medical institutions, on the
inserting legal clarities, solving technical problems of other hand, institutions involved in financing and
compatibility and standardization, as facilitating market monitorizing health sector.
development in the field of economic relations. . Legal safety represents a prerequisite for bussines
WHO, besides the consultative support, granted to support environment to invest in inovations, and for medial
countries‘ efforts in developing eHealth, designates institutions and patients to benefit of new products and
organizations that possess expertise skills and can serve as services. As long as the eHealth market will be characterized
centres of reference for developing services in the field. by the lack of legal safety, there will be blocks for progress
WHO resources can be used to priorities identification, in the field..
developing eHealth policies, strengthening the legislative, The key to succes in the eHealth initiative is putting into
normative and ethical basis in the use of health information, question at regional and national level the legal interferences
dissemination of experience about the practice of excellence between eHeath and national policy in health.
in the field and facilitating the implementation of technical As a result of the legal framework analysis for the

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implementation of e(m)Health in Moldova have been noted VII. After the analysis was found the lack of specific
the following conclusions: horizontal of legislation for implimen in the e(m)Health
At strategic level: field ;
I. Health care system in Moldova has strategic tasks of VIII. All legal useful previsions in implementing e(m)Health
implementing e(m)Health services based on National are reflected in very dispersed ares/fields which inflicts
Strategies of building a informational society „Moldova on the petential users e(m)Health from Moldova;
electronnic‖, health care system‘s strategy of At normative level:
development during 2008-2017, National Health Policy IX. There is no legal framework to stimulate and motivate
in Moldova, Integrated Medical Information System; the use the eHealth technologies in health care sector,
II. In the health system of Moldova were carried out including implementation of electronic chart of the
various activities for implementing ICT in health care, patient and traffic of electronic data;
like: – It is not established of electronic medical records;
Telemedicine and distance learning in Moldova; – There are no specific rules of usage for digital signature
Automated Informational System „Mandatory Health in health system;
Insurance‖; Automated Informational System „Blood – There is no normative framework on the interoperability
Service‖; Automated Informational System „The improved of medical electronic data;
system of epidemiological surveillance of avian influenza – There is no framework for unification of electronic
and other infectious diseases‖; Automated Informational medical terminology;
System „ the state Nomenclature of drugs‖; Automated – Etc.
Informational System „Primary Medical Assistance‖, X. There is no regulatory framework related to
„Cabimed Manager‖ within the Universitary Clinics of standardization in e(m)Health.
Primary Medical Assistance; Integrated Informational
System of medical Assistance and medical Imagistics within
III. RECOMMENDATIONS
the Institute of Neurology and Neurosurgery „Hospital
In order to overcome the situation concluded after
Manager Suite‖; Integrated Informational System of medical
analyzing the normative legal framework in e(m)Health in
assistance within the National Scientific Practical Center of
Moldova are proposing:
Emergency Medicine; Informational System of statistical
At strategic level:
data collecting, Informational System of Monitoring and
Based on the analysis, particularly the overcome in tie of
Evaluation of TB; mHealth – mobile Health; Automated
stratedic previsions in IMIS and the need to cut the prioritary
Informational System of Primary Medical Assistance
actions in accordance with international and european rigors
„MedEx‖ put into experimental exploitation; Informational
required
System of Monitoring and Evaluation of AIDS; etc.
– Developing and approving the National Strategy of
But all these initiatives remain sparodic, fragmented and
development in the field e(m)Health and
without continuity and sustainability, mostly because of the
Telemedicine;
imperfection of legislative framework of e(m)Health
implementation in Moldova.
On legislative level:
III. Some key previsions of the normative and legal
Given the non-specific characteristics, incomplete,
framework are outdated and needs radical review (ex.
disperse of the legislativ normative framework in e(m)Health
Integrated Medical Informational System Concept);
present in Moldova, the only solution the deficiencies would
IV. Despite the presence of some deficiencies in european allow allignment from the start to international and european
legislation e(m)Health, alignment to the European
standards are:
legislative framework is a primary objective and vital
– Development of the LAW ON THE E(M)HEALTH
for the development of the field. IN MOLDOVA.
At legislative level: On normative level
V. The legislative framework in Moldova, targeting both – Development of The analysis of the legal framework
the health system, as the general is unspecific in the eHealth field in Moldova, in the context of
e(m)Health and does not include express previsions for European integration electronic medical data status;
its implement; – Establish specific rules for use of digital signature for
VI. Regardless the fact that some key previsions for health system;
e(m)Health,like, Law on patient rights and – Develop of legal framework on interoperability of
responsabilities no.263 from 27.10.2007, Law on medical electronic data;
excerising the medical proffesion no.264 from – Need to adopt the framework for the unification of
27.10.2005, Law on health care no.411 from medical terminology in electronic format;
28.03.1995, Law no. 982-XIV from 11.05.2000 on the – Need to develop a set of standards in medical
access to information, Law no. 264-XV „On the informational technology (medical informatics). (Ex.
electronic documents and digital signature‖ from There are not approved the standards on the electronic
15.07.2004, Law no. 17 from 15.02.2007 on the chart of the patient, ENV 13606);
protection of personal data, Law no. 241- XVI from – To prioritize the needs of implementation– example,
15.11.2007 on theelectronic communications, etc. are electronic chart of the patient must become prioritary in
present in national legislation, although this legislative implementation, to facilitate the medical access to
normative framework reamins incomplete.; technologies;

