Copyright © 2008 American Scientific Publishers Journal of

All rights reserved Nanoscience and Nanotechnology

Printed in the United States of America Vol. 8, 3272–3299, 2008

Cadmium Sulphide (CdS) Nanotechnology:

Synthesis and Applications
N. V. Hullavarad∗ , S. S. Hullavarad, and P. C. Karulkar
Office of Electronic Miniaturization, University of Alaska, Fairbanks, AK 99701, USA

Over the past few years there has been sustained interest in the synthesis, characterization and
application of cadmium sulphide (CdS) nanostructures such as nanoparticles, nanowires, nanobelts,
nanospheres. The history of CdS, more recent advances in the chemistry and synthesis of CdS
nanostructures, and their application as nanoscale devices in diverse technology areas from elec-
tronics to targeted drug delivery is described. Although the focus is on CdS, the review provides an
excellent overview of the materials, methods, processes and promising solutions that are emerging.
REVIEW

Keywords: Cadmium Sulphide (CdS) Nanoparticles, Synthesis, Characterization, Nano-

technology, Applications.

CONTENTS that can be tailored by adding a third element to form

a ternary semiconductor, and most importantly, it makes
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3272
2. Quantum Confinement in Semiconductor Nanoparticles . . . . . . 3274 a very effective test vehicle in training as well as in the
3. Different Synthesis Routes of demonstration of innovative technologies (e.g., nanotech-
CdS NanoparticlesDelivered
and Nanostructures by Publishing
. . . . . . . . . .Technology
. . . . . . . . . 3275to: University
nology). Theof Southern
propertiesCalifornia
of CdS are summarized in Table I.
IP: 95.148.164.127
3.1. Chemical Colloidal Method . . . . . . . . . . . . . . . . . . . . . . . 3275 On: Fri, 04 Apr 2014 08:42:52
Research on CdS dates back to 1925 when Huggins2 the-
3.2. Reverse Miceller Method . . . . . . Copyright: . . . . . . . . . . . .American
. . . . . . . 3276Scientific Publishers
3.3. Sol–Gel Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3277
oretically studied the distribution of valence electrons in
3.4. Electrochemical Deposition Method . . . . . . . . . . . . . . . . . 3277 CdS and other crystals using the Lewis theory of valence
3.5. Langmuir-Blodgett (LB) Method . . . . . . . . . . . . . . . . . . . 3279 and compared them with those in diamonds. In 1947,
3.6. Solvothermal/Hydrothermal Method . . . . . . . . . . . . . . . . . 3281 Frerichs3 synthesized single crystals of CdS, CdSe, and
3.7. Micro-Fluidic Method . . . . . . . . . . . . . . . . . . . . . . . . . . . 3283 CdTe by reacting cadmium vapor with H2 S, H2 Se, and
3.8. Functionalized Chiral Method . . . . . . . . . . . . . . . . . . . . . 3283
3.9. Universal Nanoreactor Synthesis Method . . . . . . . . . . . . . 3284 H2 Te, respectively, and called them “incomplete phos-
3.10. Irradiation Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3284 phors” because they did not show any phosphorescence
3.11. Ion Implantation Method . . . . . . . . . . . . . . . . . . . . . . . . . 3285 but exhibited strong photo-conductivity. Photo-cells made
3.12. Molecular Beam Epitaxy (MBE) Method . . . . . . . . . . . . . 3285 from these CdS crystals were found to be extremely sen-
3.13. Biological Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3285
3.14. Direct Vapor Phase (DVP) Technique/VLS (Vapor
sitive throughout the entire spectrum from infra-red down
Liquid-Solid Process)/Catalytic Growth Method . . . . . . . 3285 to ultraviolet, X-rays, and gamma-rays and for corpuscu-
4. Applications of CdS Nanostructures . . . . . . . . . . . . . . . . . . . . . 3287 lar (i.e., alpha- and beta-) rays. Two different mechanisms
4.1. CdS Nanoparticle Diodes/Light Emitting Diodes . . . . . . . 3287 of photo-conductivity were observed: the normal photo-
4.2. CdS Nanoparticles in Photovoltaic Devices . . . . . . . . . . . 3289 conductivity in the region of strong absorption from the
4.3. Hydrogen Production Using CdS Nanoparticles . . . . . . . . 3289
4.4. CdS Nanowires as Optical Wave-Guides and Lasers . . . . 3289 blue to the ultraviolet and selective photo-conductivity in
4.5. Sensors Using CdS Nanoparticles . . . . . . . . . . . . . . . . . . 3290 the region of weak absorption in the visible, X-rays, and
4.6. CdS Nanoparticles in Biological Applications . . . . . . . . . 3291 corpuscular-rays regions. The phenomena observed were
4.7. CdS Nanoparticle Caps for Drug Delivery System . . . . . . 3294 in general accordance with the zonal theory of phospho-
5. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3294
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3295
rescence. Since then single crystals4–21 and thin films22–31
Referencess and Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3295 have been studied extensively. Researchers continue to
be keenly interested in CdS because of their interest in
phenomena at the nanoscale and in developing break-
1. INTRODUCTION
through materials engineered at the nanoscale for many
CdS is a popular II–VI semiconductor material. It can be practical applications. Particularly, nanoparticles, nano-
synthesized with ease, has a large band-gap (2.42 eV) 1 crystals, nanowhiskers, nanorods, and nanowires of CdS
and organic, inorganic, and biological materials based on
∗
Author to whom correspondence should be addressed. nanoscale CdS are being extensively studied.

3272 J. Nanosci. Nanotechnol. 2008, Vol. 8, No. 7 1533-4880/2008/8/3272/028 doi:10.1166/jnn.2008.145

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

The driving force behind exploring the nano area in The as-synthesized CdS nanoparticles are usually pure,
the semiconductor perspective is to achieve higher perfor- structurally uniform with either cubic or hexagonal struc-
mance for functional (optical, chemical, piezo, radiation) ture or a combination of both with hexagonal or wurtzite
devices. Devices using nanoparticles offer an alternative phase dominating. Schroeder et al.32 have reviewed the
fabrication mode to lithography and also certain unique experimental measurements on high pressure induced
opportunities due to size quantization effect. However, this phase changes in CdS, CdSe, and CdSSe nanoparticles.
in turn demands that to exploit the properties of nanopar- Nanoparticles are either capped with or coupled to dif-
ticles, they should have as narrow a size distribution ferent wide band gap semiconductor nanocomposites. The
as possible (monodisperse) and should remain thermally role of interfacial charge transfer has been studied in
stable during any device operation without coagulation. such composite systems. The majority of the work has

N. V. Hullavarad (Deshmukh) received M.Phil. for her work on Molecular Electronic

Devices and Ph.D. for her work on Investigations of CdS nanoparticles and their appli-
cation in diodes. She worked as a Research Associate in University of Maryland,
College Park (UMD) before joining Office of Electronic Miniaturization (OEM). She
has carried out research in nanoparticles and nanowires synthesis, molecular electron-
ics and heterojunction devices. Her present research focuses on investigation of nano-
structured materials for application in microelectronic devices, sensors and systems, and
novel quantum-electronic devices. At OEM, she heads Nanoelectronics Laboratory and

REVIEW
is developing nano fabrication facility to synthesize semiconductor-metal nanoparticles,
nanowires and composite materials for advanced technology applications. She has expertise
in the synthesis characterization and device fabrication of doped and undoped monodis-
persed quantum dots, for applications in electroluminescent devices. She has published over 20 technical articles in the
area of interest. She is a member of The Electrochemical Society and American Vacuum Society.

S. S. Hullavarad received Ph.D. for his work on High Energy Ion Induced Irradia-
tionbyEffects
Delivered and Plasma
Publishing Processing
Technology of GaAs.ofHe
to: University established
Southern ionizing radiation thresh-
California
olds IP:
on 95.148.164.127
GaN and AlGaNOn: UVFri,
detectors
04 Aprby DLTS
2014 measurements. He continued his work
08:42:52
on Wideband Gap Semiconductor
Copyright: growthPublishers
American Scientific and characterization for dopant activation in
SiC, passivation layer for SiC MOSFET and RF MEMS and NEMS devices at Uni-
versity of Maryland, (UMD) College Park, MD. At UMD he developed AlN based
composite structures for high frequency and Q resonators for Army Research Labo-
ratory, MD. He was involved in developing the oxide based Deep UV detectors for
space applications. At UMD he mentored students under Maryland Engineering Research
Internship Training (MERIT) program in collaboration with Federal Research Labora-
tories. He has authored over 40 technical articles and book chapter on the topics of
interest. He heads Microelectronics and Photonics Laboratory at Office of Electronic Miniaturization (OEM), University
of Alaska Fairbanks. His present research at OEM, focuses on developing the nanocomposites based thermal interface
materials for flip chip packaging platforms and nano interconnects. He is a member of American Physical Society,
Materials Research Society and American Vacuum Society.

P. C. Karulkar, the Director of Office of Electronic Miniaturization, University of Alaska

Fairbanks, headed (1993 to 2004) the Microelectronics Division of the University Research
Foundation, Greenbelt, Maryland where he was responsible for R&D and pilot production
programs involving components for high performance electronic systems. He was instru-
mental in developing materials, processes, devices, and system components in a broad range
of technologies including solid state sensors, superconducting devices, silicon, SOS, and
SOI integrated circuits, multichip modules, advanced packaging technologies, and high per-
formance interconnect. He served as the Fab Manager for the 6" wafer fab and advanced
packaging facility at the Microelectronics Research Laboratory in Columbia MD. He has
been recognized by DoD customers for playing a key role in supporting advanced elec-
tronics technology programs that resulted in fielded systems. Karulkar has held positions
in manufacturing and R&D operations in Hugh’s Aircraft Co’s Solid State Products Division, Rockwell International’s
Microelectronics Division, and Massachusetts Institute Technology’s Lincoln Laboratory. In 2004 Karulkar served as
a visiting professor in the Physics Department at the UMBC. Karulkar has published over 30 papers and holds two
patents.
J. Nanosci. Nanotechnol. 8, 3272–3299, 2008 3273
 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.

