

Investigation of Electrical and

Optoelectronic Properties of Vanadyl
 Phthalocyanine for Organic Electronic
Devices

By

Fakhra Aziz

Supervised by

Prof. Dr. Muhammad Hassan Sayyad

&

Prof. Dr. Khasan Karimov

A dissertation presented to the GIK institute in partial fulfillment of the

requirements for the degree of Doctor of Philosophy in
Engineering Sciences (Applied Physics)
(2012)

Faculty of Engineering Sciences

GIK Institute of Engineering Sciences & Technology, Topi, Pakistan
i
 In the name of

ALLAH

who is The True Guide and The All-Knowing Eternal

Source of Knowledge

ii
The greatest obstacle to discovery is not ignorance;

it is the illusion of knowledge.

Daniel J. Boorstin

iii
 Dedication

This dissertation is dedicated to:

Ruqayya Aziz and Aziz-ur-Rahman (late), my parents, who always wanted me to

acquire higher education and whose prayers and unconditional love made this uphill

task possible.

Shahid, Rafia and Aashir, who provided the foundation for all I accomplish.

Fauqia and Faryal, who never left my side and were always ready to help and support

me through the years till got to my final destination.

v
 Acknowledgments

Acknowledgments

It gives me a great pleasure and satisfaction to acknowledge the blessings of Almighty

Allah, the most gracious, compassionate and beneficent to all his creatures. The
research undertaken in this dissertation was an uphill task and it was only His favors,
which enabled me to complete all the requirements for my PhD degree very well in time.

I feel great honor to express the deepest sense of appreciation and gratitude to my
reverend supervisor Prof. Dr. Muhammad Hassan Sayyad for his inspiring guidance and
skillful suggestions to carry out the research work conducted at the Organic Electronics
Laboratory, GIK Institute. He enabled me to conduct this research and provided
suggestions and critiques necessary for me to complete this work.

I owe my deepest gratitude to Prof. Dr. S. Ikram A. Tirmizi (Dean, FES) for administering
my research activities and providing moral support throughout my stay at the GIK
Institute. I would like to thank Jehangir Bashar (Rector, GIKI) and Prof. Dr. Fazal A.
Khalid (Pro-Rector Academics) for their extended support and co-operation. I am very
much obliged to the members of the Faculty Graduate Research Committee Prof. Dr.
Jameel-un-Nabi, Prof. Dr. Irgaziev Bakhadir and Dr. Ghulam Shabbir for sparing their
precious time to evaluate this dissertation.

I would like to gratefully acknowledge the inappreciable technical and moral support of
Prof. Dr. Kh. S. Karimov as my co-supervisor. He has made his support available
anytime in a number of ways. I would like to show my gratitude to Dr. Zubair Ahmad for
lending his precious time and extended co-operation.

It is an honor for me to acknowledge Prof. Dr. Rasat Muhammad Rasat, University of

Malaya especially for his guidance and granting access to the labs and equipment. This
dissertation would not have been possible without the guidance and encouragement of

vi
 Acknowledgments

my foreign co-supervisor Dr. Khaulah Sulaiman, Low Dimensional Materials Research

Center (LDMRC), Department of Physics, Faculty of Science, University of Malaya. She
did not hesitate to provide materials, expertise and good atmosphere at the LDMRC that
made working in her group worthwhile.

Finally, I am forever indebted to Prof. Dr. Fazal-ur-Rehman Sethi, University of

Peshawar, for his endless encouragement. I would like to show my deepest gratitude to
Prof. Dr. Nasir Jamal Khattak for his invaluable moral support. I am also grateful to my
parent University of Peshawar for supporting me in completion of my PhD.

I am indebted to many of my colleagues Dr. Muhammad Saleem, Dr. Mutabar Shah, Mr.
Shahid Mehmood, Mr. Dilnawaz Khan, Mr. Fazal Wahab and Mr. Muhammad Tahir to
help me complete this dissertation. It is a pleasure to thank Saipul, Fahmi, Lim, Toong,
Gan, Goh, Richard and Selvi who made my research work possible at the LDMRC. I
am truly indebted and thankful to Mr. Ismatullah, Mr. Sajjad Ahmad, Mr. Younas Imran,
Mr. Tila Muhammad, Mr. Muhammad Tariq, Mr. Abdul Jamil, Mr. Abid ur Rehman, Mr.
Faulad Khan, Mr. Wilson Javed, Mr. Alif Khan, Mr. Zaman Sher, Mr. Qamar Zaman, Mr.
Afzal Mehmood and Ms. Arshia for their help and co-operation during the period of my
stay at GIK Institute.

I owe my deepest gratitude to my friend Ms. Mehwish Khan who was always ready to
lend her ears to me whenever I was in distress during my entire period of PhD. It was
her moral support which enabled me to remain focused on the research work.

I would like to acknowledge the Higher Education Commission (HEC), Pakistan for
financial assistance through the “5000 Indigenous PhD Fellowship Program” and the
“International Research Support Initiative Program” (IRSIP). Without this opportunity, I
wouldn’t be where I am today.
Fakhra Aziz

vii
 Declaration

Declaration

This dissertation is my original work except where specific acknowledgement is given.

This dissertation has not been submitted in whole or in part to any other university.
Certain aspects of this dissertation have been published or submitted for publication
as follows:

Reviewed Journal Papers:

1. F. Aziz, M. Hassan Sayyad, K. Sulaiman, B. Majlis, Kh. S. Karimov, Z. Ahmad

and G. Sugandi (2012) Influence of humidity conditions on the capacitive and
resistive response of an Al/VOPcPhO/Pt co-planar humidity sensor,
Measurement Science and Technology, 23, 014001.

2. F. Aziz, M. H. Sayyad, Kh. S. Karimov, M. Saleem, Z. Ahmad and S. M. Khan

(2010) Characterization of vanadyl phthalocyanine based surface-type
capacitive humidity sensors, Journal of Semiconductors, 31, 114002.

3. F. Aziz, M. H. Sayyad, Zubair Ahmad, K. Sulaiman, M. R. Muhammad and

Kh. S. Karimov and “Spectroscopic and Microscopic Studies on Vanadyl
Phthalocyanine Complex Thin Films for Electronic Photo-devices”, Physica E
(In Press).

viii
 Declaration

Conference Papers:

4. F. Aziz, K. Sulaiman, M. R. Muhammad, M. Hassan Sayyad and Kh. S.

Karimov “Influence of thermal annealing on the structural properties of vanadyl
phthalocyanine thin films: A comparative study” International Conference on
Condensed Matter and Materials Physics (ICCMMP2011), Venice, Italy April
27-29, 2011.

5. F. Aziz, K. Sulaiman, Kh. S. Karimov and M. Hassan Sayyad, “The Influence of

Doping of Fullerene Derivative (PCBM) on the Optical Properties of Vanadyl
Phthalocyanine complex (VOPcPhO)” International Conference on Computer,
Electrical and Systems Sciences and Engineering (ICCESSE 2011), Bali,
Indonesia, October 26‐28, 2011.

6. F. Aziz, K. Sulaiman, M. R. Muhammad, M. Hassan Sayyad, K. S. Karimov and

B. Y. Majlis, “Investigation of optical and humidity-sensing properties of
vanadyl phthalocyanine-derivative thin films” KJF 2011:International
Conference on Organic Materials for Electronics and Photonics, Gyeongju,
Korea, September 15-18, 2011.