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– To identify the nomenclature on national level and

establish technologies that would provide automatic [5] Commission decision of 28 November 2005 on the
dissemination of nomenclature approved by the Ministry application of Article 86(2) of the EC Treaty to State aid
of Health in automatic mode; in the form of public service compensation granted to
– Establish standards for data exchange between certain undertakings entrusted with the operation of
Ministry of Health, Health Inssurance Company and services of general economic interest, O.J., L 312 of 29
Health facilities (example, establish standrads of November 2005, pp. 67-73.
electronic reports based on Statistic Ticket) [6] Council Directive 90/385/EEC of 20 June 1990 on the
approximation of the laws of the Member States relating
REFERENCES
to active implantable medical devices
[1] National Strategy of Informational Society Edification ―Electronic
[7] Directive 98/79/EC on in vitro diagnostic medical
Moldova‖, Available: http://www.e-moldova.md
devices
[2] Communication from the European Commission on
[8] Directive 2001/83/EC of the European Parliament and
social services of general interest in the European
of the Council of 6 November 2001 on the Community
Union, SEC 2006/516.
code relating to medicinal products for human use
[3] Commission communication on ‗Professional Services‘
[9] Council Directive 93/42/EEC of 14 June 1993
of 5 September 2005, COM 2005/405.
concerning medical devices
[4] Council Regulation (EC) No 139/2004 of 20 January
[10] Thomas S. Deisboeck, J. Yasha Kresh, Complex
2004 on the control of concentrations between
Systems Science in Biomedicine. Springer, 2006.
undertakings (the EC Merger Regulation)
[11] Lacramioara Stoicu-Tivadar, Sisteme informatice
aplicate în servicii de sanatate, Editura Politehnica,
Timisoara, 2004.

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The Intelligent Support System for Remission in

Patients with Psychiatric Disorders in Epilepsy
Maria BUTNARU1, Ana CAPATANA1, 2, Gheorghe CAPATANA1,
Oleg COBILEANSCHI 3, 4, Alexandru POPOV 4
1
State University of the Republic of Moldova
2
Yale University
3
State Medical and Pharmaceutical University "Nicolae Testemitanu" of the Republic of Moldova
4
Psychiatric Hospital of the Republic of Moldova
[email protected], [email protected], [email protected], [email protected]

Abstract – In the paper is related a project of an Intelligent Support System development for research and
treatment of epilepsy. The tasks of this study are: a) to prove on material of over 100 patients with remissions
that epilepsy is curable; b) to classify these persons by remissions groups; e) to develop and implement an
intelligent support system for research, diagnostics and treatment assistance in epilepsy, d) principles
development and implementation for psychological and psychiatric assistance and for critical situations
remedy with which epileptics patients face, inclusively with socio-psychological assistance service conditions
and within psycho neurologic consulting rooms. At the moment are developed: an expert system for diagnosis
of epileptic patients with psychiatric disorders, an electronic textbook in the area of epilepsy problems, a
support system for development of treatment programs of epileptic patients.