Table I. Properties of cadmium sulphide. volume of literature. However, most of the directions of
Basic properties the research are covered.
Other names Greenockite, Cadmium(II) sulphide
Molecular formula CdS 2. QUANTUM CONFINEMENT IN
Color Yellow to orange SEMICONDUCTOR NANOPARTICLES
Appearance Crystalline solid
Group and type n-type semiconductor belonging to II–VI group In 1983, Brus44 45 studied the effect of size variation on
Density and phase 4.82 g/cm3 , solid. ionization potential and electron affinity of small inor-
Solubility in water Insoluble
ganic semiconductor crystallites. He proposed a theoret-
Melting point 1750  C at 100 bar
Boiling point 980  C sublimation. ical model based on effective masses of electrons and
Crystal structure Hexagonal and cubic structure with a large holes in bulk. Quantum confinement effects are observed
contribution from the hexagonal phase. in all materials as the particle size is reduced to nano-
Band gap Direct band gap 2.42 eV dimensions.
Mass of electron me 0.19
According to the Effective Mass Approximation theory,
Mass of hole mh 0.8
Bohr radius aB 2.06 nm the energy gap between valence band and conduction band

f Hsolid −144 kJ/mol is equal to the energy required to create a Wannier exciton

Ssolid 71 J/(K mol) (electron–hole pair) in direct band-gap materials. The Bohr
(Ref:http://en.wikipedia.org/wiki/Cadmium_sulfide#column-one,
radius of an exciton is given as
http://encyclopedia.thefreedictionary.com/cadmium + sulphide).

REVIEW

2
1 1
aB = 2 +
e me m h
discussed investigations of the optical properties, structure
and morphology of polydispersed CdS. Materials like where, me and mh are electron and hole mass and
is the
33 34
Eu, Mn, etc. have been used to dope CdS nanopar- dielectric constant of the semiconductor. The Bohr radius
ticles in varying concentrations and have resulted in of an exciton in a particular material helps in estimat-
luminescence enhancement or quenching. CdS nanopar- ing the size dependent region for semiconductor nanopar-
ticles are also used as a catalyst for the photocatalytic ticles. If the dimension of nanocrystallites is comparable
decomposition of water. This will be discussed in detail
Delivered by Publishing Technology to: to the Bohr
University radius ofCalifornia
of Southern an exciton dimension, then they
IP: 95.148.164.127 On:
later. There have been attempts to form core–shell, cou- Fri, 04are
Aprdrastically
2014 influencing
08:42:52 the spatially localized excitation
Copyright: American Scientific Publishers
spectrum as illustrated by Brus. This is similar to energy
pled (Figs. 1 (Ref. [35]) and 2 (Ref. [36])), and doped
37
nanoparticles of CdS with other materials. A p–n diode, quantization for a Particle in a box which results in dis-
n-CdS/p-AgGaS2 was fabricated by decorating the surface crete excitation energy levels for the particle. According to
of AgGaS2 with nanoparticles of n-type CdS using the Brus, the size dependent energy gap (E  ) for a nanoparticle
hydrothermal method. The nanoparticles tend to coagulate having a physical radius (R) is given as
upon annealing and form larger particles. The coagulation E  = Eg + E (1)
of CdS nanoparticles and the effect of annealing upon the

structural phase transform phonon modes based on particle
2 2 1 1 18e2
E = + − + polarization term (2)
growth are discussed in details by Sivasubramanian et al.38 2R2 me mh
2 R
There have been review articles on II–VI semiconduc- Where, Eg is the bulk semiconductor band gap, E is the
tor nanoparticles, starting with Brus39 (1986), “Experiment size-induced shift in the energy of the lowest excited state
and theory of electronic wave function in semiconductor (the traditional conduction band), R is the particle radius,
clusters;” Henglein40 (1989) “Physicochemical properties and
is dielectric constant. The first term in Eq. (2) rep-
of extremely small colloid metal and semiconductor par- resents the particle-in-box localization energy. The polar-
ticles;” Wang and Herron41 (1991), “The material syn- ization term being very small does not affect the equation
thesis, quantum size effects and photophysical properties and can be neglected.
of nanometer-sized semiconductor clusters;” Schroeder42 The bulk semiconductor band gap widens as the size
(1996), “Spectroscopy of II–VI nanocrystals at high pres- of the particle decreases to the nanoregime. It is mea-
sure and high temperature” Trindade43 (2000), “The sured similar to the energy gap between the Highest Occu-
synthesis, properties and perspectives of nanocrystalline pied Molecular Orbital and Lowest Unoccupied Molecular
semiconductor.” A number of diverse techniques used to Orbital (HOMO-LUMO) in the case of molecules. The
synthesize bare as well as surface passivated (or some- dependence of the energy gap on the change in particle
times called “capped”) CdS nanostructures (and materials size has been verified for CdS nanoparticles along with
based on CdS nanostructures) are discussed in this paper. the size dependent behaviors46 of the energy gaps of ZnO,
A number of interesting applications of CdS nanotech- GaAs, and InSb as seen in Figure 3. Recently attempts
nology are also discussed. The review is not intended to have been made to modify the effective mass approxima-
include every publication in nano CdS because of the large tion theory.47

3274 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

TiO

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Fig. 1. Thin films of TiO2 (core)/CdS (shell) nanorods. (a) and (b) SEMs of thin films of TiO2 nanorods without the attachment CdS nanoparticles.
(c) A schematic of how nanoparticles of CdS are attached to TiO2 nanorods. (d) and (e) SEMs of thin films of TiO2 nanorods with the attachment
CdS nanoparticles. (f) TEM of a single TiO2 (core)/CdS (shell) nanorod. Reprinted with permission from [35], H. Jia et al., Electrochem. Comm. 9,
354 (2007). © 2007, Elsevier.

3. DIFFERENT SYNTHESIS ROUTES OF salt solution in the presence of a capping agent in an

CdS NANOPARTICLES AND inert atmosphere under continuous stirring. Nanoparticle
NANOSTRUCTURES size is determined by the concentrations of the cadmium
salt, sulphur salt and capping agents. Aqueous or non-
3.1. Chemical Colloidal Method aqueous media and organic or inorganic capping agents
Small particles homogeneously dispersed in a solution can be used. The final products can be dried to obtain
are known as colloids. Two such particles are attracted nanoparticle powders. Redispersion of nanoparticle pow-
to each other by Van der Waals force when the dis- ders in aqueous or non-aqueous media is possible. The
tance between them is small. Hence, a colloidal suspen- room temperature (25  C) synthesis method was employed
sion needs to be stabilized against aggregation. Chemical by us to synthesize nearly monodisperse (particles having
colloidal method48 49 of producing nanoparticles involves same size) nanoparticles that exhibited the UV absorption
a chemical reaction to produce the particles and preventing spectra shown in Figure 4. It was observed that as the
coagulation by capping them with organic molecules50–54 size of the nanoparticle reduces, the optical and electrical
or surfactants55 i.e., long chain molecules. properties change (Fig. 5).
Most commonly, CdS nanoparticles are produced by Thioglycerol,56 57 mercaptoethano,58 alkanethiols,
gradually mixing a sulphur salt solution into a cadmium alkylphosphine, thioacetamide glacial acetic acid and

J. Nanosci. Nanotechnol. 8, 3272–3299, 2008 3275

 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.

A B C D E

1.19 nm 1.77 nm 1.93 nm 2.4 nm ~Bulk CdS

Fig. 2. A schematic and a TEM image of n-type CdS nanoparticles

shell/AgGaS2 core. Reprinted with permission from [36], J. S. Jang et al.,
Catal. Today 120, 174 (2007). © 2007, Elsevier.
REVIEW

2-methoxy ethanol,59 tyrosine, tryptophan60 or dithiols61 62

D
are some of the capping agents used in this method.
Similarly, porous silicate casts, called zeolites, can be
C
used to form nanoparticles. Zeolites having different pore B
A
sizes are used instead of organic capping agents. (Zeolites
are crystals having a honeycomb structure made from sil-
icates). Similar to the colloidal chemical method, Cd-salt
solutions are addedDelivered by Publishing
to zeolite Technology
solutions under continu-to: University of Southern California
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UV/Vis absorption spectra of CdS nanoparticles of different
08:42:52
ous stirring. The precipitate is then washed with
Copyright: doubleScientific
American sizes and the corresponding nanoparticles in the dried powder form.
Publishers
distilled water and dried. This dried precipitate is then From N. V. Hullavarad, unpublished data, Ph.D. Thesis, Investigation
added to a S-salt solution resulting in CdS nanoparticles. of CdS Nanoparticles for Fabrication of Diodes, University of Pune,
Ganeshkhind, Pune, India (2001). © 2001.

The non-active zeolite matrix is removed by treating the

final product with an HF solution. The CdS particles
that are not dissolved in the HF solution are washed in
hot water until the pH becomes neutral.63 Keeping the
nanoparticles thus produced separate is a continuing tech-
nological challenge. Size-selected nanoparticles of high
quality are produced only in limited cases, and some of the
notable attempts have been made using procedures such as
size selective precipitation64 or pyrolysis of organometallic
compounds65 66 injection into hot coordinating solvent.

3.2. Reverse Miceller Method

This method is similar to water-in-oil microemulsions.