Fakhra Aziz

ix
 Abstract

Abstract
The characterization of organic semiconducting materials, such as Metal
Phthalocyanines (MPcs), has received great attention because of the increased activity
in the potential use of these conjugated species in a broad range of electronic and
photonic devices. MPcs are used in a variety of applications such as solar cells, field-
effect transistors, sensors, etc., due to their thermal and chemically stability.

In the research work reported in this dissertation, optimization and characterization of

Vanadyl 2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine (VOPcPhO) thin films is
undertaken for potential applications in organic electronic devices, such as, humidity
sensors and solar cell. This study has been carried out in four phases. In the first phase,
the effect of annealing is examined on the structural, morphological and optical
properties of Vanadyl Phthalocyanine (VOPcPhO) thin films. Phase two comprises
spectroscopic absorption studies made on different proportions of the blends VOPcPhO
and (6,6)-phenyl C61 butyric acid methyl ester (PCBM). In phase three, symmetrical
and asymmetrical electrodes with gaps of 40 µm and 17 µm are fabricated using
shadow mask and lithography. Then using these electrodes VOPcPhO based surface
type sensors are fabricated and humidity sensing properties of VOPcPhO thin films are
investigated. Finally, photovoltaic properties of VOPcPhO films are studied in the fourth
phase of this work.

The effect of thermal annealing on the structural, morphological and optical properties of
Vanadyl Phthalocyanine (VOPcPhO) thin films is investigated for optoelectronic
applications. The AFM results show that the surface roughness increases with
increasing annealing temperature making the annealed films more prone to high
absorption rather than the pristine sample. The thermal annealing processes on the
spin-coated VOPcPhO thin films are observed to significantly enhance the features of
light absorption and surface morphology. Hence, annealed thin films of VOPcPhO can

x
 Abstract

be incorporated in the organic electronic devices, where such features are of prime
importance.

The spectroscopic studies on a VOPcPhO and (6,6)-phenyl C61 butyric acid methyl
ester (PCBM) blend, are performed. The blends of VOPcPhO and PCBM, with three
different concentrations, are prepared in chloroform and their thin films are deposited by
casting process. Spectroscopic studies have been carried out on these films to study
the effect of doping of PCBM on VOPcPhO. An increase in the absorption coefficient
has been observed with increasing dopant concentration. Optical energy gap appears to
decrease from 3.32 eV to 3.26 eV with a variation of 0–75 % of PCBM concentration in
the VOPCPHO films.

To examine the sensing potential of VOPcPhO, Ag/VOPcPhO/Ag and Al/VOPcPhO/Pt

surface-type structures are fabricated using the techniques of vacuum thermal
evaporation, photolithography and spin casting. The effect of humidity is investigated on
the electrical properties of these sensors. The symmetric type Ag/VOPcPhO/Ag devices
of three different thicknesses are fabricated using thermal evaporator. Thin films of
VOPcPhO are deposited on thoroughly cleaned glass substrates with pre-patterned Ag
electrodes of 40 µm gap obtained using shadow mask. The effect of humidity is studied
on their capacitance and the device with lesser thickness is observed more sensitive
towards humidity. The asymmetric type Al/VOPcPhO/Pt device is fabricated using
photolithography and spin casting. Thin film of VOPcPhO is spin casted on glass
substrate with lithographically pre-patterned Al and Pt electrodes of 17 µm gap. Effect of
moisture is examined on the capacitive and resistive response of Al/VOPcPhO/Pt co-
planar structure. A 100-folds increase was observed in the capacitance of the VOPcPhO
sensing material with an elevation of relative humidity level from 0 – 95 %RH. The
resistance of the sensor reduced from 2.9 GΩ to 2.1 MΩ with increasing level of
humidity. Adequate sensing properties, such as enough sensitivity, reasonable
response and recovery times have been obtained. The humidity-dependent properties
of the sensor make it a good match for its potential application in commercial
hygrometers. The sensor with asymmetric electrodes has shown better sensitivity which

xi
 Abstract

may be ascribed to the relatively smaller gap between the electrodes or different work
functions of the electrodes.

A thin‐film, single‐layer organic solar cell has been fabricated from the VOPc derivative.
The photoactive layer of VOPcPhO has been sandwiched between aluminum (Al) and
indium tin oxide (ITO) electrodes to produce photovoltaic device. The device has
exhibited photovoltaic effect with the values of Jsc, Voc, and FF equal to 5.26 x 10-6
A/cm2, 0.62121 V and 0.33, respectively. However, the device results in low efficiency
which can be improved by introducing an acceptor material to form bulk heterojunction
solar cell. The VOPcPhO blended with a matched acceptor material has potential
application for improved efficiency of the bulk heterojunction type organic solar cells.
The electronic parameters of the cell have also been extracted from I-V characteristics
in dark. The ideality factor and barrier height were found to be 2.69 and 0.416 eV,
respectively.

xii
 Contents

Contents
Abstract .............................................................................................................................. x
List of Figures ................................................................................................................... xv
1 Introduction ................................................................................................................. 1
1.1 Genesis ................................................................................................................... 1
1.2 Aims and Objectives ................................................................................................ 2
1.3 Layout of Dissertation .............................................................................................. 4
1.4 References .............................................................................................................. 5
2 Literature Review ........................................................................................................ 8
2.1 Vanadyl Phthalocyanine (VOPc) and Its Soluble Derivatives (VOPcPhO) .............. 8
2.2 Organic Thin Films ................................................................................................ 10
2.2.1 Thin Film Deposition ..................................................................................... 10
2.2.2 Thin Film Structural Characterization ........................................................... 11
2.2.3 Thin Film Applications ................................................................................... 15
2.3 Organic Thin Film Based Devices ......................................................................... 15
2.3.1 Humidity Sensors ......................................................................................... 16
2.3.2 Solar Cells .................................................................................................... 23
2.4 References ............................................................................................................ 30
3 Materials and Methods .............................................................................................. 44
3.1 Organic Materials Used ......................................................................................... 44
3.1.1 VOPcPhO ..................................................................................................... 44
3.1.2 PEDOT:PSS ................................................................................................. 46
3.1.3 PCBM ........................................................................................................... 47
3.1.4 Solvent and Substrates................................................................................. 48
3.1.5 Substrate Cleaning Procedures .................................................................... 48
3.2 Fabrication Techniques .......................................................................................... 50
3.2.1 Vacuum Thermal Evaporation....................................................................... 50
3.2.2 Spin-Coating Technique ................................................................................ 53
3.2.3 Photolithography Technique ......................................................................... 55
3.3 Experimental Procedures ...................................................................................... 57
3.3.1 Preparation of Stand-Alone Thin Films ......................................................... 57
3.3.2 Fabrication of VOPcPhO-thin-film Based Devices ........................................ 58
3.4 Characterization Techniques ................................................................................. 65
xiii
 Contents