Index Terms — artificial intelligence, epilepsy, expert systems, decision support systems.

methods of treatment for resistant types of epilepsy,

I. INTRODUCTION development and implementation of intelligent support
The task of treatment of epileptic patients with system for diagnosis and treatment of epilepsy will be
psychological disorders became drastically a global problem. attempt to develop for the first time in our republic an
Many neurologist and psychiatrist doctors are more and intelligent support system for treatment and diagnosis of
more preoccupied with this problem and the obtained results epilepsy.
became more important and precious. Recent statistical data We propose a new project composed of six stages, which
shows an increase of up to 10.2 persons per 1000, while in unifies the expertise in the area of medical science,
developed countries from West Europe, US and Canada are physiology, decision support systems and artificial
related data of 2.4-7.2 persons per 1000. People with intelligence. Our research combines the development of: an
epilepsy need not only appropriate treatment, but the social- expert system for diagnosis of epilepsy patients, a support
psychological support and they require mandatory society system for doctor assistance during program process
understanding and moral support. Every day, scientists and development for epilepsy patients treatment, selection and
practitioners in the area of epileptology, make great efforts data results classification regarding patients with epilepsy
to find outstanding remedies involving experts from other remission, database development based on medical histories
areas with scope to solve an important task as treatment of of epilepsy patients with remission, analysis of these data
epilepsy with psychological disorders. from database and retrieval of knowledge regarding the
The number of patients in Republic of Moldova with effect of remission of these data, expert system development
revealed epilepsy increases from year to year, even in to forecast the new patient with remission group with
conditions of massive migration, fact proved by increased symptoms of epilepsy, developing a distance learning system
number complains from population and in particular from of epilepsy and prophylaxis of this disease.
young persons to neurologists and psychiatrist. The first stage of the project is to develop an expert
The epilepsy is a problem multidisciplinary. The success system for diagnosis of epilepsy patients. The system is
in epilepsy treatment requires collaboration of high planned to assist doctors from Moldova clinics and abroad.
qualification experts from different areas as: neurologists, The system will provide a higher level of medical diagnosis
psychiatrists, geneticists, pediatrician, mathematicians, from provinces and respectively, a smaller quantity of errors
immunologists, neurophysiologists, neuro-pharmacologists, in diagnosis. The expert system is projected to be used in the
artificial intelligence specialists. training process in Medical Universities. It also could be
Impressive discoveries from last years in the areas of used to support remote diagnosis process of patients with
genetics, immunology, neurophysiology, practical research symptoms of epilepsy and to be used for population
and artificial intelligence encourage that in the near future information on epilepsy and prophylaxis of this disease.
the medicine will overcome the dogma of incurability of The second stage of the project is planed for development
epilepsy. of a support system for doctor‘s assistance within the
process of development of patient epilepsy treatment. The
II. THE SCIENTIFIC NOVELTY AND EXPECTED system will be developed following specialty classifiers.
RESULTS The third stage of the project consists in data selection and
Based on a complex analysis on research material, systematization based on patients with remission of epilepsy,