Two immiscible liquids (e.g., water and oil) form a
microemulsion when mixed into a macroscopically homo-
geneous but microscopically heterogeneous single phase
by addition of one or more surfactants. Microemulsions
have characteristic properties such as optical clarity, ther-
Fig. 3. Energy of the lowest excited electronic state for a crystallite as a modynamic stability, low viscosity, dissolvability, low
function of its diameter for ZnO, GaAs, CdS and InSb. Bulk band gap is interfacial tension and large interfacial area. The molecules
represented by solid dashed lines. Reprinted with permission from [46], in microemulsions orient themselves (self-assemble) in
L. E. Brus et al., J. Chem. Phys. 80, 4403 (1984). © 1984, American forms known as micelles, reverse micelles or vesicles as
Institute of Physics.
3276 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008
Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

aligned-nanowire bundles. Based on this strategy, CdS

aligned-nanowire bundles with high yields were success-
fully prepared in a water system at room temperature using
a soft template. The results revealed that the morpho-
logy of the CdS aligned-nanowire bundles were uniform
in lengths of several microns and the diameters of each
single wire were 10–30 nm for CdS.87

3.3. Sol–Gel Method

The sol–gel88 technique is well-known for fabrication of
pure and homogeneous silica matrices.89 Sols are disper-
sions of colloidal particles in a liquid.90 Gels are inter-
connected, rigid networks with pores of sub micrometer
dimensions and polymeric chains whose average length is
greater than a micrometer.91 CdS nanoparticles have been
synthesized by sol gel technique starting with a mixture of
TEOS- (Si(OC2 H5 )4 ), (C2 H5 OH) and H2 O that is stirred
continuously. Either an acid or a base is used as a cata-

REVIEW
lyst. Cd-salt solution is added to the above mixture and
then S-salt solution is added very gradually to obtain CdS
nanoparticles. In some cases, the sol containing Cd-ions is
exposed to H2 S gas92 to form CdS nanoparticles. The onset
of nanoparticle formation becomes evident from the imme-
Fig. 5. Photoluminescence (PL) and the corresponding UV/Vis absorp- diate change of color of the solution to yellow. The entire
tion spectra of the as-prepared CdS nanocrystals having different sizes. solution is stirred continuously until a gel is formed. The
Reprinted with permission from [151], W. W. Yu and X. Peng, Angew. sol–gel process
Delivered
Chem. Int. Ed. 4, 2368 (2002). by Publishing
© 2002, WILEY-VCH Technology
Verlag GmbH. to: University of needs either
Southern a slow or supercritical con-
California
trolled drying
IP: 95.148.164.127 On: Fri, 04 Apr 2014 08:42:52 process to obtain porous materials in the
form of alcogel,
Copyright: American Scientific Publishersxerogel or aerogels. For the synthesis
shown in Figures 6(a)67 and (b)68 . This microemulsion of CdS nanoparticles in monolithic form, the mixture is
technique69–76 has been applied to synthesize CdS nanopar- allowed to dry for about a month under ambient con-
ticles. An aqueous solution of CdCl2 · 5H2 O was added ditions. In one of our studies,93 this technique yielded
gradually in minute quantity to a solution of77 cyclohex- monoliths of white and yellow color, indicating the parti-
ane and surfactant (Tween-80, Peregals, C12E9 or Tri- cle size variation of CdS nanoparticles embedded in them.
ton X-100) and after that n-pentanol was added. This Figures 8–10 show the UV-absorption spectra and SEM
solution was mixed vigorously to form microemulsion. images of CdS nanoparticles embedded in SiO2 matrix.
Similarly, a microemulsion of Na2 S · 9H2 O was prepared CdS nanoparticles embedded in the fibrous network have
using the same surfactants. Then an equal volume of also been reported.94 Ptatscheck et al.95 have synthesized
two microemulsions with the same surfactant were mixed CdS nanoparticles in a silica matrix in the size range of
together followed by gentle shaking. The final solution was 0.4 to 1.6 nm using this method. CdS nanoparticles can
left for 12 hrs to allow formation of nanostructures of dif- be embedded into zirconia96 or titania97 matrices instead of
ferent morphologies. CdS nanostructures were harvested silica matrices using the sol–gel technique. Morita et al.98
by adding propanol to break up the micelles. Precipitates used a Zr-sol–gel matrix to prepare CdS nanoparticles
were washed repeatedly by centrifuging with propanol and doped with Mn2+ and Eu3+ . Silica-titania sol–gel compos-
ethanol to remove the excess surfactant. The final product ite matrices are also used for CdS nanoparticle synthesis.99
was light yellow in color, insoluble in water and ethanol The sol–gel method has many advantages including
and could be stored in ethanol. reproducible homogeneous CdS nanoparticle doped thin
Brien et al.78 79 studied monodispersed CdS nanopar- films,100 achievement of simple material modification by
ticles in two sizes (3.5 nm to 5.9 nm) that were pro- incorporating organic functional groups,101 102 and use of
duced using the miceller method. CdS-nanocomposites80–85 readily available processes to attain specific device struc-
either in the form of core–shell nanoparticles, or grown on ture with low cost materials and equipment.
top of latex spheres, may find application in bio fluores-
cence. CdS nanostructures are also embedded in polymer 3.4. Electrochemical Deposition Method
microfibers86 as seen in Figure 7, forming nanocomposite
fibers. A 1-dimensional inorganic coordination polymer Electrochemical deposition103 is widely used to form
template route was developed to synthesize metal sulfide thin films of metals,104 semiconductors,105 polymers,106

J. Nanosci. Nanotechnol. 8, 3272–3299, 2008 3277

 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.

(a) (b)
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Fig. 6. (a) Oversimplified representation of organized structures formed from surfactants. Reprinted with permission from [67], J. H. Fendler, Chem.
Rev. 1907, 877 (1987). © 1987, American Chemical Society; (b) Schematic of CdS nanoparticles stabilized by polyacrylamide in the inner cavities
and on the outer surface of the ethylendiaminetetraacetate (EDTA) vesicle membrane. Reprinted with permission from [68], T. I. Igumenova and V. N.
Parmon, J. Photochem. Photobiol. A: Chem. 90, 159 (1995). © 1995, Elsevier.

polymer-semiconductor composites107 and insulators108 on aqueous solution and then were oxidized. Using these
conductive substrates. It is possible to grow quasi-one and modifications, it is possible to obtain high monodispersiv-
-two dimensional structures normal to the substrate sur- ity due to diffusion decoupling of Cd nanocrystals. The
face by confining electrodeposition to cells of appropriate oxidized Cd nanocrystals were later exposed to H2 S to
dimensions. Porous aluminum oxide templates formed by form passivated CdS nanoparticles.113 The exposure of
anodic etching work well as ordered templates to con- the solution during electrochemical deposition to light is
fine the growth of structures.109 CdS nanowire arrays, termed as photo-chemical electrodeposition and is used
1 m in length and 9 nm in diameter have been formed to deposit CdS films.114 Stickney and co-workers pro-
by electro chemical method from an electrolyte solu- posed electrochemical atomic layer epitaxy (ECALE) as a
tion consisting of Cd2+ and dimethyl sulfoxide.110 This low-cost procedure for producing structurally well-ordered
method has been adopted by Chen et al.111 to fabri- ultrathin layers of CdS and other compound semiconduc-
cate the photoelectrodes consisting of TiO2 nanotubes/CdS tors on polycrystalline as well as on single-crystal gold
nanoparticles core–shell structures (nanotubes core and electrodes. ECALE is an improvement on the conven-
CdS nanoparticles shells). Ensembles of 200,000–400,000 tional direct current electrochemical deposition technique.
sulfur capped, CdS nanoparticles have been synthesized The ECALE method is based on the alternate underpo-
by modified electrochemical method.112 In this method, tential deposition (the potential required to electrodeposit
the Cd nanocrystals were first electrodeposited from an an element on another element occurs before the required

3278 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

(a) CdS03 TEOS/H2O: HCl/H2O –0.5:0.2

CdS04 TEOS/H2O: HCl/H2O –0.5:3.5
CdS05 TEOS/H2O: HCl/H2O –0.25:0.1
CdS06 TEOS/H2O: HCl/H2O –0.08:1.25
CdS07 TEOS/H2O: HCl/H2O –0.065:0.025
CdS08 TEOS/H2O: HCl/H2O –0.054:0.81

Absorption (arb.units)
(b)

200 300 400 500 600

Wavelength (nm)

REVIEW
Fig. 9. SEM of CdS nanoparticles embedded in SiO2 matrix. The inset
shows UV absorption spectra for six different samples. Combined 2
figures. Reprinted with permission from [93], N. V. Hullavarad and S. S.
Hullavarad, Photonics and Nanostructures—Fundamentals and Applica-
tions 5, 156 (2007). © 2007, Elsevier.

potential to deposit the element on itself) of atomic layers

of both elements forming the compound semiconductor.
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There of Southern
have been reports onCalifornia
the formation of thin films of
Fig. 7. (a) SEM images of polystyrene fibers containing CdS nanopar-
IP: 95.148.164.127 On: Fri, 04 Apr 2014 08:42:52
ticles. (b) TEM images of PS fibers containing CdS nanoparticles.
Copyright: CdS, CdSe, and
American Scientific Publishers CdTe by the ECALE method on poly-
Reprinted with permission from [86], X. Lu et al., Mater. Lett. 61, 2288 crystalline gold115 and silver substrates.116 5 nm sized CdS
(2007). © 2007, Elsevier. nanostructures have been deposited on multi-wall carbon
nanotubes (MWCNT) and titanate nanotubes using electro-
1.0
% (CdS02)
chemical deposition.117 These studies revealed nucleation
350 nm
% (CdS01) of CdS nanoparticles at the tip of MWCNT and a smaller
3.5 eV
260 nm number of particles on the body of CNT at higher cathodic
4.7 eV
potential. Figure 11 shows dark and illuminated I–V for
CdS/MWCNT. In this case MWCNT grown by CVD on
n++ type (100) Si wafer were used as working electrodes
Absorption (arb.units)

TEOS:Cd -1:1

for CdS deposition.