3.4.1 Surface Profilometer ..................................................................................... 65

3.4.2 UV-Vis-NIR Spectrophotometery .................................................................. 67
3.4.3 Atomic Force Microscopy (AFM) Characterization ....................................... 68
3.4.4 X-Ray Diffractometery .................................................................................. 69
3.4.5 Humidity Measurements ............................................................................... 71
3.4.6 Current-Voltage Measurements (I-V) in Devices .......................................... 73
3.5 References ............................................................................................................ 76
4 Characterization of VOPcPhO based Thin Films ...................................................... 77
4.1 Optical and Spectroscopic Studies ........................................................................ 78
4.1.1 Absorption spectra of VOPcPhO .................................................................. 78
4.1.2 Effect of thickness on the absorption spectra ............................................... 81
4.1.3 Effect of doping of Fullerene derivative on the absorption spectra ............... 84
4.2 Optical Energy Band gap ....................................................................................... 86
4.3 Morphological and Structural Studies .................................................................... 91
4.3.1 Atomic Force Microscopy ............................................................................. 91
4.3.2 X-Ray Diffraction........................................................................................... 94
4.4 Influence of Thermal Annealing on the Optical, Morphological and Structural
Properties of VOPcPhO ......................................................................................... 95
4.4.1 UV/Vis Absorption Spectra Measurements ................................................... 95
4.4.2 AFM Images ............................................................................................... 101
4.5 References .......................................................................................................... 105
5 VOPcPhO-Thin-Film Based Devices....................................................................... 110
5.1 Humidity Sensors ................................................................................................ 112
5.1.1 Humidity Sensing Studies of VOPcPhO Film Using Symmetric Electrodes 114
5.1.2 Humidity Sensing Studies of VOPcPhO Film Using Asymmetric Electrodes
……………………………………………………………………………………..124
5.1.3 Photovoltaic Studies of VOPcPhO Film Based Cell .................................... 132
5.2 References .......................................................................................................... 144
6 Conclusions and Future Work ................................................................................. 152
6.1 Conclusions ......................................................................................................... 152
6.2 Future Work ......................................................................................................... 155

xiv
 List of Figures

List of Figures

Figure 2.1. Working mechanism for X-Ray Diffraction technique................................14

Figure 2.2. A flexible resistive humidity sensor………………………...…………..........18

Figure 2.3. A typical response characteristics of the resistive humidity sensor

measured at room temperature………………………………….…………..21

Figure 2.4. A polymide based capacitive humidity sensor…………………….….…...22

Figure 2.5. Electron donors and electron acceptors…………………………..……….25

Figure 2.6. An ideal structure for the bulk heterojunction organic solar cell…...……27

Figure 2.7. (a) FE-SEM cross-section image of the ZnO nanorod, (b) Schematic
structure of a ZnO/organic hybrid device…………………………….……28

Figure 2.8. A degradation process in polymer solar cells……………………….…….29

Figure 3.1. A molecular structure of VOPcPhO……………………………………..….45

Figure 3.2. A molecular structure of PEDOT:PSS. The “dot’’ and “plus’’ represent the
unpaired electron and positive charge on the PEDOT chain,
respectively………………………………………………………………..….46

Figure 3.3. A molecular structure of (PCBM)………………………………………...…47

Figure 3.4. A photograph of Edward AUTO 306 Vacuum Evaporator…………...…..51

xv
 List of Figures

Figure 3.5. A schematic diagram of thermal evaporators used in our labs………..….52

Figure 3.6. A photograph of WS-400B-6NPP-Lite spin coater used to deposite thin

films of VOPcPhO……………………………………………………...…...…53

Figure 3.7. A schematic diagram of spin coating technique………………….……..….54

Figure 3.8. Types of photoresist coating: (Positive and negative photoresist)…..……55

Figure 3.9. Three different kinds of exposure methods……………………….....……..56

Figure 3.10. Cross-sectional view of Ag/VOPcPhO/Ag capacitive-type humidity

sensor……………………………..………………………………….………..59

Figure 3.11. The steps employed in the photolithography for the fabrication of the
asymmetric sputtered metal-electrodes for humidity sensors; (a,f) mask,
(b,g) exposure to light, (c,h) development, (d,i) Au/Pt sputtering, (e,j)
photoresist lift-off…………………………………...……………..…………...61

Figure 3.12. A 3-D device structure of a co-planar humidity sensor……………..…..…62

Figure 3.13. A photograph of the thin films of VOPcPhO coated on glass substrates for
optical studies and a fabricated solar cell………………………..…...…….63

Figure 3.14. A device structure for single layer VOPcPhO based solar cell….....……..64

Figure 3.15. A photograph of KLA Tencor P-6 surface profilometer capable of

measuring film thickness…………………………..…………………...…….66

Figure 3.16. A photograph of Jasco V-570 UV/Vis/NIR spectrophotometer used for UV-
Vis spectra measurements………………..………………………...………..67

Figure 3.17. A Veeco D3000 microscope AFM system used in the characterization....68

xvi
 List of Figures

Figure 3.18. AFM close-up view, showing the sample chuck and scanner…….…...….69

Figure 3.19. A photograph of Siemens D5000 Diffractometer used in the work reported
in this dissertaton…….……………..…………………………………...…….70

Figure 3.20. A photograph of the experimental setup for humidity measurements

prepared at Organic Electronics Lab, FES, GIK
Institute……………………………………………………………………....…72

Figure 3.21. A photograph of Keithley 236 source meter used for characterization of
solar cell reported in this dissertation………………………..…………..….74

Figure 3.22. A photograph of Oriel 67005 solar simulator used for measuring the
response of solar cell made from the organic materials reported in the
dissertation………………………………..………………………………..…..75

Figure 4.1. Absorption spectra of spin coated VOPcPhO thin film on glass……….…79

Figure 4.2. Absorption spectra of spin coated VOPcPhO thin films on glass at different
spin rates………………..……………………………………………….……..83

Figure 4.3. Optical absorption spectrum of VOPcPhO:PCBM blend for different

dopant
concentrations………………………………..……………………….…….....85

Figure 4.4. The variation of the absorption coefficient (α) as a function of photon
energy for different dopant concentrations, (1) 0 %; (2) 25 %; (3) 50 % and
(4) 75 %, showing reduction in band-gap with increasing dopant
concentration………………………………………..……………….………...87

xvii
 List of Figures

Figure 4.5. The variation of the absorption coefficient (α) as a function of photon
energy for different dopant concentrations (1) 25 %; (2) 50 % and (3) 75
% indicating red-shift along the absorption edge………………..……..…..90

Figure 4.6. AFM micrographs for spin coated thin film of VOPcPhO employed for
humidity sensor: (a) 3-D micrograph, (b) 2-D micrograph and (c) section
analysis…………………………………………………..…………..…………92

Figure 4.7. XRD spectra of a spin-coated thin film of VOPcPhO for humidity
sensor…..…………………………………………………..………..…………94

Figure 4.8. Optical absorption spectrum of the VOPcPhO thin films in the Q-band
egion before and after thermal annealing. Inset shows a spectrum before
and after annealing in the Soret-band region……………..………………..96

Figure 4.9. Relation between absorption spectra and temperature for UV and visible
spectrum regions……………..……………………………..…………………97

Figure 4.10. Plot of dln(αhν)/dhν versus hν for the as-cast sample. Inset shows a plot of
ln(αhν) versus ln(hν –Eg) to determine the type of transition……..…..….99

Figure 4.11. The variation of the absorption coefficient (α) as a function of photon
before and after annealing of the films in the Soret-band region. Inset
shows a Q-band region……………..………………………………….……100