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database development regarding medical histories of conclusions that can be derived based on responses provided
epilepsy patients with remission. In present there are found by the user (doctor). To facilitate the decision process of an
110 former epilepsy patients and brought with contribution accurate diagnosis, it was quickly developed an expert
of a new treatment (non-conventional) methodology into system for diagnostics. The expert system provides
remission of the disease. Data regarding on medical reports conclusions that are drawn based on responses provided by
of these group of patients will be prepared according to the system user (healthcare professional) to a series of
requirements of Data Mining technology for preparing data questions proposed by the system. Development and
based of patients‘ peculiarities (age, social group, diagnosis, implementation of expert system in medicine is a
etc.). requirement of the time due to its use will help to increase
The fourth stage of the project will consist of database the accuracy of making a diagnosis, reducing the time
knowledge retrieval. Knowledge will be collated into groups required set a diagnose and reduction of diagnostic errors.
of patients according to diagnosis and degree of remission. Exploiting an expert system is actually for Moldova and due
Our experience of treating patients with epilepsy and insufficient number of specialists in epilepsy field in many
bringing on remission status allows us to distinguish rural health facilities. All the responsibility bears the family
following classes of patients with remission: doctors who would welcome a "diagnostics algorithm" of
a) patients with therapeutic remission – patient is expert level. It is expected to use the expert system
maintained in this condition on a background of daily developed for both diagnosis and treatment of patients with
therapeutic treatment; mental disorders, also in the process of health professionals
b) patients with therapeutic remission with stable training.
compensation – to patient are not prescribed any drugs; With the aim of developing an expert system in psychiatry
c) patients with spontaneous remission – after a short [1-3] it was taken into account a particular group of
period of anti-epileptic drugs prescription (3-6 months); diagnosed diseases of mental disorders. Thus, the diagnosis
d) after anti-epileptic drugs prescription (6-12 months); of diseases of the group mentioned above has some
e) patients judged by differential diagnosis with other peculiarities; they are based on clinical investigations.Using
diseases (early metabolic disorders, deficiency of Mg expert system can be established nine groups of diagnoses
ions, Ca etc.); mental graded from F00 to F09 in ICD-10 classification of
f) cured patients, with diverse long term remission and mental and behavioral disorders [4]. Epilepsy expert system
intermission; is equipped with a knowledge base. In the computer this
g) patients, who eventually are diagnosed and then cured. base is stored in two forms: a) a version in Prolog - to
The fifth stage of the project – development of an expert diagnose epilepsy, and b) a version in HTML - to develop
system for prognosis of a new patient with epilepsy treatment programs for epilepsy patients with psychiatric
symptoms within remission group. disorders. Expert system can be used both as support to
The sixth stage of the project – development of a distance diagnosis of epilepsy patients with psychiatric disorders and
learning system on epilepsy and an information system of in teaching.The expert system is developed in Prolog
population regarding epilepsy and prophylaxis of this illness. language and contains the following main components:
As result of performed investigations we intend to promote  Knowledge Base for Diagnosis, which contains specialty-
and implement a series of original and differentiated specific facts and rules based on which is operated
programs of family and social rehabilitation, epilepsies knowledge base for diagnosis with the aim to carry out
prophylaxis through information and education, provisions reasoning to obtain solutions, recommendations or
and suggestions for epilepsy prophylaxis and treatment. conclusions that are related to setting patient epilepsy
At the moment are developed: diagnosis. The presentation model of knowledge is a map.
 an expert system for diagnosis of epilepsy patients with  Dialog Interface - allows dialogue with end users during
psychiatric disorders; the consultation sessions, and users access to base facts
 epilepsy knowledge base; and knowledge;
 an electronic textbook in epilepsy;  Knowledge Acquisition Module - provides to expert user
 a support system for development of epilepsy treatment querying types of the system with aim of obtaining
programs; solutions as well as methods of knowledge base
 other software components in the context of the project. modification (adding, removing or modifying cognitive
units);
III. THE EXPERT SYSTEM  Explanatory Module – have the role to explain the user, as
The results of performed research will be translated into well data available to the system, as reasoning process that is
valuable applicative suggestions, which will explore the performed or solutions obtained within professional advice.
topic in all its biological, psychological and social aspects. The presentation model of knowledge is a Map that
Prognosis and prophylaxis recommendations, and curability reflects the link between disease and symptoms.
of epilepsy under medical and psychological indicators, Developed expert system establishes mental disorders
estimation of recovery methods and their reasoning for according to symptoms that patients have. It asks questions
practical thinking in stationary conditions, in mental health concerning 132 symptoms. The software result can be one of
centers and within family will facilitate the development of 24 different diagnoses.
new organization forms of epilepsy patients recovery, given Knowledge base for diagnosis keeps information
the particular pathology detected. regarding treatment rules of mental illness. The conclusion,
In the process of diagnosis setting may occur more choice, obtained by inferential Engine of Expert System serves as a
despite all medical data were collected. An expert system prerequisite for the next phase - development of treatment
suggests a series of questions and provides the best clear programs for epilepsy patients.