TEOS:Cd -1:0.5

0.5
3.5. Langmuir-Blodgett (LB) Method

The Langmuir-Blodgett118 technique is used to form

homogeneous, large area ultra-thin films with a precise
control over their thickness. It leverages the spreading of
a liquid drop of a lighter, immiscible liquid on the surface
of another, heavier liquid. In the limit, the film spreads to
form a monolayer. The thickness of such ultra-thin films
0.0
250 300 350 400 450 500 550 600
(the so-called monolayers) can be controlled by controlling
Wavelength (nm)
the area over which the film is allowed to spread. The film
is then transferred onto a substrate by dipping and with-
Fig. 8. UV-absorption spectra of two particle sizes of CdS nanoparticles drawing it vertically. The technique requires very simple
embedded in SiO2 matrix and the monoliths having two different colors
equipment: a chemical resistant trough, movable barriers
(white and yellow) indicative of formation of different sized nanoparti-
cles. Reprinted with permission from [93], N. V. Hullavarad and S. S. for controlling continuous area the surface of the liquid,
Hullavarad, Photonics and Nanostructures—Fundamentals and Applica- and a mechanism for controlled dipping and retracting of
tions 5, 156 (2007), © 2007, Elsevier. the substrate. This method has been used effectively to

J. Nanosci. Nanotechnol. 8, 3272–3299, 2008 3279

 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.
REVIEW

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Copyright: American Scientific Publishers

Fig. 10. SEM of CdS nanoparticles embedded in SiO2 matrix. The inset shows UV absorption spectra for six different samples. Combined 2 figures.
Reprinted with permission from [93], N. V. Hullavarad and S. S. Hullavarad, Photonics and Nanostructures—Fundamentals and Applications 5, 156
(2007). © 2007, Elsevier.

form CdS nanoparticles in a wide range of diameters.119–127 with monolayers of Cd-arachidate using LB technique,
The process starts with the formation of an LB film of which when exposed to H2 S gas formed CdS nanopar-
a Cd containing organic liquid on the surface of water ticles attached to CNT surfaces. In this experiment, the
(Fig. 12). The film is then transferred to a substrate, expos- CdS nanoparticles self assembled on the surface of the
ing the film to H2 S to convert it to CdS nanoparticles. carbon nanotubes as seen in Figure 13. Zhang et al.,130
The thickness of the film on the substrate can be increased synthesized CdS nanoparticles on a DNA template as
by repeated application of the LB films resulting in CdS seen in Figure 14. In another work, multiple layers
nanoparticles that are a few nanometers in size or are large of CdS nanoparticles fabricated by using LB technique
enough to exhibit bulk material properties.128 were connected to an aromatic bifunctional molecule,
Valentini et al.129 synthesized CdS nanoparticles on 4-carboxythiophenol. However, the quality of LB films
the surface of carbon nanotubes using this technique, formed in this work deteriorated after seven monolayers.131
where carbon nanotubes were deposited on Si3 N/Si sub- CdS nanoparticles have been incorporated into conducting
strates by CVD method. The nanotubes were then coated and nonconducting polymers by depositing composite

3280 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

REVIEW
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Copyright: American Scientific Publishers

Fig. 11. SEM and HRTEM images of CdS particles deposited on the surface a typical multiwalled carbon nanotube (MWNT). Dark and light I–V
curves for CdS/MWNT: (a) under white light from halogen lamp (100 mW/cm2 ); the insert is an AFM image of a CdS/MWNT channel for device
and (b) under blue light from blue-LED, (470 nm, 1 mW/cm2 ). Reprinted with permission from [117], Y. Kang and D. Kim, Sens. Actuators A 125,
114 (2006). © 2006, Elsevier.

multilayers of poly(3-octylthiophene)-cadmium-arachidate the detailed mechanism of growth leading to the formation

(POT-CdA) and poyaniline-cadmium-arachidate (PANI- of remarkably well-ordered Langmuir-Blodgett (LB) films,
CdA) by LB technique.132 LB technique has been used to the implications of melting process in lower dimensions
obtain alternate layers of CdS/CuS nanostructures.133 and recent results obtained by X-ray scattering technique
This technique was also used to demonstrate the effect have been discussed.137
of C60 atoms placed in close proximity to CdS nanoparti-
cles in long chain fatty acids. The long chain fatty acids 3.6. Solvothermal/Hydrothermal Method
keep the CdS nanoparticles separated from each other.
However, the presence of C60 quenched the photolumi- This technique,138–142 is based on the deposition of nano-
nescence of CdS nanoparticles. The CdS nanoparticles structures out of a supersaturated vapor media in an auto-
were found to be oval in shape.134 However, spherical clave. A measured amount of a cadmium salt is first mixed
CdS nanoparticles that did not exhibit two-dimensional thoroughly with a polymer like polyethylene glycol (PEG).
platelet appearance were produced in hydrophilic inter- A sulfur containing compound is then added to this mix-
layers using the LB technique.135 Doped CdS particles ture which is then put in a chemical resistant autoclave
can be produced using LB technique. Mn doped CdS containing a solvent like diethlyamine. Combinations of
nanoparticles of diameter 3 nm were obtained by reaction various polymers and solvents can be used. Temperature
of arachidate LB films containing both Cd and Mn with and pressure in the autoclave are raised to pre-optimized
H2 S in NH3 atmosphere.136 In a comprehensive review, levels and then allowed to cool to room temperature.

J. Nanosci. Nanotechnol. 8, 3272–3299, 2008 3281

 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.

Fig. 12. A schematic diagram of stearic acid/eicosylamine alternate layer Langmuir-Blodgett (LB) films. Reprinted with permission from [122],
R. Capan et al., Thin Solid Films 515, 3956 (2007). © 2007, Elsevier.
REVIEW

Different types of nanoscale precipitates (nanoparticles,

nanorods or nanowires) are formed depending on the
chemicals, temperature-pressure cycle, and the time in the
autoclave. Nanostructures are filtered out and are washed
to remove excess unreacted starting materials. Li et al.143
synthesized 10 nm size CdS particles using this method.
Yao et al.144 applied this technique to synthesizing thin
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films of of Southern California
nanocomposites with CdS nanowires in poly
IP: 95.148.164.127 On: Fri, 04 Apr 2014 08:42:52
vinyl alcohol (PVA).
Copyright: American Scientific Publishers Though the underlying mechanism is
unknown, the presence of the host material PVA encour-
aged the formation of long CdS nanowires with large

50 nm

Fig. 14. TEM image and electron diffraction pattern of the selected
region of CdS nanoparticles on oligomeric DNA (oligo[A]10 ) mono-
layer film at the surface pressure of 20 mNm−1 . Schematic diagram of
n-octadecylamine (ODA) and oligo[A]10 at the gas/liquid interface at dif-
Fig. 13. SEM image of CdS nanoparticles coated on carbon nanotube. ferent surface pressures and the corresponding top-view of the gas/liquid
Reprinted with permission from [129], L. Valentini et al., Chem. Phys. interface. Reprinted with permission from [130], X. Zhang et al., Mater.
Lett. 392, 214 (2004). © 2004, Elsevier. Chem. Phys. 77, 899 (2002). © 2002, Elsevier.

3282 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

aspect ratios (Fig. 15). CdS nanoparticles attached to

titanate nanotubes have also been synthesized145 using
solvo-thermal method. This technique has been used to
fabricate the CdSe core/CdS shell nanocrystals, the pho-
toluminescence quantum yield for which was found to
be higher than that for CdSe nanoparticles without the
CdS shell.146 CdS nanowires doped with Mn2+ have been
synthesized by extending this method by first mixing the
desired amounts of Mn and Cd salts in an autoclave.147
In principle, this technique has the potential to become a
volume production technique acceptable for an industrial
environment where hazardous chemicals could be reused,
recycled or segregated.
3.7. Micro-Fluidic Method
Hung et al.148 developed a very novel microfluidic149
device to synthesize monodispersed CdS nanoparticles by
rapidly mixing minute but well controlled quantities of salt
precursors in a silicone oil environment. The microfluidic

REVIEW
device (Fig. 16) consisted of three inlets in the form of
a double T junction; one inlet for introducing silicone oil
that acts as the carrier fluid and the other two inlets for
dispensing nanoscale droplets of aqueous Cd and S salt
solutions. The design of the expansion chamber allowed
the droplets of Cd and S salt solutions that are dispersed
into the oil medium to experience a velocity gradient
andUniversity
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Southern micro- (or nano-) reactors.
California
IP: 95.148.164.127 On: Fri,Nanoparticles
04 Apr 2014were eventually formed in these merged
08:42:52
Copyright: American Scientific Publisherswhen the stream of the droplets tra-
droplets especially
versed through a long channel that involved several zigzag
turns. The size of the fused (Cd + S) droplets was as
large as 60 microns (the diameter of the channel) with
CdS concentration at 5 × 10−5 M. The technique involves
very clever use of microfluidics to produce very uniform
nanoparticles down to 4 nm size.

3.8. Functionalized Chiral Method

Helical arrays of CdS nanoparticles were grown on a
functionalized lipid nanotube (FLNT) template. This kind

Water inlet 1

Pinch Exiting
junction junction
Oil inlet Outlet
stream

Wedge shaped
chamber

Water inlet 2

Fig. 15. TEM images of CdS nanowires (a) prepared in the absence of Fig. 16. Schematic diagram for the synthesis of CdS by micro-fluidic
Poly vinyl-alcohol PVA, (b) prepared at 140  C for 10 h, and (c) prepared method. Reprinted with permission from [148], L. H. Hung et al., The
at 140  C for 48 h. Reprinted with permission from [144], J. Yao et al., Royal Soc. Chem. Lab Chip 6, 174 (2006). © 2006, The Royal Society
Mat. Lett. 59, 3652 (2005). © 2005, Elsevier. of Chemistry.

J. Nanosci. Nanotechnol. 8, 3272–3299, 2008 3283

 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.

of helical ordered alignment of inorganic materials has

specific applications as asymmetric reaction catalysts,
sensors, optical materials and electronic nanodevices.150
Similarly, tunable reactivity of monomers for CdS
nanoparticles was studied by Yu et al.151 The tunable reac-
tivity of monomers provides a required balance between
nucleation and growth of the nanoparticles. The tempo-
ral course of the nucleation and growth of semiconductor
nanocrystals can be tuned by changing the concentration
of ligands in a non-coordinating solvent. The requirement
for such a reaction is to have a fast but short nucleation
stage and a slow but long growth stage.

3.9. Universal Nanoreactor Synthesis Method

This method was developed by Yue et al.152 The metal

(Cd-ion) containing domains serve as localized reaction
sites for cluster synthesis via reaction with H2 S or any
sulphur containing gas to form metal sulphides (CdS).
REVIEW

The domains which were distinctly spaced, behave as

nanoreactors within which nanoclusters were synthesized.
Mixed cluster synthesis is also possible using this method.
This scheme can be used with various combinations of
metal salts to yield many different doped semiconduc-
tor nanocluster species. Lemon et al.153 have reported the
synthesis of CdS nanoparticles using this method. The
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luminescent assemblies wereby Publishing
prepared usingTechnology
dendrimers asto: University of Southern California
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both nanoreactor and stabilizer. The dendrimers
Copyright: first actScientific Publishers
American
2+
as a nanoreactor that sequesters Cd ions and then after
reacting with S—it stabilizes the resulting CdS nanoparti-
cles by preventing agglomeration.