Figure 4.12. AFM images (2D and 3D ) of VOPcPhO thin films spun-cast on glass
substrates; scan size is 5 µm x 5 µm: (a) as-cast and annealed at (b) 95
oC, (c) 125 oC, (d) 155 oC: (e) Relation between grain size and different
annealing temperatures………..……………………………………..……..102

xviii
 List of Figures

Figure 5.1. Capcitance versus relative humidity relationship for the Ag/VOPcPhO/Ag
capacitive sensors for the VOPcPhO thicknesses equal to (1) 50nm, (2)
100nm, (3) 150nm………………………………..…………………..………115

Figure 5.2. VOPcPhO film thickness relationships for Ag/VOPcPhO/Ag capacitive

sensor at relative humidity of 70%(1), 80%(2), 90%(3)…………………..117

Figure 5.3. Capacitance-relative humidity relationship for Ag/VOPcPhO/Ag capacitive

sensor with film thickness of 150nm: (1) experimental (2) Simulated….122

Figure 5.4. Current-Voltage characteristics of the device under two different humidity
levels (40 and 60 % RH)…………………..……………………………..….123

Figure 5.5. Capacitance versus relative humidity relationship for the Al/VOPcPhO/Pt
co-planar humidity sensor………………..………………………...……….125

Figure 5.6. Resistance versus relative humidity relationship for the Al/VOPc/Pt co-
planar humidity sensor…………………..……………………………..……129

Figure 5.7. Response recovery versus time relationship for the Al/VOPcPhO/Pt co-
planar humidity sensor………………………..………………………..……131

Figure 5.8. Current-voltage characteristics of VOPc-based single-layer device in dark

and under illumination…………………..…………………………...………134

Figure 5.9. Current-Voltage characteristics of VOPc–based solar cell in semi log

scale……………………………………………...…………………………....136

Figure 5.10. The junction resistance versus applied voltage for single layer solar
cell………………………………..……..………………………………..……139

xix
 List of Figures

Figure 5.11. Current–Voltage characteristics of the solar cell in Log (I)–Log (V)
representation……………………………………..……………….………...140

Figure 5.12. F(V) versus voltage plot of VOPcPhO based cell………………….…......142

xx
Chapter 1 Introduction

1 Introduction

1.1 Genesis

Organic semiconducting materials, such as metallophthalocyanines (MPc),

metalloporphyrins, perylenes, AZO dyes, etc., are of great interests for applications in
numerous electronic and optoelectronic devices. Among these materials,
metallophthalocyanines are most attractive because of their interesting electrical and
optical properties, such as, broad spectral responses [1] and thermal, chemical and
photochemical stabilities [2-4]. These compounds have never lost their popularity as
excellent functional materials since 1930s and are commercially available pigments and
dyes occurring in blue, green and blue-green colors [5]. Such colors are produced due
to the high-intensity absorption in the visible spectral region. More recently, Pcs have
become very important for molecular materials applications and nano-scale device
fabrication [6]. These materials find applications in semiconductor devices like
information storage systems [2], sensors [7, 8], nonlinear optics [ 9 ] etc.

Some Pcs are very sensitive to various factors present in our environment for example
humidity [10, 11] and different types of gases [12]. The development of various types of
sensors is made possible due to ambience-dependent-properties of these materials [10,
11]. These compounds have large absorption coefficient in the visible region [13] and
are very sensitive to infra-red visible and ultraviolet radiation [14] . There is further active
research into exploiting these materials in widening the absorption band towards near
infrared region for more technologically advanced applications in the optical data
storage and security printing [15]. The formation of colored mesophases and

1
Chapter 1 Introduction

reorganization in metal-phthalocyanines films have been revealed by thermal optical

spectroscopic studies [16].

Among various phthalocyanines, VOPc and its substituted solution process-able

derivatives have received considerably less attention. In this dissertation, optimization
and characterization of Vanadyl Phthalocyanine derivative (VOPcPhO) thin films is
undertaken for potential applications in organic electronic applications, such as,
humidity sensors and photovoltaic devices.

1.2 Aims and Objectives

Investigations on organic materials have increased rapidly in recent years because they
are inexpensive, less complex and easy to fabricate. They also offer attractive electrical
and optical features. In near future, no doubt, these materials will find more appropriate
place in the vast field of electronic materials.

To acquire a complete knowledge of the material, characterization techniques are

employed to explore its potentially interesting properties. Thus the aim of this work is to
provide deep insight into the electronic and optoelectronic properties of VOPcPhO and
introduce it as a novel low molecular organic material for its potential applications in
organic electronics. The scope of this dissertation is a two-fold task. One of the tasks is
to exploit the structural, morphological and optical properties of VOPcPhO thin films and
the second objective is to explore electrical and optoelectronic properties of the organic
electronic devices based on this organic semiconductor. Since VOPcPhO is a less
explored organic material therefore another objective of the present work is to introduce
this material as a potential candidate for commercial applications.

2
Chapter 1 Introduction

VOPc and its soluble derivatives have proved to be favorable candidates for electronic
applications due to their high stability, low cost, easy availability and better performance
[17]. The color of phthalocyanine range from dark-blue to green, however, VOPcPhO
occurs in a green-color organic compound, which possesses a macrocyclic and
heterocyclic ring structure. It comprises nitrogen atoms in addition to carbon as a part of
the ring. Like many other metal based Pcs, VOPc is also a p-type semiconductor [18]
and offers considerably high mobility (~1 cm 2 /Vs) [19] which makes it very useful for
numerous potential applications. VOPcPhO is insoluble in water and can be
conveniently dissolved in a variety of organic solvents due to non-rigid structure. The
thin films of VOPcPhO can be easily prepared not only by vacuum evaporation [20, 21]
but also by numerous low cost wet processing techniques [22, 23]. These properties
make it a very suitable candidate for being employed as an active sensing material to
sense the moisture present in the atmosphere.

The investigation of VOPcPhO under the effect of post-deposition thermal annealing is

undertaken to study the structure, surface morphology and optical properties of the thin
films. The purpose of this study is to optimize thin films for improved device
performance. As a number of organic solar cells are prepared using low molecular
organic materials [24, 25], VOPcPhO is used in the fabrication of organic solar cell and
investigated under dark and illumination. The employment of VOPcPhO in photovoltaic
applications further opens the doors to fully exploit this material for being used in bilayer
and bulk-heterojunction solar cells incorporating a fullerene derivative as an electron
acceptor material.

3
Chapter 1 Introduction

1.3 Layout of Dissertation

Chapter two focuses on the background theory and relevant literature review of thin
films based on VOPc and its soluble derivative VOPcPhO, which are used to make
humidity sensors and solar cells. Chapter three is devoted to the description of organic
materials used, in device fabrication techniques and details of the methods employed
during characterization of VOPcPhO based thin films. The first set of experimental
results of this work concerning findings of VOPcPhO thin films are contained in chapter
four, which include the study of optoelectronic, spectroscopic, structural, morphological
and thermal properties. Chapter five constitutes the investigation of humidity sensors
employing VOPcPhO as an active sensing layer. This chapter also encompasses
fabrication and characterization of solution processed VOPcPhO based organic solar
cells. Finally, chapter six highlights and summarizes conclusions of the research work
carried out umbrellas part of this dissertation and also provides a list of suggested future
studies.