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Due to this the expert system is equipped with two of the electronic manual. The system can be used as well in
knowledge bases: first - to support the diagnosis, the second medical practice, as for training of healthcare professionals.
- to support development of treatment programs. The strategies implemented within system are based on the
knowledge of expert specialists in the area.
IV. ELECTRONIC TEXTBOOK IN EPILEPSY
Electronic textbook on epilepsy is a database for support
of programs‘ development for treatment of patients with
epilepsy. The electronic manual contains tables with
information about the group diseases F00 to F09 (Fig. 1).
The first page is introductory and contains psychiatry
symbolism placed on a graphic background. The end user
accessing this page confirms the intention to browse the
textbook by activating the button: "Welcome". Then the
electronic manual switches to view the 2nd page. This page
contains information on the textbook cover for mental
illness. Clicking on cover book, it makes the transition to
Contents of the book. All information relating mental illness
is presented on separate pages. Here it is possible to click on
any link from Contents, going to the page describing the
requested theme. Can be used following options to browse Fig. 2. A fragment of the Database „Treatment‖
the electronic textbook "Next page" (from first page to last), VI. CONCLUSION
"Previous page" (from the current to the homepage). In the paper was described a project of development of an
Browsing is carried out in accordance click the arrows on the intelligent support system within research and treatment area
right field (moving forward) or left (backward) of the of epilepsy. The tasks of the research are: a) to prove based
electronic manual. on material of over 100 patients with remissions that
epilepsy is curable, b) to group these people by remissions
groups, c) to develop and implement an intelligent support
system for epilepsy research, diagnosis and treatment
assistance, d) to develop and implement the principles of
psychological, psychiatric and to remedy the critical
situations with which face epileptics, including support
services under the socio-psychological and psycho-
neurological clinics. Currently are developed: an expert
system for diagnosis of epilepsy patients with psychiatric
disorders, an electronic textbook in the area of epilepsy, a
support system for developing treatment programs for
patients with epilepsy and other components in the context
of research.
REFERENCES
[1] Butnaru M., Căpăţână Gh., Popov Al. Dezvoltarea
sistemului de diagnosticare în medicină. În: Conferinţa
Fig. 1. Electronic Textbook Internaţională ‖Telecomunicaţii, Electronică şi
V. THE DECISION SUPPORT SYSTEM FOR Informatică‖ ICTEI 2010, ediţia a treia , Volumul II,
DEVELOPMENT EPILEPSY TREATMENT PROGRAMS Chişinău 20-23 mai, 2010, p.306-311.
The problem of treatment programs is a weak-structured [2] Carcea Iu., Butnaru M., Căpăţână Gh., Popov Al.
problem and it may have several solutions. Therefore, for Generator de sistem expert în medicină. În: Conferinţa
solving problem of issuing advices regarding treatment Ştiinţifică „Dezvoltarea cercetării ştiinţifice,
peculiarities was developed a decision support system. promovarea şi cultivarea creativităţii şi a inovării în
Database of support system for developing treatment procesul instruirii academice‖. 5 mai 2010. Rezumatele
programs is organized in pages (Fig. 2). comunicărilor. Ştiinţe reale şi exacte. – Chişinău: CEP
The tables contain information on diseases of the group USM, 2010, p. 115-116.
F00 to F09 [4], including data about: [3] Moscalenco S., Butnaru M., Căpăţână Gh., Popov Al.
• Laboratory investigations; Sistem suport de asistare a tratării pacienţilor. În:
• advices provided by specialty doctors; Conferinţa Ştiinţifică „Dezvoltarea cercetării ştiinţifice,
• treatment schemas; promovarea şi cultivarea creativităţii şi a inovării în
• daily dosage; procesul instruirii academice‖. 5 mai 2010. Rezumatele
• costs. comunicărilor. Ştiinţe reale şi exacte. – Chişinău: CEP
On top of the table is the table of contents, which contains USM, 2010, p. 129-130.
information on the groups of diseases. [4] The ICD-10 Classification of Mental and Behavioural
By clicking on the row of the table contents, it is accessed Disorders. Clinical descriptions and diagnostic
information about this group of diseases. Pressing the button guidelines. Geneva, World Health Organization, 1993.
labeled "Return to top", we return to contents of this book. – 263 p.
The table Treatment can be accessed from the Contents page