3.10. Irradiation Method

It is well known that energetic electromagnetic radiations as

well as charged particles cause both physical and chemical
reactions on a nanoscale. This simple principle was lever-
aged by Zhu et al.155–158 to prepare nanocrystalline metals,
metal-sulfides, metal-oxides and glass-metal nanocompos-
ites. CdS nanoparticles can be synthesized159 160 by irra-
diating an aqueous or anhydrous ethanol based solution
containing metal-salts and one of the sulfur sources; such
as sodium thiosulphate, mercaptoethanol, or carbon disul-
phide; with gamma rays. Isopropyl alcohol is added as a
scavenger for hydroxyl radicals in this process carried out
at the room temperature and ambient pressure (Fig. 17).
Qiao et al.161 illustrated that sulfur ions are released from Fig. 17. Evolution of CdS nanoparticles with varying dose of gamma
radiation at pH 7 and pH 4.5 is observed. (a) UV–visible absorption at
HS− ions when sodium thiosulphate and mercaptoethanol
pH 7, (b) photoluminescence at pH 7 and (c) UV–visible absorption at pH
solutions are irradiated with gamma rays, and they in turn 4.5. Reprinted with permission from [159], A. Chatterjee et al., J. Colloid
react with Cd ions to form CdS nanoparticles. Interface Sci. 294, 334 (2006). © 2006, Elsevier.

HS− (from the solution) −→ S2− + H+ Hayes et al.162 obtained CdS colloids by irradiating solu-
 ray irradiation tions containing cadmium ions and a thiol (3-mercapto-
propane-1, 2-diol, RSH) with -rays. CdS nanoparticles
Cd2+ + S2− → CdS with a mean size of 2.3 nm have been prepared by

3284 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

irradiating a solution containing cadmium chloride and 3.13. Biological Method

carbon disulfide in ethanol with -rays.163 164 Similarly,
CdS nanoparticles of different sizes were formed by illu- Dameron et al.180 (1989) discovered biosynthesis of CdS
minating Cd and S salt solutions with UV radiation from quantum crystallites in yeasts, – Candida glabgrata and
a mercury lamp.165 protein, – Schizosaccharmyces pombe (S pombe), cultured
in the presence of Cd-salt. First, a stoichiometric amount
of Cd-salts are titrated into S pombe producing a complex-
3.11. Ion Implantation Method peptide. Then sulphide is titrated into this metallo-
peptide complex forming nanoparticles. These particles
Ionization method is another unique way to produce
are purified by anion exchange chromatography using a
compound-semiconductor nanoparticles.166–169 It has been
cellulose column and a buffer. Martinez et al.181 synthe-
used to deposit II–VI nanocrystals170 171 by implanta-
sized uniformly sized peptide-bound CdS particles from
tion of constituent elements. First, clusters of metals or
C. glabrata, S pombe and the extracellular CdS particles
semiconductor are produced by using laser vaporization,
from S pombe. The colloidal synthesis of CdS nanopar-
and then an electron beam ionizes the clusters. These are
ticles with the biostabilizers cysteine and glutathione,182
then accelerated towards a substrate. As stable clusters,
at pH values ranging from 4 to 10, respectively, allows
these do not coalesce.
the simultaneous variation of the synthesis parameters in
CdS nano particle embedded in SiO2 were obtained by
a systematic manner, thereby obtaining the synergistic
implanting equal doses of charged Cd ions and S into
interaction effects. The band gap energies of the quantum
amorphous SiO2 .172 The synthesis of the nanoparticles

REVIEW
dots can be tuned from 3.32 to 4.26 eV by varying the
took place during ion implantation either at room or LN2
type and concentrations of stabilizer, pH value, and con-
temperature. Annealing the samples at higher tempera-
centration of sulfide source. The energy position is signif-
tures caused an increase in the average size of synthesized
icantly dependent on the interaction between the pH value
nanoparticles.
and the concentration of the stabilizer, and the effect of
Meldrum et al.173 have reviewed the use of ion irradi- high glutathione concentration is opposite at acidic and
ation to fabricate nanomaterials and their applications in alkaline conditions thus leading to energy gaps of 4.10 eV
devices. This technique produces a high density of nano- at pH = 6 and of 3.64 eV at pH = 10. Similar efforts are
crystal precipitates, offers flexibility
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Technology University of Southern California
made to synthesize CdS nanoparticles using various bio-
IP: 95.148.164.127
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183–188
logical molecules.
Copyright: American Scientific Publishers A comprehensive review on the
and has found applications in producing materials that application of CdS in view of biological synthesis and
exhibit third order nonlinear optical effects due to the pre- applications is reported elsewhere.189
cise transfer of energy localized on a nanoscale.
3.14. Direct Vapor Phase (DVP) Technique/VLS
3.12. Molecular Beam Epitaxy (MBE) Method (Vapor Liquid-Solid Process)/Catalytic
Growth Method
MBE174 175 is used for preparing nanostructure arrays hav-
ing specific sizes.176 An MBE growth chamber consists The Direct Vapor Phase technique has been explored to
of an extensive liquid N2 cryoshroud for efficiently freez- grow CdS nanostructures. DVP, also known as VLS pro-
ing out of high vapor pressure materials such as sul- cess or catalytic growth process, is a modification of the
fur. The growth of nanostructures using MBE is carried vapour transport and thermal evaporation method, in which
out using two separate standard low temperature effusion the precursor material is first heated and the vapors are
cells for cadmium and sulfur. The sulfur effusion cell is transported to the substrate location due to the gas pres-
heated independently in the range of (110–380  C) and is sure gradient, leading to the formation of nanowhiskers,
equipped with a post heating zone that is operated at about nanobelts, and nanowires. However, the concentration of
200  C. Ueta et al.177 demonstrated the selective growth of the precursors, amount of gas flow, and most importantly
pyramid shaped CdS quantum dots (nanoparticles grown the location of the substrate is chosen such that the final
on the substrates) on GaAs (001) substrates. The formation products are directly deposited onto substrates. The evap-
of small islands (typically 3–10 nm) during the growth of oration temperatures of DVP (∼600–800  C) are lower
quantum well structures makes it relevant for fabricating than those of thermal evaporation (1800–2000  C). This
room temperature opto-electronic devices.178 These small is an inexpensive technique and has the potential to grow
islands lead to the formation of quasi-zero dimensional materials on a large scale. Zhang et al.190 have grown CdS
states. The significant development in the MBE growth of nanowires with Sn particles attached at the end of each
quantum well structures of CdSe/ZnSe has been reported nanowire using this technique as seen in Figure 18. Sin-
where CdS is used as a source of Cd along with the substi- gle crystalline CdS nanobelts were also grown by physical
tution of sulfur by selenium that leads to the suppression evaporation.191 In a similar experiment, Dong et al.192 have
of Cd segregation.179 shown the formation of CdS nanobelts and nanowires on

J. Nanosci. Nanotechnol. 8, 3272–3299, 2008 3285

 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.

(a)

(a)

(b)
REVIEW

(b)
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Copyright: American Scientific Publishers

Fig. 19. SEM images of CdS nanobelts (a) and CdS nanowires (b)
formed on tungsten substrates. Reprinted with permission from [192],
L. Dong et al., Chem. Phys. Lett. 376, 653 (2003). © 2003, Elsevier.

(c)

Fig. 18. (a) A SEM image of the as-synthesized products. (b) A typical
SEM image of the CdS hierarchical nanostructures. (c) A SEM image
of the CdS nanoneedle. It has a large head and another tip exhibits
sharp morphology. Reprinted with permission from [190], J. Zhang et al.,
J. Cryst. Growth 293, 236 (2006). © 2006, Elsevier.

tungsten (W) substrates as seen in Figure 19. Most CdS

nanowires are hexagonal in structure. Tao and Wu193 , how-
ever, have shown the formation of cubic as well as hexag-
onal CdS nanowires. CdS nanowires doped with different
percentage of Sb194 show a red shift in the PL peak up
to 55 nm with an increase in PL intensity (Fig. 20). The
large scale CdS nanobelts were synthesized using this tech-
nique without any catalyst and the nanobelts were found Fig. 20. The PL spectra of the (a) control CdS nanowires (b) doped
to have hexagonal structure with PL emission at 512 and with 1% Sb and (c) doped with 2% Sb. Reprinted with permission from
713 nm.195 Li et al.196 have reported nanobelts with lengths [194], S. M. Zhou, Mater. Lett. (2006). © 2006, Elsevier.

3286 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

in micrometer and 100–200 nm width, grown by decom- ITO PPV CdS Metal
position of CdS at 650  C in pure H2 as a carrier gas. The
self assembly nano-electrochemistry growth of dendrite- 4.6 eV
2.7 eV 3.8 eV
CdS assisted CdS/SiO2 nanowire arrays were formed upon Ag - 4.2 eV Ag 4.2 eV
thermal evaporation of CdS and CdO on Si substrates.197 2.4 eV
The evolution of CdS nanowires during the thermal evap- Al - 4.4 3.5 eV
Al 4.4 eV
oration of CdS has been investigated and detailed anal-
ITO
ysis made on the structural and morphological variation
PPV
under deposition conditions of 900  C, 250 Torr of Argon
at 80 sccm. It was shown that the CdS nanostructures Fig. 21. Proposed energy level diagram for the thin film diode structure
appeared as amorphous spherical particles, followed by consisting of ITO/PPV/nano-CdS/Ag structure. The smallest particle CdS
nucleation of nanorods from cusps on the particle surface diodes exhibited largest current density. Reprinted with permission from
and different growth modes at each heating interval.198 [212], N. V. Deshmukh, J. Elect. Mat. 36, 634 (2007). © 2007, Springer.
With this understanding of synthesis methods, various
applications of CdS nanoparticles and nanowires will be thin films and on-off ratio greater than seven orders of
discussed. magnitude. This approaches a theoretical limit which is
attributed to the low density of surface states. The CdS
nanoribbons in this work were fabricated by the vapor
4. APPLICATIONS OF CdS
transport method.209 Single electron transistors210 211 made
NANOSTRUCTURES