4
Chapter 1 Introduction

1.4 References

[1] M. Wang, H.-Z. Chen, and S.-l. Yang, "Photoconductivity of phthalocyanine

composites I: Double-layered photoreceptor of CuPc PVK," Journal of
Photochemistry and Photobiology A: Chemistry, vol. 53, pp. 431-436, 1990.
[2] J. Jiang, O. C. O. N. Bekaroglu, and Y. C. O. N. Bian, Functional Phthalocyanine
Molecular Materials vol. 135: Springer Verlag, 2010.
[3] H. S. Soliman, A. M. A. El-Barry, N. M. Khosifan, and M. M. El Nahass,
"Structural and electrical properties of thermally evaporated cobalt
phthalocyanine (CoPc) thin films," The European Physical Journal - Applied
Physics, vol. 37, pp. 1-9, 2007.
[4] F. H. Moser and A. L. Thomas, The phthalocyanines vol. 1: CRC Press Boca
Raton, FL, 1983.
[5] M. J. Cook, "Phthalocyanine thin films," Pure and Applied Chemistry, vol. 71, pp.
2145-2152, 1999.
[6] G. de la Torre, C. G. Claessens, and T. Torres, "Phthalocyanines: old dyes, new
materials. Putting color in nanotechnology," Chemical Communications, pp.
2000-2015, 2007.
[7] Z.-g. Zhao, X.-w. Liu, W.-p. Chen, and T. Li, "Carbon nanotubes humidity sensor
based on high testing frequencies," Sensors and Actuators A: Physical, vol. 168,
pp. 10-13, 2011.
[8] K.-i. Shimizu, I. Chinzei, H. Nishiyama, S. Kakimoto, S. Sugaya, W. Matsutani,
and A. Satsuma, "Doped-vanadium oxides as sensing materials for high
temperature operative selective ammonia gas sensors," Sensors and Actuators
B: Chemical, vol. 141, pp. 410-416, 2009.
[9] P. Innocenzi and B. Lebeau, "Organic–inorganic hybrid materials for non-linear
optics," Journal of Materials Chemistry, vol. 15, pp. 3821-3831, 2005.

5
Chapter 1 Introduction

[10] F. Gutman and L. E. Lyons, Organic Semiconductors Part A, Robert E, 1981.

[11] F. Gutman, K. H., L. E. Lyons, and S. R.B., Organic Semiconductors Part B,
Robert E. Florida, USA: Publishing, Malabar, FL, 1983.
[12] M. I. Fiodorov, Russia Patent, 1999.
[13] I. Rosenthal, "Phthalocyanines as photodynamic sensitizers," Photochemistry
and photobiology, vol. 53, p. 859, 1991.
[14] K. S. Karimov, K. Akhmedov, A. A. Dzhuraev, M. N. Khan, S. M. Abrarov, and M.
I. Fiodorov, Eurassion Chemical Technological Journal, vol. 3-4, p. 251, 2000.
[15] R. M. Christie and B. G. Freer, "Colour and constitution relationships in organic
pigments:: Part 3--phthalocyanines," Dyes and Pigments, vol. 24, pp. 113-124,
1994.
[16] A. N. Fernandes, T. H. Richardson, D. Lacey, and J. Hayley, "Langmiur-Blodgett
studies of silicon (IV) phthalocyanine bis (trihexylsilyoxide) and its optical
properties," Dyes and Pigments, vol. 80, pp. 141-148, 2009.
[17] L. Li, Q. Tang, H. Li, and W. Hu, "Molecular orientation and interface compatibility
for high performance organic thin film transistor based on vanadyl
phthalocyanine," The Journal of Physical Chemistry B, vol. 112, pp. 10405-
10410, 2008.
[18] Y.-l. Pan, Xiao-Dong Liao, Ying juan Wu, Ling-bing Chen, You-yuan Zhao, Yuan-
hua Shen, Fu-ming Li, Shu-yin Shen, De-yin Huang, "Steady-state photovoltaic
and electroreflective spectra in Al/vanadyl phthalocyanine (VOPc, in phase
II)/indium-tin-oxide (ITO) sandwich cell," Thin solid films, vol. 324, pp. 209-213,
1998.
[19] H. Wang, J. Yang, B. Yu, Y. Geng, and D. Yan, "High mobility vanadyl-
phthalocyanine polycrystalline films for organic field-effect transistors," Applied
Physics Letters, vol. 90, p. 253510, 2007.

6
Chapter 1 Introduction

[20] Q. Chen, H. Tada, H. Yamada, and K. Matsushige, "Local electrical properties of

vanadyl phthalocyanine multilayers studied by atomic force microscopy,"
Molecular Crystals and Liquid Crystals, vol. 337, pp. 505-509, 1999.
[21] Y. Zhang, T. Learmonth, S. Wang, A. Matsuura, L. Plucinski, S. Bernardis, C.
O'Donnell, and K. E. Smith, "Electronic structure of the organic semiconductor
vanadyl phthalocyanine (VO-Pc)," Journal of Materials Chemistry, vol. 17, pp.
1276-1283, 2007.
[22] V. Zaitsev, N. Levshin, and S. Yudin, "Changes in adsorption and optical
properties near the phase transition of super thin vanadyl phthalocyanine
Langmuir films," Moscow University Physics Bulletin, vol. 64, pp. 191-194, 2009.
[23] Y. Wang, J. Si, J. Zhao, B. Zou, P. Ye, L. Qiu, Y. Shen, Z. Cai, and J. Zhou,
"Ultrafast optical bistable behaviors of vanadyl phthalocyanine-doped polymer
film quasi-waveguide and waveguide," Thin solid films, vol. 298, pp. 215-220,
1997.
[24] P. Peumans, S. Uchida, and S. R. Forrest, "Efficient bulk heterojunction
photovoltaic cells using small-molecular-weight organic thin films," Materials for
Sustainable Energy: A Collection of Peer-Reviewed Research and Review
Articles from Nature Publishing Group, p. 94, 2010.
[25] P. Peumans, A. Yakimov, and S. R. Forrest, "Small molecular weight organic thin-
film photodetectors and solar cells," Journal of Applied Physics, vol. 93, p. 3693,
2003.

7
Chapter 2 Literature Review

2 Literature Review

This chapter provides (i) a review and scope of the previous studies reported in the
literature on the optical, morphological and structural properties of the thin films of VOPc
and its derivatives, (ii) scope, background and types of the humidity sensors and solar
cells, (iii) review of the metal phthalocyanine based humidity sensors and single layer
solar cells, and (iv) the other organic materials used in the fabrication of sensors and
solar cells.

2.1 Vanadyl Phthalocyanine (VOPc) and Its

Soluble Derivatives (VOPcPhO)

The growing interest in obtaining new organic devices requires the development of new
organic materials. In the past few decades, research has focused on organic materials
such as phthalocyanines (Pcs) [1-3]. Pcs, an important class of molecular functional
materials, are potential candidates in many applications due to their high optical
absorption in the visible spectral region [3-5]. A number of applications such as
colorants, laser printers and catalysts, etc., have made use of phthalocyanines and their
derivatives [6]. In the present era, emphasis has been put on the design and synthesis
of novel phthalocyanine species, the structure–property relationship, molecular
electronics and opto-electronics [7]. Pcs are conjugated, symmetrical, 18-π electron
macrocyclic systems, which posses planar structure. They contain four isoindole units

8
Chapter 2 Literature Review

linked by four nitrogen atoms [3]. More recently, Pcs have become very important
building blocks for molecular materials and nanotechnological devices [8].