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BRANZANIUC K. 387
AUTHORS INDEX BREYMANN T. 319
A BURTSEVA L. 441
ABABII I. 263,271,281 BUTNARU M. 452
ABABII P. 263,271,406 BUZURNIUC S.A. 133
ABASHKIN V. 198
ABDEL SALAM-
C
CALABRESE P. 285
HAMDY MAKHLOUF 48
CAPATANA A. 452
ACHIMOVA E. 194,198
ADELUNG R. 25 CAPATANA G. 452
ALAPATT G.F. 154 CARAMAN IU. 211
ALEXEEVA N. 310 CARAUȘ T. 438
ANDRIES I. 194, CARSTENSEN J. 13,16,21
ANDRIESH A.M. 90,194,198 CASIAN A. 164
ANGELOV O. 320 CAZACU A. 319
ANGELSKY V. 239 CEBOTARI S. 319
ANGHILOGLU D. 307,445 CEBOTARI V. 294
ANTROPOV E. 172 CEKMAN I. 350
AOKI T. 245 CELIS J.-P. 75
ARAMĂ E. 281,301 CEPOI L. 354
ARORA S. 252 CERBU F. 60
ASIMOV M.M. 257 CEREMPEI L. 387
ASIMOV R.M. 257 CHAKRABARTI D. 252
ATKINSON P. 28 CHEPTANARU E. 319
AZAMFIREI L. 387 CHETRUSH P. 211
BABUCI A. 301 CHIHAI V. 277
CHIRIAC A.P. 335,365
B CHIRIAC T. 354
BACONNIER P. 285 CHOW L. 29,186
BADINTER E. 43 CIUBOTARU A. 319
BAKERENKOV A. 236 COBILEANSCHI O. 452
BALANETSKA V. 395 COJOCARU A. 21,39
BALICA Ş. 273 COJOCARU I.A. 124
BALMUS I. 164 COJOCARU S. 441
BARNACIUC S. 319 COJOCARU V. 80
BELENCHUK A. 97 COLIBABA G. 39
BELIC O. 301 COLOMEICO E.P. 90,124
BELOTSERKOVSKII I. 218 COMŞA S. 362
BELOUSSOV I. 101 CONDREA E. 104
BENEA V.G. 90,124 CONEV A. 313
BESLEAGA T. 285 CRETESCU I. 243
BETS L. 194 CREŢU A. 304
BLUNIER M. 438 CUHARUC A. 72
BOETHIG D. 319 CULEAC I. 133
BOGDAN A.V. 67 CULIUC L. 72
BOLOGA L. 387 CURTEANU A. 438
BOLOGA V. 294
BOOR J. 21
D
BRAGARENCO A. 445 DANILA M. 207
BRANISTE T. 36 DANILOV L. 263,271

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DAS J. 161 GISBRECHT A.I. 257

DASCALU D. 247 GOERLER A. 319
DASCALU T. 207 GOLOVIN A. V. 180
DEGROOT S. 161 GOMIS O. 59
DEKHTYAR Y 255,344 GONCIAR V. 350
DEMSKI H. 419 GORBANYUK T.I. 66
DIACONESCU C. N. 175 GORCEACOVA N. 350
DIACOVA S. 263,271 GRANCIUC G. 369
DIMOVA-MALINOVSKA D. 320 GRIŢCO A. GRITZCO A. 266,290,297
DING F. 28 GROMOV E. 231
DMITROGLO L. 211 GROZAVU N. 434
DOROGAN A. 83,142,273 GSELL S. 172
DOROGAN V. 273 GUDUMAC V. 357
DÖRR K. 28 GUEORGUIEV V.K. 325
DRAGUTAN N. 83,142 GULEA A. 357
DRAHNEA S. 194 GUPTA N. 154
DUBOLAZOV A.V. 377,409 GUTSUL T. 354
DUCLOS C. 340
DUMANOV E.V. 60
H
DUSCIAC V. 164 HAREA D.V. 124
DUSHKIN C. D. 320 HARTNAGEL H.L. 24
HAVERICH A. 319
E HEARD P. 36
EBERHARD A. 172,285 HILDEBRAND C. 419
EMELCHENKO G.A. 49 HORN S. 172
ENACHI M. 33 HUBER T. 168
ENGELBRECHT R. 419
ESHANU D. 266
I
ESINENCO D. 207 IAKOVLEV V. 148
EVANS G. 186 IASENIUC O. 198
EVTODIEV I. 211 IAVORSCHI A. 301,307,310,445
IAVORSCHI C. 294
F IGNAT M. 243
FENDRI MOHAMED AYMEN 404 IOISHER A. 43
FERRER-ROCA CH. 59 IORDATII M. 340
FLOWER S. 161 IOVU M.S. 90, 124,133
FÖLL H. 13,16, 20,21,39 ISTRATIY V. 409
FOSSEY J. 161 IVANENCO I. 108,111
IVANOVA I. A. 320
G
GAINDRIC C. 441 J
GANENCO A. 288 JAMES T. D. 161
GARABA I. 117 JULA N. 175
GAVRILUŢA A. 72
GERMAIN M. 161
K
GERNGROSS M.-D. 16 KACHANOVSKA A. 344
GHEORGHIU D. 362 KANTSER V. 97, 117, 157
GHERCIU L. 94 KAPON E. 142, 83
GHERMAN C. 72 KARACHEVTSEV A.O. 377,409
GHIMPU L. 138,207 KATASHEV A. 80
GHIŢU I. 128 KAVAS B. 75