REVIEW
out of CdS nanoparticles have also been studied.
CdS thin films are used to fabricate photocells which In a recently published paper,212 we have shown a
are sensitive to visible light and exhibit photoconductiv- method of synthesizing monodispersed CdS nanoparti-
ity ratios (resistance in dark/resistance in light) as high as cles and their effect on current density of heterojunctions
10,000 for visible light. They are often found on street formed between CdS and PPV. Figure 21 shows the energy
lights as automatic on/off switches and are also used in level diagram for the Metal/nano-CdS/PPV/ITO hetero-
cameras and light meters. They were once even used in junctions. The flow of the injected holes towards the neg-
heat-seeking missiles to sense targets.199 ative electrode is blocked by the CdS layer, and the PPV
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layer of Southern
blocks the California
electron flow to the positive electrode.
4.1. CdS Nanoparticle Diodes/Light IP: 95.148.164.127 On: Fri, 04 Apr 2014 08:42:52
The field across
Copyright: American Scientific Publishers the CdS layer is increased due to the
Emitting Diodes accumulation of positive charges at the PPV/CdS inter-
face. The energy level mismatch at the PPV/CdS inter-
P-N junction diodes are building blocks200–203 for many
face further localizes the electrons and holes near the
advanced semiconductor devices and are also very valu-
able as diagnostic tools for understanding semiconductor junction. This increases the probability of recombination
materials and devices. A large segment of CdS nanotech- of charge carriers near the PPV/CdS interface, and hence
nology literature addresses the fabrication, characteriza- the efficiency and lifetime of the device is enhanced. We
tion, and application of homo-junction or hetero-junction have also reported heterostructures formed between p-type
diodes using CdS nanoparticles and conducting polymers porous silicon substrates and n-type CdS nanoparticles.213
(p-type).204 205 CdS nanostructures are an excellent choice (Fig. 22). Very good forward current-densities can be
for integration of thin film transistors (TFT) (Weimer obtained from such a device due to the reduced defect
206
1962) since they closely resemble the single crystal thin densities observed in nanostructured based materials as
films and possess intrinsically low density of surface trap- opposed to thin films where the current density is governed
ping states. It is possible to manipulate the device struc- by grain boundaries.
ture and configuration (heterostructures) by dissolving the In another study, CdS nanoparticles were synthesized
nanostructures in solution to coat onto desired substrates. intercellularly by using S pombe to fabricate the diode.
Various substrates can be used regardless of lattice match- S pombe and CdS nanoparticle diodes exhibited a rapid
ing in the light emission applications of nanoparticles that rise in the forward current (about 75 mA at 10 V) whereas
clearly indicate the advantage of nanoparticles over epi- the reverse bias breakdown occurred at 15 V. Linear char-
taxially grown207 quantum dots. Nanoparticles have been acteristics were observed for the protein sample without
deposited on Si wafers in order to integrate Si based cadmium sulphide nanoparticles.214 In another study, bulk
light sources with electronics for easy control of display CdS and CuS nanoparticle heterostructures, CdS/CuS/CdS,
devices and optical interconnection.208 Such heterostruc- deposited using the Langmuir-Blodgett technique showed
tures formed by chemical methods are technologically and voltage–current characteristics that indicated tunneling
scientifically important because they have unique opto- through the resonant levels.215
electronic properties. In an interesting article, the CdS Layers of CdS nanoparticles have been used as
nano TFT’s were demonstrated with a carrier mobility of active emission layers in light-emitting diodes (LEDs)216
200–300 cm2 V−1 s−1 that is comparable to the bulk CdS (Fig. 23).217 The bandgap can be tuned by alloying CdS

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 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.

configuration emit UV, green and red light respectively218

(Fig. 24). Conjugated polymers have been used as active
layers. The emission range in such diodes is determined
by the chemical structure of the polymer. Therefore, the
heterostructure devices made up of inorganic layer of
CdS nanoparticles and a polymer light emitters’ have
the advantage of high-charge transport properties of an
inorganic semiconductor and the enhanced emission effi-
ciency of the polymer emitter.219 The work function of
the nanoparticles can be matched with that of the metal
contacts in order to improve the electron injection effi-
ciency. And the magnitude of the external voltage can
control the emission color. Due to the quantum confine-
ment effect there is an increase in the oscillator strength
and hence, radiative recombination lifetime for traps gets
lowered to give an efficient luminescent transfer. Hence
this type of hybrid polymer-nanoparticle heterojunctions
CdS NPs
can be used as LEDs in the forward bias and photodetec-
Ag Ag tors in the reverse bias. CdS nanoparticles are also used
REVIEW

Porous Si in electroluminescent device fabrication at room temper-

ature on silicon substrates.220 A spectral shift of 86-meV
of free exciton transition arises due to the passivation
of p-hydroxyl thiophenol molecules around nanoparticles.
Heat treatment with an oxygen-rich environment has a sig-
Fig. 22. I–V characteristics of nano-CdS and porous silicon hetero- nificant influence on emission spectra. Polymers embedded
junction. Reprinted with permission from [213], N. V. Deshmukh et al., with CdS nanoparticles synthesized by a chemical route
Nanotechnology 12, 290Delivered
(2001). © by Publishing
2001, using polyvinyl
Technology to: University
Institute of Physics. alcoholCalifornia
of Southern as the desired matrix, were used
IP: 95.148.164.127 On: Fri, 04inApr 2014 08:42:52
fabricating nano-CdS/Ag junctions. Electrical studies
with various materials to produce Copyright:
different American
color lightScientific Publishers
of silver-CdS heterojunctions show that surface traps are
emitters and detectors. The multiple color nanostructure mainly responsible for determining the nature of I–V and
heterojunction consisting of three different nanowires of C–V response at different ranges of frequencies. Kumar
n-type, CdS, GaN, and CdSe and p-type Si nanowire LED et al.221 fabricated CdS/PPV heterojunction electrolumi-
nescent devices. An n-type CdS layer of ∼150-nm thick-
ness was spin coated to form a thin film from a solution
containing cadmium acetate and thiourea in 2-methoxy
ethanol. The resulting heterostructures exhibited PL and
electroluminescence (EL) at 510 nm with a satellite peak
at 530 nm. The transport properties of nanostructures and
various mechanisms causing the drastic changes in the car-
rier modulation have been studied and reported.222 223
The metal–insulator–semiconductor (MIS) capacitor is
the most useful device to study the surfaces of semicon-
ductors. This kind of structure was first proposed as a volt-
age variable capacitor by Moll224 and Pfann-Garrett225 in
1959. Capacitance measurements can be used to character-
ize the two interfaces (M–I and I–S). Dielectric studies on
chicken egg membrane deposited with CdS nanoparticles
were carried out by Uchil et al.226 High molecular weight
chicken egg membrane was found to be a polar dielec-
tric material. When CdS nanoparticles are embedded in
Fig. 23. EL spectrum for the device consisting of ITO/HTL/ membrane, the capacitance drops substantially in the entire
(Cdx Zn1−x Se)Cdy Zn1−y S QD monolayer/HBL/ETL/Mg:Ag/Ag. The frequency range of measurement and the magnitude of the
emission of the QD-LED peaks at 527 nm with a FWHM of 35 nm.
The inset on the left is a photograph of the working green QD-LED.
capacitance drop depends on the reaction parameters. The
Reprinted with permission from [217], J. S. Steckel et al., Angew. Chem. drop is maximum for small reaction times, low concentra-
Int. Ed. 45, 5796 (2006). © 2006, Wiley-VCH Verlag GmbH & Co. tions and high pH values.

3288 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

Fig. 24. Schematic of LED array consisting of heterostructures between common p-Si and n-GaN, CdS and CdSe emitting in UV and visible
regions and the corresponding EL from the diode arrays. Reprinted with permission from [218], Y. Huang et al., (2005). © 2005, Wiley-VCH Verlag

REVIEW
GmbH & Co.

4.2. CdS Nanoparticles in Photovoltaic Devices improvement in the energy conversion efficiency of MEH-
PPV solar cell was observed from 0.0012% to about
CdS nanoparticles are widely used to enhance the 0.60% when combined with the vertically aligned CdS
performance of inorganic heterojunction photovoltaic nanorods.
devices.227–229 An electrical voltage builds up as radiation
is absorbed by these devices. Electrons and holes should 4.3. Hydrogen Production Using CdS Nanoparticles
travel without any radiative recombination
Delivered in photovoltaic
by Publishing Technology to: University of Southern California
devices following different pathsIP: 95.148.164.127
towards On: Fri,Researchers
the respective 04 Apr 2014 have 08:42:52
tried to improve the photocatalysis pro-
Copyright: American Scientific
cess to Publishers
obtain sustainable energy sources for hydrogen pro-
electrode. The role of CdS nanoparticles is to separate the
charge by providing electron pathways. As the polymer/ duction using sunlight. CdS nanoparticles are used for this
nanoparticle photovoltaic device is irradiated, the exciton purpose, because CdS shows light absorption in the visible
(electron–hole pair) gets dissociated, with the hole travel- region and has suitable conduction band potential to effec-
+ 237
ing through the polymer and the nanocrystals providing the tively reduce the H ion. Comparison of photo catalytic
path for the electrons. The quantum efficiency of highly activity in bulk CdS and CdS embedded systems reveal
concentrated and well connected polymer/nanoparticle that the CdS embedded systems show comparatively better
composite solar cells is below 100% as some electrons activity.
come to a dead-end in the network and are forced to jump
to the neighboring polymer and thus recombine, lowering 4.4. CdS Nanowires as Optical Wave-Guides
230
the quantum efficiency. Some reports have indicated the and Lasers
possibility of replacing the organic sensitizer dye in pho- There is an ever increasing quest in the field of communi-
tovoltaic cells (DSSE)231 232 by CdS nanoparticles. CdS cations and data transmission with emphasis on integrated
nanoparticles were hybridized with poly[2-methoxy-5-(2 0- optical circuits capable of performing sophisticated func-
ethylhexyloxy)-1,4-phenylenevinylene MEH-PPV to fabri- tions like all optical signal routing, active multiplexing and
cate photovoltaic devices.233 The RF sputtered CdS/CdTe demultiplexing.238 The emergence of semiconductor doped
heterojunction photodiodes with a leakage current of 10 nA waveguides lead to the all optical non-linear signal pro-
cm−2 at a reverse voltage of 20 V exhibiting a photorespon- cessing waveguides. Semiconducting nanowires function
sivity of 0.5 A cm−2 have been studied.234 235 as nanoscale wave propagation tracks in which the high
Similar to CdS nanoparticles, CdS nanorods have also contrast in the refractive index between the nanowire and
been used in solar cell applications.236 Cadmium sulfide the surroundings gives rise to a nanodiameter optical cav-
nanorods mixed with a conjugated polymer, MEH-PPV, ity. These submicron optical cavities function as waveg-
formed hybrid solar cells. These nanorods were grown uides in which the precise control of defects leads to the
by electrochemical deposition through a porous alumina bending and manipulation of light. The semiconducting
template giving rise to vertical nanorods on Ti substrates. waveguides are distinct from the conventional transparent
Reduction in photoluminescence signal from MEH-PPV waveguides due to the fact that the optical emission or
film was observed as a result of mixing, whereas, absorption occurs for modes of energies close to the band