Usually, central metals are greatly responsible for the photo-electronic properties of Pcs.
Moreover they occur in numerous morphological forms due to a variety of their packing
structures [9, 10]. The properties of Pcs can be altered by the choice of central metal
atoms and by chemical substitution in the periphery [3]. Initially, the phthalocyanine had
no substitutions on the periphery and possessed a low solubility in most organic
solvents. The introduction of substituents at the periphery of Pcs results in the
enhancement of their solubility in organic solvents. The peripheral substituents are also
useful for accurate tuning of their unique optical properties. Currently, the substituted
phthalocyanines find applications in industrial catalytic systems [11], printing,
semiconductors, sensors, nanotechnology [12] and non-linear optics [13].

Although VOPc and its soluble derivatives are rare explored, however a few
investigations on VOPc, regarding its structure and spectroscopy, have been carried out
in the past few decades. Three different phases of VOPc i.e. phases I, II, and III are
reported in the literature [14-17]. Many studies have been conducted on the ultra thin
films of VOPc grown epitaxially on potassium bromide (KBr) [18-22]. Molecular
orientation and surface structures of VOPc adsorbed on KBr, potassium chloride (KCl)
and Sodium bromide (NaBr) are extensively studied [23-26]. The control of molecular
packing structure of a derivative of VOPc has been studied by S. Takami [27]. Thin films
of VOPc are prepared on alkali halide surfaces by molecular beam epitaxy. These films,
when investigated by various microscopy techniques, exhibited densely packed
crystallites [25].

9
Chapter 2 Literature Review

The effect of Vanadyl ion on the organization of VOPcPhO complex is demonstrated

through scanning tunneling microscopy (STM) [28]. The degradation of VOPcPhO
through the application of ultra sound has been reported by Banks [29].

2.2 Organic Thin Films

During the last few decades, progress in thin film technology has been a major concern.
The attractive properties of organic thin films are that they can be fabricated at relatively
low temperatures using simple techniques. They can also be fabricated on flexible
substrates at very low cost. The production of inexpensive and large scale electronic
devices is one of the biggest advantages of organic thin films. Very recently, there is an
increasing interest in the fabrication and study of organic sensors [30, 31] and solar
cells (OSCs). For the device performance high charge carrier mobilities are essential
therefore, the structural properties of the organic films are being investigated and
optimized.

2.2.1 Thin Film Deposition

To produce organic thin films, numerous techniques have been explored and employed.
There are a variety of techniques, having different complexity and applicability, used for
the deposition of organic thin films and multi-layers [32]. The choice of deposition
technique depends upon three key factors: (i) physicochemical properties of the
material, (ii) film quality requirements and (iii) type of the substrate used. Basically there
are two ways to prepare ultrathin organic films: one is a wet processing technique and

10
Chapter 2 Literature Review

the other is a dry processing method [33]. The former process, which is considered as a
simplest method, involves the application of a liquid solution of an organic material in a
volatile solvent, including aerosol, Langmuir-Blodgett, spreading, screen printing, inkjet
printing, doctor-blading, spray coating, drop-casting, dip-coating and solvent casting
methods [34]. However, while the later, solvent-free process, can be accomplished by
conventional methods [32] such as vacuum evaporation, e-beam deposition, pulsed
laser deposition and sputtering processes, etc. Besides these dry-coating techniques,
some other methods include plasma polymerization [33, 35], or photo-activated
processes [36, 37] are used to coat organic thin films on the substrates. According to
the type of material, the films can be vapor deposited with different strategies [38].

2.2.2 Thin Film Structural Characterization

The fabrication of efficient thin film based devices requires a deep insight of
spectroscopic, photophysical and electronic properties of thin films of the materials of
interest. The detailed understanding of the materials cannot be accomplished with a
single technique. Instead a number of analytical tools must be combined to fully
characterize the specific material.

The optical characterization of organic thin films is a basic method applied in the field of
organic electronics to yield information on the chemical structure and orientation of
molecular units. Spectroscopic studies are helpful in providing knowledge about
chemical bonding, energy levels, molecular geometries etc. The optical spectra can also
be used to calculate optical constants of the materials such as absorption coefficient,
optical energy band gaps and refractive index of thin films.

11
Chapter 2 Literature Review

The UV-Vis spectroscopy is a very attractive tool for optical measurements because
absorbance is linearly related to the absorber concentration [39]. The UV-Vis range
also spans human visual range, which makes it useful for the absorption, transmission,
and reflectivity of various materials. Insight into the optical and electronic properties of
materials, for their applications in electronics, communication and solar energy
conversions, can also be obtained by UV-Vis spectroscopy [39].

For organic materials, atomic force microscopy (AFM) is gaining popularity [40]. This
technique is especially useful for the topography of the surface of sample with
nanometer-scale-resolution.

The AFM technique, which is often called the “eye of nanotechnology” can be used for
imaging any conducting or non-conducting surface. AFM has a number of advantages
over other techniques which are shown in the Table 1:

12
Chapter 2 Literature Review

Table 1: Comparison of Atomic Force Microscopy and other Techniques

AFM TEM SEM Optical

Max resolution Atomic Atomic 1's nm 100's

nm

Typical 100-200 500 or 200- 10-50

cost higher 400
(x $1,000)

Imaging air, fluid, vacuum, vacuum vacuum air, fluid

Environment special gas

In-situ Yes No No Yes

In fluid Yes No No Yes

Sample Easy Difficult Easy Easy

preparation

The AFM technique is basically used for the determination of the sample topography
but with a few variations of the technique, characterization of the chemical structure of
the sample can also be obtained [41]. Scanning probe tips can also be chemically
modified and the spatial variation of the sample tip interaction can be used to infer local
chemical composition [40].

13
Chapter 2 Literature Review

The schematics for XRD are shown in Figure 2.1[42]. Bragg Law is the basic principle of
the XRD technique. The major components of X-ray diffractometer are a source of
monochromatic radiation and an x-ray detector. One set of divergent slits is located
between the specimen and the source, while the other is situated between the
specimen and the detector. The purpose of these slits is to limit scattered (non-
diffracted) radiation, background noise and also to collimate the radiation.

Figure 2.1. Working mechanism for X-Ray Diffraction technique.

In the samples diffraction occurs simultaneously at all the angles of 2θ. The diffraction
pattern can be obtained by rotating the detector to various 2θ angles in order to
measure diffraction from the sample. X-ray diffraction (XRD) and other diffraction
techniques are also extensively used to determine organization on a range of distance

14
Chapter 2 Literature Review

scales. The structural properties of organic materials have been extensively studied
using XRD [43-47].

2.2.3 Thin Film Applications

Recently, organic thin film materials have acquired great attention due to their
applications in a variety of fields such as mechanics, flexible electronics and optics [32,
48-51]. Organic thin films and multilayers are used typically in a wide range of
applications such as microelectronics devices, sensors, non-linear optical (NLO) and
molecular devices [50].

2.3 Organic Thin Film Based Devices

Organic electronics is capable of creating a new range of devices and applications. The
low cost of materials and fabrication processes, including printing type processes, mean
that large devices can be produced economically. Fabrication on flexible substrates is
also possible. Some of the devices fabricated in this study are discussed in the following
sections.