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KEHRLE J. 172 MEREUŢA A. 83,142

KERNER I. 121 MESHALKIN A. 194
KERNER Y. 381 MIMURA H. 145
KHODOS I.I. 49 MIRONOV B. 221
KHSDZHI P. 101 MIROVSCII V. 114
KIM N. 117 MITIOGLU A. 72
KISELYOVA E.S. 94 MLADENOV G.M. 67
KOIKE A. 145 MOCAN E. 347
KONOPKO L. 168 MOCREAC O. 86
KOVAL V.M. 67 MOGADDAM N.A.P. 203
KRASTEVA L. 320 MOLDOVANU I. 285,288
KUBALL M. 36,161 MONAICO E. 39,43
KUDELINA O. 431 MORARI R. 172
KUDRENKO E.A. 49 MOSHNYAGA V. 97
KUMAR S. 28 MOSKALENKO S.A. 60, 94
MUELLER C. 172
L MULLER R. 207
LANCERE L. 255 MUNTEANU E. 273
LASCOVA R 72 MUSTEATZA V. 266
LAVÍN V. 59
LAZAR G. 211 N
LECA A. 207 NACU V. 347
LEISNER M. 13, 16 NAGAO M. 145
LELYAKOV I.A. 94 NAHABA V. 294
LEÓN-LUIS S. F. 59 NEAMTU I. 335
LEPORDA N. 43 NEDEFF V. 221
LEV-OR A. 400 NEDEOGLO D. D. 39
LIBERMAN M.A. 60 NEGOESCU R. 414
LIN Y. 186 NEMERENCO L. 108, 111
LITOVCHENKO V.G. 66 NEO Y. 145
LOZOVANU S. 288 NICA I. 266, 294, 297
LUPAN O. 29, 53, 138,186 NICIC V. 164
NICORICI A. 354
M NIKOLAEVA A. 168
MAGERL E. 28 NISTOR M.T. 335, 365
MALAHOV L.A. 133 NISTOR YU.H. 133
MALIGA O. 319 NITA L.E. 335, 365
MALKIN E. 183 NOLD E. 172
MANIUC L. 319 NOVIKOV B.V. 94
MANIUC M. 271,406
MANJÓN F.J. 59 O
MARGINEAN C. 387 OBERMEIER G. 172
MARGINEAN O. 387 OBREJA R. 175
MARIA S. 362 ORDONEZ A. 186
MARTÍNEZ-GARCÍA D. 59
MASALOV V.M. 49
P
MASNIC A. 114 PACIOGA A. 362
MASOUD M. 404 PAHOMI V. 307, 445
MAUSER J. 252 PAPAZOVA K. 320
MAXIMOV E. 294 PARVAN V. 114
PĂSTRĂVANU C. 243

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PATMALNIEKS A. 344 SANG HOON PARK 252