J. Nanosci. Nanotechnol. 8, 3272–3299, 2008 3289

 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.

gap energies. CdS nanowires with 80–200 nm diameters than 106 Ohm-cm for CdS and 109 for CdTe Ohm-cm
and wurtzite structures were used for fabricating lasers thin films were reported for X-ray imaging sensors.244
239
and also as optical waveguides. The advent of sophis- Electrohydrodynamic sprayed CdS and thermally evapo-
ticated semiconductor growth and processing techniques rated CdSe oxygen gas sensors have been studied using
paved the way for achieving the superior quality, epitax- X-ray Photoelectron Spectroscopy measurements in which
ial planar semiconductors that enabled the fabrication of the shift in binding energy was found to vary with the
integrated, electrically driven devices reproducibly. Duan chemical nature of oxygen radicals.245 A highly sensitive
240
et al. have observed that it is indeed possible to inte- gas sensor246 for detection and analytical identification of
grate the same quality device performance level using hazardous gases was reported by Miremadi et al.247 The
a controlled approach with a catalytic induced chem- sensors were fabricated by depositing partially crystalline
ical reaction. They have fabricated single crystal CdS powder from an aqueous suspension of CdS powder on
nanowires that function similar to the Fabry-Perot opti- an alumina substrate and the deposited layers were pro-
cal cavities with mode spacing inversely proportional to moted with catalysts from Pt-group metals. The sensors
the nanowire length. Nano LED based on the cross wire exhibited high sensitivity to different gas molecules upon
semiconductor approach has been discussed by Lieber modulation with light of certain frequency, depending on
and Wang in a topical review.241 The authors have pre- catalyst and impurity concentration. Dark resistance and
sented the nanoscale electronic injection lasers using photosensitivity of the sensors were studied against gas
n-CdS nanowires. Jerominek et al.242 demonstrated the concentration, sensor temperature, and frequency of the
CdS nanocrystallites of diameters close to 10 nm (the modulating light. Recently, a novel fiber optic surface plas-
REVIEW

authors termed it as microcrystalline) doped thin film mon resonance sensor with a metal-semiconductor core
waveguides by RF sputtering technique. The semiconduct- shell nanocomposite layers of CdS, PbS, ZnO, and CdSe
ing nanowire waveguides have been termed as active wave- has been reported and the sensors have been studied with
guides because they are operated near the band edge. respect to different metals. The sensor performance has
Barrelet et al.,243 have quantitatively studied the light prop- been evaluated for sensitivity and signal to noise ratio
agation in the CdS nanowire waveguides and observed and compared with Au-SiO2 surface plasmon resonance
the moderate optical losses (through sharp and even acute sensor.248 249 Highly resistive CdS and ZnSe layers grown
angle bends) by scanning optical
Delivered microscopy
by Publishing technique into: University
Technology on CdS surface have California
of Southern been used to fabricate UV sen-
which the CdS nanowire is excited by the laser light. These sors with
IP: 95.148.164.127 On: Fri, 04 Apr 2014 08:42:52 high quantum efficiency.250 The preparation of
measurements demonstrate that itCopyright:
is possible to inject,Scientific
American nano Publishers
and microcrystalline sensors using thin films of CdS
guide and manipulate light on a subwavelength scale using (30–200 nm) and CdSe (10–100 nm) by physical vapor
nanowire components that can be fabricated into integrated deposition is reported. The thin films were found to have
platforms thus paving the way for the integrated nanoscale crystallite sizes of 8 nm and the authors noted that the CdS
photonic systems. In this work, the authors have studied photoconducting devices were more sensitive to water,
the electro-optic modulation of the CdS waveguides (fabri- ethanol, ammonia, acetone, and iodine than CdSe photo-
cated by using a gold catalyst and single source precursor conducting sensors.251 In CdS/CdSe nanocrystals and core
of cadmium diethyldithiocarbamate or by laser ablation
of a polycrystalline CdS target) and compared the optical
loss to the Si and InGaAs waveguides. They have noted
the unoptimized CdS nano waveguides show better perfor-
mance of 1 dB/10 m as compared to 0.015 dB/10 m for
Si. Though all the optical non-linear photonic nanocrystals
have shown bright prospects for assembling more com-
plex structures in the future, the issue still remains about
the error free measurements of optical losses in nanowire
guides. This is due to ambiguity in the optical excitation
and the detection of the signal which diffuses through the
surface and the roughness of the sample that scatters the
light.

4.5. Sensors Using CdS Nanoparticles

Unique properties of structures based on CdS nanopar-
Fig. 25. The author’s concept of directional energy flow scheme
ticles are now being leveraged for many sensor appli-
observed in electrochromic nanoparticles. The smaller particle transfers
cations. Before nanoparticle research took a hike, its energy to a larger particle through fluorescence resonance energy
CdS/CdTe heterojunction devices fabricated by RF sput- transfer. Reprinted with permission from [246], D. M. Willard et al.,
ter deposition method with electrical resistivities greater Anal. Bioanal. Chem. 384, 564 (2006). © 2006, Springer.

3290 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

shells the application of cathodic potential leads to an very versatile pressure sensor in which the current at a
electron injection dramatically increasing the efficiency of fixed applied bias voltage can, for example, be used to
chemoluminescence (Fig. 25). This phenomenon is called monitor the pressure. CdS nanoparticles in this film exhibit
as electro induced chemoluminescence (ECL). The sen- electroluminescence that is a function of the current pass-
sitivity of this technique lies in effective electron trans- ing through the films (Fig. 26). Thus, the light emission
fer between nanocrystals and the chemical to be detected. from such a thin film at a constant bias voltage can also be
ECL has been observed in electrochemically reduced Si252 monitored to monitor the applied pressure. Sensors based
and CdSe253 nanocrystals when they interact with coreac- on this nanostructured film have been used to detect sur-
tant chemicals. ECL is highly sensitive, rapid, and con- face details at a pressure of approximately 10 kilopascals,
trollable and has been accepted for analytical applications distinguish features as small as 40 micrometers in width,
such as organic analysis and biosensors. Jie et al.254 have and resolve surface texture comparable to that of a human
reported the novel CdS ECL sensor for H2 O2 detection finger. The device is believed to have immense potential in
with a detection limit of 0.1 M. Zayats et al.255 have recording and recognizing fingerprints in the security and
studied the photo-electro-chemical processes in Au-CdS law enforcement industry.
nanoparticle arrays by surface plasmon resonance. The
sensors thus fabricated were used for detecting the acetyl- 4.6. CdS Nanoparticles in Biological Applications
chlorine esterene inhibitors.
Very novel pressure sensors have been fabricated by Bioentities such as antibodies, receptors, antigens and
embedding alternating layers of gold and CdS nanoparti- folded DNA exhibit nanodimensions and are comparable

REVIEW
cles in 2 to 3 nm thick polymer layers to the final thickness in size with nanowires, nanorods and nanoparticles. With
of about 100 nm.256 The electrical conductivity of this film the engineering of biomolecules with nanoscale materi-
depends on the pressure applied to the surface in the direc- als, it is possible to develop the hybrid materials that
tion perpendicular to the nanolayers. These films make a encompass the novel optimized recognition and reaction

Delivered by Publishing Technology to: University of Southern California

IP: 95.148.164.127 On: Fri, 04 Apr 2014 08:42:52
Copyright: American Scientific Publishers

Fig. 26. Pressure imaging device characteristics. (A) Schematic of the setup to take image texture of a metal coin (diameter ∼2 cm) and the pressure
images taken on CCD camera (device ∼2.5-cm square) at three different compressive stresses. The bias between the coin and the ITO electrode is fixed
at 18 V. (B) Comparison between optical microscope (inset) and pressure image of a TEM Cu grid. (C) The horizontal line in the pressure image is
the IEL scan. (D) Comparison between optical microscope and pressure image of the coin, showing the finer structure. The magnified image shows the
letters “RTY” of the word “LIBERTY” on the coin. (E) and (F) Comparison between the topographic and IEL scan across letter “Y” of “LIBERTY.”
The inset of (F) shows the local roughness of the coin. Reprinted with permission from [256], V. Maheshwari and R. F. Saraf, Science 312, 1501
(2006). © 2006, American Association for the Advancement of Science.