PAUPORTÉ T. 29 SARIKOUCH S. 319
PAVLIDIS D. 36 SARUA A. 36,161
PENIN A. 215 SAULEA A. 277,310
PESHKOVA T. 320 SCERBII D. 313
PÎRŢAC V. 301, 307, 310, 445, SCHMIDT O.G. 28
PITEA A.M. 387 SCHMIDT V. 21
PLUMHOF J. D. 28 SCHRECK M. 172
PODLESNY I.V. 94 SCHULLER T. 162
POGORELSCHI L. 294 SCHULTE A. 252
POLYAKA N. 255 SCRIPNIC V. 310, 445
POOLE K.F. 154 SCUTARI C. 350
POPA V. 36 SECRIERU I. 441
POPCOVA O. 441 SECRIERU V. 273
POPESCU L. 138 SEGURA A. 59
POPOV A. 452 SERGENTU V. 33
POPOVICI E. 243 SHAPOVAL O. 97
PORAT M. 381, 400 SHEMYAKOVA T. 101
POSTOLACHE V. 43 SHISHIYANU S.T. 203, 325
POSTORONCA S. 317 SHISHIYANU T.S. 203, 325
POTAPOV E. 117 SIDOR M. 395
PREPELITSA A. 172 SIDORENKO A. 117, 172, 215
PRILEPOV V. 128 SINGH R. 154
PUMPENS P. 344 SIRBU L. 207
SKRASTINA D. 344
R SLOBOZEANU A. 304
RAILEAN S. 445, 307,313 SMYSLOV V. 218
RASTELLI A. 28 SOCOLOV V. 310
RAY S. 59 SOCROVISCIUC A. 172
RENHOFA R. 344 SOLTYS I.V. 190
REPIN O. 319 ȘONTEA V. 248, 304, 307,310
REVENCO N. 387 SPIVAK V.M. 67
REVENCU T. 347 STALBE A. 266, 290, 297
RODRÍGUEZ-MENDOZA U.R. 59 STAMOV I. 108
ROGOVSCHI N. 434 ŞTEFANEŢ M. 301
ROMANOVA M. 344 STEFANOV P.S. 325
ROSCA A. 279 STEINMAN E.A. 49
ROŞIORU A. 448 STRATULAT P. 248, 438
ROTARU A. 313 STRUNGARU R. 373, 391
ROZORYNOV G.N. 404 SUDNIKOVICH A. 255
RUBINOV A.N. 257 SYRBU N. 83, 108, 142
RUDI L. 354
RUDIC V. 354, 357 T
RUDZEVICH Y. 186 TAGADIUC O. 347,357
RUSSEV I. 313 TAGIROV L. 172
RUSU E. 128 TANASĂ F. 328, 329
RUSU S. 60,101 TARALUNGA D. 391
TELENHA O. 395
S TEODORESCU H.-N. 80
SAINSUS I. 313 TERESHENKO A.N. 49

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TIDECKS R. 172 VOICU R. 207

TIGINYANU I.M. 39, 43, 138, 207, VOLCIUC O. 36
ŢÎMBALARI E. 294 VOVC V. 285, 288, 317,
TIRON I. 266, 297
TODOSICIUC A. 354
W
TROTTA R. 28 WERLEIN R. 248
TSIULYANU D. 86 WOLF W. 391
TSURKAN A. 168 Y
TSYNTARU N. 75 YAKIMENKO Y.I. 67
TUDORACHE I. 319 YAKUNIN A. 218
TURAN R. 203 YAKUNIN V. 218
ŢURCAN M. 227 YILMAZ E. 203
TURTA C.I. 133 YOSHIDA T. 145
TYULKIN F. 255 YU.A. AGAFONOV 49
U Z
UNGUREANU G.M. 373, 391 ZALAMAI V. 128, 142
UNTILA D. 211 ZALLO E. 28
URSAKI V. 33,128, 207 ZĂNOAGĂ M. 328, 329
URSU T. 175 ZASAVITSKY E. 97, 117
USHENKO A. G. 377 ZATUȘEVSKI I. 304, 310
USHENKO V. 409 ZAUGG C. 427
USHENKO Y. A. 395, 424 ZAVRAJNYI S. 266, 290, 297
V ZDRAVKOV V. 172
VASILIEV V. 234 ZEMȚOVSKI E. 310
VENOT A. 340 ZENKOVA C.YU. 190, 239
VERLAN V.I. 133 ZHOKHOV A.A. 49
VIERU S. 273 ZINENKO V.I. 49
VIERU T. 83, 142, 273 ZUBAREVA V.E. 133
VODA I. 207

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