J. Nanosci. Nanotechnol. 8, 3272–3299, 2008 3291

 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.

enhancing properties of biomaterials with the excep- to generate unique photoelectrochemical systems. Curri
tional opto-electronic and catalytic properties of nanoscale et al.262 reported the immobilization of nanocrystalline
materials. There has been good progress in the use of CdS by self-assembly onto a gold electrode in order to
CdS nanomaterials in biological applications. Microscopic prepare (in combination with formaldehyde dehydrogenase
sensor devices have been fabricated using fluorescent (FDH) enzyme) a biological-inorganic hybrid. The pre-
nanoparticles that can be attached to biological molecules. liminary results indicated that quantum-sized CdS layer
Nanoparticles of CdS and silicon dioxide coated with poly- on gold, in close contact with the enzyme, was an effec-
mer chains with biotin attached to the ends were reported tive photoactive material needed as a charge transfer
recently.257 molecule in the enzymatic reaction. A nanoparticle tagged
When a protein known as avidin that binds to biotin is oligonucleotide (ODN) probe sensor based on the physical
added to the solution, the larger aggregates of nanoparti- entrapment of a target oligonucleotide on electropolymer-
cles clusters were formed. It has been proposed that ized film with enhanced sensitivity due to the presence
these nanoparticles could be used to fluorescently label of CdS nanoparticles (enhanced amplification) has been
biological molecules and also as a means to transport reported by Travas-Sejdic et al.263 An increase in the
them in an electric field. Microscopic needles would be charge transfer resistance upon binding of complementary
used by these proposed devices. These needles would CdS–ODN nanoparticle probes is believed to be the main
be used to take up very small volumes of tissue fluid
through the skin and mix it with nanoparticles designed
to detect particular molecules and then transport them to
REVIEW

another part of the device for detection. A semiconductor

nanoparticle attached to a biomolecule (nano-bio hybrid)
is used in photoelectrochemical sensors and optoelectronic
systems.258
CdS nanoparticles synthesized using quaternary water-
in-oil microemulsion techniques have been used in
fabricating biosensors. Immobilization of CdS nanopar-
ticles onto gold Delivered
working electrodes was carried
by Publishing out byto: University of Southern California
Technology
IP: 95.148.164.127
259
sealed assembled monolayer method. The electrochem- On: Fri, 04 Apr 2014 08:42:52
Copyright: American Scientific Publishers
ical sensors thus formed were used for detecting enzymes
such as glycine, ascorbic acid, cysteine, and sulphide
in the presence of formaldehyde under continuous illu-
mination. CdS nanoparticles play a role of charge car-
rier in the enzymatic oxidation of formaldehyde. Graphite
electrode modified with CdS nanoparticles was used
for detecting an enzyme, (glucose oxidaze) with signifi-
cantly enhanced electron transfer reactivity. Similarly, CdS
nanoparticles modified with thionvanic acid were used
as fluorescent probes for the detection of peptides,260
because CdS nanoparticles have a narrow, symmetric emis-
sion spectrum and are photo-chemically stable due to
long fluorescence lifetime and high fluorescence quantum
yields.
CdS nanoparticles passivated with mercaptoacetic acid
are water-soluble (i.e., they are hydrophilic and distributed
uniformly in water) and have been used as a fluores-
cence probe to detect bovine serum albumin (BSA).261
Such CdS nanoparticle probes are brighter, more stable
against photobleaching, and do not suffer from blinking.
They showed a response that is linearly proportional to the
concentration of BSA between 0.1 and 3.2 g ml−1 with
the detection limit of 0.08 g ml−1 . This method is very Fig. 27. Schematic of CdS nanoparticle-capped mesoporous silicon
simple and provides unambiguous, quantitative detection nanosphere (MSN) based drug/neurotransmitter delivery system. The
controlled-release mechanism of the system is based on chemical reduc-
of BSA rapidly. Nanoscale semiconductor crystals can also tion of the disulfide linkage between the CdS caps and the MSN hosts.
enhance the rate of photochemical reactions and can be Reprinted with permission from [268], C.-Y. Lai et al., J. Amer. Chem.
effectively coupled to bimolecular units such as enzymes, Soc. 125, 4451 (2003). © 2003, American Chemical Society.

3292 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

mechanism underlying the amplification. The constructed which the cadmium rich nanoparticles were found to form
sensor has shown good selectivity between exact matches a stable complex with DNA and the complexes exhibited
and mismatched sequences. The simple addition of DNA strong fluorescence.264 Nanowires, too, have applications
during the chemical synthesis of CdS nanoparticles in in detecting biological molecules.265

(a)

REVIEW
(b) Delivered by Publishing Technology to: University of Southern California
IP: 95.148.164.127 On: Fri, 04 Apr 2014 08:42:52
Copyright: American Scientific Publishers

(c)

Fig. 28. Directional electroswitchable photocurrents in the CdS-nanoparticles/DNA/intercalator system. Enhanced generation of anodic photocurrent
in the presence of the (a) doxorubicin intercalator (b) reduced methylene blue intercalator. (c) Oxidized methylene blue intercalator. Reprinted with
permission from [270], R. Gill et al., Angew. Chem. Int. Ed. 44, 4554 (2005). © 2005, Wiley-VCH Verlag GmbH & Co.

J. Nanosci. Nanotechnol. 8, 3272–3299, 2008 3293

 Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications Hullavarad et al.

Fig. 29. Schematic of the analytical protocol of the multi-target electrical DNA detection protocol based on different nanoparticle tracers (CdS, ZnS
and PbS), modified with the corresponding probe P1 , P2 , and P3 . The detection is performed using square wave anodic stripping voltametry. Reprinted
REVIEW

with permission from [272], A. Merkoci et al., Revista Mexicana De F’Isica S 52, 1 (2006). © 2006, Sociedad Mexicana de Física, A.C.

4.7. CdS Nanoparticle Caps for Drug Delivery System nanoparticles functionalized with the dithiol-tethered com-
plementary nucleic acid (ca. 3 nucleic acid residues
How CdS nanoparticles act as caps, for covering the two per nanoparticle) were hybridized with the nucleic acid
ends of a tube holding drugs is explained here. Con- associated with the gold electrode that was pretreated
trolled drug-release delivery266 systems based on meso- with dithiol-tethered single-stranded (ss)-DNA as seen in
porous silica are chemically inert to the matrix–entrapped Figure 28.of An anodic California
photocurrent was observed when
compounds.267 The Delivered by Publishing
system consists Technology
of mesoporous silicato: University Southern
DNA/CdS–nanoparticle-modified
IP: 95.148.164.127 On: Fri, 04 Apr 2014 08:42:52 electrode was photo-
nanospheres functionalized with 2-(propyldisulfonyl) ethy-Scientific
Copyright: American irradiated in the presence of triethanolamine (TEOA). The
Publishers
lamine. The average particle size of mesoporous silica imperfect structure of the CdS–nanoparticles/DNA duplex
nanospheres is 200 nm with an average pore diameter of gives rise to the photocurrent. Nondensely packed inter-
2.3 nm. The silica mesopores are used as reservoirs to faces formed by CdS–nanoparticles/DNA duplexes enable
soak up aqueous solutions of various pharmaceutical drug
the tilting of the monolayer components with respect to the
molecules and neurotransmitters. The neurotransmitters
electrode surface. Due to this, intimate contact between the
such as vancomyin and adenosine triphosphate—ATP are
CdS–nanoparticles and the electrode is formed, that may
used. Mercaptoethanol capped CdS nanoparticles are used
then lead to the photocurrent. Whether DNA shows con-
as in-situ caps for the opening of the drug/neurotransmitter
ductivity is a subject of substantial controversy.271 Merkoci
loaded mesoporous silica as seen in Figure 27. Disulphide
et al.272 have studied DNA detection using CdS nanopar-
linkage arises between the CdS nanoparticles and meso-
ticles (Fig. 29). Similarly, CdS nanoparticles are also used
porous silica that can be cleaved with various disulphide
to enhance the sensitivity of DNA sensors by incorporating
reducing agents like mercaptoethanol. So, the release of
CdS nanoparticles with the probe.273
the CdS nanoparticle caps from the drug/neurotransmitter
loaded mesoporous silica can be achieved by introduction
of variable amounts of release triggers.268 5. SUMMARY
According to a recent article in Nature, the chaper-
onin proteins GroEL (from Escherichia coli) and T.th CdS has been a very useful II–VI semiconductor for
(‘T.th cpn,’ from Thermusthermophilus HB8) can also decades and has now become a potential material for
enfold CdS semiconductor nanoparticles, giving them high research, development, and demonstration of innovative
thermal and chemical stability in aqueous media. These practical applications in the field of nanotechnology. Nano-
nanoparticles can be readily released from the protein structures of CdS exhibit many unique properties and they
cavities. Integration of such biological mechanisms and can be combined with various inorganic, organic, biolog-
materials science will open the door to conceptually new ical materials to provide materials and devices that have
bioresponsive devices.269 extraordinary practical applications.274 Nanoscale struc-
Layers of CdS nanoparticles that are attached to DNA tures, devices, and systems based on CdS have widely
molecules forming a photo-electrochemical system are dis- been used to demonstrate the potential of nanotechnol-
persed on a gold substrate.270 Another report on CdS ogy in providing breakthrough solutions in every area

3294 J. Nanosci. Nanotechnol. 8, 3272–3299, 2008

Hullavarad et al. Cadmium Sulphide (CdS) Nanotechnology: Synthesis and Applications

of technology as well as day-to-day life. Efforts in fab- 20. U. Venkateswaran, M. Chandrasekhar, and H. R. Chandrasekhar,
rication of CdS nanostructures and nanodevices have Phys. Rev. B 30, 3316 (1984).
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107, 206 (1960).
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REVIEW
(2007).
ing and preserving, (2) characterization and metrology, 34. V. C. Costa, Y. Shen, and K. L. Bray, J. Non-Cryst. Solids 304, 217
(3) manufacturability (process control, shelf life, and reli- (2002).
ability), and (4) environmental and safety need to be 35. H. Jia, H. Xu, Y. Hu, Y. Tang, and L. Zhang, Electrochem. Comm.
addressed separately. 9, 354 (2007).
36. J. S. Jang, D. W. Hwang, and J. S. Lee, Catal. Today 120, 174
(2007).
Acknowledgments: The work at UAF was sponsored 37. S. K. Kulkarni, U. Winkler, N. Deshmukh, P. H. Borse, R. Finkb,
by the SPAWAR System Center San Diego Grant, num- and E. Umbach, Appl. Surf. Sci. 169/170, 438 (2001).
ber N66001-07-1-2011, with thebysupport
Delivered Defense to:38.University
of theTechnology
Publishing V. Sivasubramanian, A. K.California
of Southern Arora, M. Premila, C. S. Sundar,
Advanced Research Projects Agency IP: (DARPA)
95.148.164.127 On: Fri, 04 and
and by the AprV.2014
S. Sastry, Physica E-Low-Dimensional Systems & Nano-
08:42:52
Copyright: American Scientific structures 31, 93 (2006).
Publishers
Defense Microelectronics Agency (DMEA). Authors also 39. L. E. Brus, J. Phys. Chem. 90, 2555 (1986).
acknowledge the help from Ms. C. Corwin and Ms. A. 40. A. Henglein, Chem. Rev. 89, 1861 (1989).
Rask during manuscript preparation. 41. Y. Wang and N. Herron, J. Phys. Chem. 95, 525 (1991).
42. J. Schroeder and P. D. Persans, J. Lumin. 70, 69 (1996).
43. T. Trindade, P. O’Brien, and N. L. Pickett, Chem. Mater. 13, 3843
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Received: 23 August 2007. Accepted: 23 November 2007.

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