15
Chapter 2 Literature Review

2.3.1 Humidity Sensors

As water molecules are present in abundance everywhere in the atmosphere, therefore

the measurement and control of humidity becomes quite ticklish. The water molecules
can be adsorbed easily on the surface in the form of a single layer or multilayers of
molecules. The evaluation of humidity is thus crucial and at the same time quite
essential for the improvement of life quality and enhancement of commercial production.
Humidity sensors encompass a wide range of measurements and control applications
which include human comfort, health care, process control, environmental monitoring,
storage, meteorology and agriculture. The making of a good humidity sensor is an
intricate and a challenging process due to its various shortcomings such as low
sensitivity, slow response time, limitations in the sensing range, larger hysteresis, poor
chemical and physical stability and drift of humidity response. The humidity sensors
must meet the following requirements in order to be incorporated in a wide range of
applications:

 Better sensitivity over a wide range

 fast response time
 small hysteresis
 long life
 Resistance against contaminants
 Negligible temperature dependence
 Low cost

16
Chapter 2 Literature Review

The amount of water molecules in the atmosphere can be determined by employing

numerous measurement techniques. Depending on these techniques humidity can be
measured in terms of Relative Humidity (RH), Dew/Frost point (D/F PT) and Parts Per
Million (PPM). Relative Humidity (RH) can be defined as the ratio of the actual water
vapor pressure to the saturation water vapor pressure at a given temperature [52] and is
measured as a percentage. The relative humidity is defined as [53]:

2.1

where Pw is the pressure of water vapors and Ps is the saturated pressure.

For the practical applications regarding humidity sensors, a variety of new organic
materials [54-56] are being extensively studied. The incorporation of organic materials
offers advantages of low cost, easy fabrication, light weight and flexibility [57, 58]. A
flexible resistive type humidity sensor is shown in Figure 2.2 [59] below.

17
Chapter 2 Literature Review

Figure 2.2. A flexible resistive humidity sensor.

2.3.1.1 Classification of Humidity sensors

Humidity sensors are generally categorized into several types such electrical
impedance change sensors, hygrometric, gravimetric, thermo-elemental and integrated
type based on their measuring principles [52, 53, 60, 61]. There are several other
methods used to measure humidity, which include, surface acoustic wave (SAW)
sensors [62], optical fiber systems [63] and etc. The capacitive-type [64-68] and
resistive-type [69, 70] sensors are the two major types of electrical impedance change
humidity sensors which are most commonly used [71].

18
Chapter 2 Literature Review

For the fabrication of capacitive-type sensors, a variety of organic materials are being
extensively investigated [72, 73] . The sandwich type structure is usually employed for
the fabrication of most of the capacitive type sensors, in which organic thin film is
deposited on a suitable substrate with a top metallic electrode. This often damages the
active material and causes device failure due to shortening [74]. Surface-type devices
offer low cost and simple technology to study various properties of organic materials,
which include charge transport [75], electrolumiscence [76], light sensitivity [77], effect
of temperature [72] and effect of humidity [72, 78] etc.

2.3.1.1.1 Capacitive Humidity Sensors

Today, almost 75% of various humidity sensors are the capacitive type humidity sensors
which are most commonly employed in commercial applications [53]. Capacitive
humidity sensors comprise a thin film of organic material contacted by a pair of
electrodes, whereas the permittivity of the thin film depends on the relative humidity[79].
In the capacitive sensors the dielectric of thin films changes upon the adsorption of
water vapors. These sensors show responses proportional to relative humidity and are
capable of being operated over a wide relative humidity range. Capacitive-type sensors
can be used in swimming pools or livestock areas [80]. The performance of these
sensors depends on the choice of the material used for sensing film and the geometry
of the sensing electrodes. The sensitivity of the sensor greatly depends on the
morphological characteristics such as film thickness and surface morphology [81].
Capacitive sensors are relatively more costly as compared to the resistive-type
counterparts. However, some of the main advantages of capacitive-type sensors are
linear response to humidity, simple electronics and operation over wide range of relative

19
Chapter 2 Literature Review

humidity [80]. Therefore, in low-cost applications capacitive-type sensors are preferable

over resistive-type counterparts.

2.3.1.1.2 Resistive humidity sensors

Resistive humidity sensors correspond to a change in the resistance of a sensing

material, which is inversely proportional to humidity [82]. Resistive humidity sensors
measure humidity in terms of electrical quantities such as current, voltage or resistance.
Resistive-type sensors require sophisticated electronics. Such types of sensors show a
logarithmic response to relative humidity, which typically vary from 1 kΩ to 10 MΩ for the
humidity levels between 90 and 10 %RH. Below 20% of relative humidity, the response
of resistive-type sensors is very insignificant. However, these sensors are generally
cheaper as compared to the capacitive-type sensors and offer good interchangeability
[80, 83]. A typical response characteristic of the resistive humidity sensor measured at
room temperature is presented in Figure 2.3 [84].

20
Chapter 2 Literature Review

Figure 2.3. A typical response characteristics of the resistive humidity sensor

measured at room temperature.

2.3.1.2 Materials and Applications

Many type of humidity sensing materials have been investigated for their advantages
and disadvantages [85]. Organic materials are observed to have high sensitivity,
chemical stability and low hysteresis [86-90]. Various materials are used for humidity

21
Chapter 2 Literature Review

sensors, but recently polymers have been widely employed as sensing element [71, 91].
Polymers such as polyimide [92, 93], cellulose acetate butyrate (CAB) and polymethyl
methacrylate (PMMA) [71] are used in capacitive humidity sensors. A polyimide based
capacitive humidity sensor is presented in the following Figure 2.4 [94].

Figure 2.4. A polymide based capacitive humidity sensor.

Metal phthalocyanines (MPcs) and their soluble derivatives are very stable both
thermally and chemically, therefore, their thin films can be deposited without
decomposition [77]. Many surface-type humidity sensors have been prepared by
employing nickel phthalocyanine [65], copper phthalocyanine [64], Vanadyl
phthalocyanine [30, 31], using different deposition techniques such as vacuum
evaporation and spin coating methods.

22
Chapter 2 Literature Review

Capacitive type humidity sensors find applications in automotive industry, transport,

commercial and weather telemetry high temperature catalyst control systems [53]. They
can be used over wide range of temperature, due to their low temperature effect. These
sensors can be operated at temperatures up to as high as 200°C. The advantages of
resistive type sensors are long-term stability, usage from distant locations,
interchangeability, small size and low cost [82]. These features make resistive sensors
suitable for their application in industrial, commercial and residential areas.

2.3.2 Solar Cells

Nowadays the in-use solar cells are all silicon-based and extremely expensive. One
way to reduce the manufacturing cost of the photovoltaic devices is to introduce organic
thin film solar cells. Organic dyes fulfill many requirements to be used in solar cells:
They have high absorption coefficients and most of them exhibit p-type or n-type
semiconductor behavior. Organic solar cells offer a variety of advantages for example
they are relatively cheap, can be made on flexible substrates and the materials used for
solar cells can be tailored for various architectural applications. The demerits of the
organic solar cells include low power conversion efficiency (PCE) and limited
lifetime/stability issues. The organic semiconducting materials have gained great
attention because they can also be used as photovoltaic materials. Organic solar cells
possess many attractive features, such as organic materials used for the active layer
can be conveniently dissolved in most of the organic solvents, which make them useful
for bulkheterojunction. The flexible substrates and printing processes can be used for
the fabrication of such type of organic solar cells [95]. Recently reported PCE of the
organic solar cell is very less which cannot be used for daily applications [96, 97]. The
study of operation mechanisms and new materials for organic photovoltaic devices are

23
Chapter 2 Literature Review

introduced [96]. Besides improving PCE, another prime concern is a lifetime of organic
solar cells, which by so far is more than a year reported by Konarka technology [98].
Some of the types of organic solar cells are discussed below:

2.3.2.1 Materials and Performance Parameters for Solar Cells

For the fabrication of organic solar cells, a variety of organic semiconducting materials
have been explored. These materials posses certain features such as presence of
delocalized π-electrons, capability of sunlight absorption, generation of excess carriers
and transport of photo-generated carriers, which make them feasible for solar cell
applications [95]. These materials are generally classified into two groups i.e. electron-
donors and electron-acceptors. Majority of organic semiconductors are hole-conductors
and are known as electron donors. Some of the electron donor materials reported in the
literature are poly(3-hexylthiophene) (P3HT) and poly(N-9’-hepta-decanyl-2,7-
carbazole-alt-5,5-(4’,7’- di-thienyl-2’1’,3’-b3nzothiadizaole)) (PCDTBT), etc. [99, 100].
Fullerene (C60) and its derivative such as (6,6)-phenyl-C61-butyric acid methyl ester
(PCBM) are considered to be the best electron acceptors. The structure of electron
donors and electron acceptors are given in Figure 2.5.

24
Chapter 2 Literature Review

Figure 2.5. Electron donors and electron acceptors.

25
Chapter 2 Literature Review

Recently the efficiency of a organic solar cell, based on a single-layer, reaching 6% has
been reported [101, 102]. Among others, the solar cells made of polymer-fullerene blend
have shown drastically very high efficiency.

One of the limitations in the organic solar cells is low absorption. Large band gap of the
organic materials allow only 46% of the photons from the terrestrial solar spectrum to be
harvested as compared to their inorganic counterparts which allow 90 % of photons to
be absorbed. The band gap of donor materials, used for single-layer organic solar cells,
should be as low as 1.7 eV in order to obtain efficiency above 10% from [103]. The
strategy is to select electron-donors having high ionization potential and electron-
acceptor with high electron affinity for low band gap organic materials. The development
of new electron acceptor materials is another approach to enhance absorption with wide
absorption region.

Many factors, such as difference between LUMO of the electron-acceptor and HOMO of
the electron-donor, relating to an effective band gap and the active layer-electrodes
interface and morphology of the active layer, limit the open circuit voltage (VOC) of the
organic solar. Various organic materials have been employed as buffer layer to enhance
the VOC. One of the most widely employed buffer layer is PEDOT:PSS, which is used
with post deposition thermal treatment to improve its conductivity, morphology and work
function [104, 105]. Lithium Flouride (LiF) and pentacene are some of other organic
materials used as buffer layers [95].

The morphology of the photoactive layer greatly affects the charge transport efficiency.
Janssen et al. has observed that the increased PCE obtained in P3HT:PCBM devices is
due to improved morphology achieved by post thermal annealing [106]. The morphology
can be enhanced by another widely used method of adding processing additives [107,
108]. A device structure shown in Figure 2.6 [109], was proposed by Hoppe to optimize

26
Chapter 2 Literature Review

the solar cell performance. In this structure, efficient charge separation and charge
transport can be facilitated by the narrow space (~ 5-20 nm) between the n-type and p-
type phases.

Figure 2.6. An ideal structure for the bulk heterojunction organic solar cell.

A cell structure reported by Takanezawa et al. is shown in Figure 2.7 [110], in which a
ZnO nanorods-layer is placed between the ITO and the active layer.

27
Chapter 2 Literature Review

Figure 2.7. (a) FE-SEM cross-section image of the ZnO nanorod, (b) Schematic
structure of a ZnO/organic hybrid device.

The mechanism of the degradation of organic solar cells has been investigated by
Jorgensen et al., which is shown in Figure 2.8 [111]. The degradation process, which
causes short lifetime of organic photovoltaic cells, can be ascribed to the reaction of
organic material and metal electrodes with water and oxygen introduced from both
electrodes and lateral of the device. Krebs et al. has used thermo-cleavable materials,
which are more stable than other materials, for bulk heterojunction solar cells [112, 113].

28
Chapter 2 Literature Review

Figure 2.8. A degradation process in polymer solar cells.

The main focus of the research on organic solar cells has been to improve their
efficiency through optimizing materials. It is equally important to improve processing
techniques for the mass production. Krebs with colleagues has investigated a variety of
possible manufacturing processing techniques for organic solar cells [114-119].

Some of the deposition methods discussed in this chapter have been employed to
fabricate thin films of VOPcPhO and VOPcPhO based devices undertaken in the
present research. Moreover, the stand-alone films and devices are characterized in
order to have understanding of the optical and structural properties of the material and
underlying processes of the devices which are presented in the next chapters.

29
Chapter 2 Literature Review

2.4 References

[1] N. B. McKeown, Phthalocyanine materials: synthesis, structure, and function vol.

6: Cambridge Univ Pr, 1998.
[2] S. R. Forrest, "Ultrathin organic films grown by organic molecular beam
deposition and related techniques," Chemical Reviews, vol. 97, pp. 1793-1896,
1997.
[3] C. C. Leznoff and A. B. P. Lever, Phthalocyanines: Properties and Applications
VCH, New York 1996.
[4] A. T. Davidson, "The effect of the metal atom on the absorption spectra of
phthalocyanine films," The Journal of Chemical Physics, vol. 77, p. 168, 1982.
[5] I. Rosenthal, "Phthalocyanines as photodynamic sensitizers," Photochemistry
and Photobiology, vol. 53, p. 859, 1991.
[6] L. Li, Q. Tang, H. Li, W. Hu, X. Yang, Z. Shuai, Y. Liu, and D. Zhu, "Organic thin-
film transistors of phthalocyanines," Pure and Applied Chemistry, vol. 80, pp.
2231-2240, 2008.
[7] J. Jiang, O. C. O. N. Bekaroglu, and Y. C. O. N. Bian, Functional Phthalocyanine
Molecular Materials vol. 135: Springer Verlag, 2010.
[8] G. de la Torre, C. G. Claessens, and T. Torres, "Phthalocyanines: old dyes, new
materials. Putting color in nanotechnology," Chemical Communications, pp.
2000-2015, 2007.
[9] T. Saito, W. Sisk, T. Kobayashi, S. Suzuki, and T. Iwayanagi, "Photocarrier
generation processes of phthalocyanines studied by photocurrent and
electroabsorption measurements," The Journal of Physical Chemistry, vol. 97,
pp. 8026-8031, 1993.

30
Chapter 2 Literature Review

[10] T. Saito, Y. Iwakabe, T. Kobayashi, S. Suzuki, and T. Iwayanagi,

"Thermochromism of specific crystal form oxotitanium phthalocyanines studied
by electroabsorption and X-ray diffraction measurements," The Journal of
Physical Chemistry, vol. 98, pp. 2726-2728, 1994.
[11] N. B. McKeown and P. M. Budd, "Polymers of intrinsic microporosity (PIMs):
organic materials for membrane separations, heterogeneous catalysis and
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43
Chapter 3 Materials and Methods

3 Materials and Methods

This chapter presents the details related to organic semiconducting materials used and
the highlights of fabrication processes and characterization techniques adopted in this
study.

3.1 Organic Materials Used

The organic materials used, as the active layers in the invested devices and in stand-
alone thin films are Vanadyl 2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine
(VOPcPhO), poly(3,4-ethylenedioxythiophene) and poly(styrenesulfonate)
(PEDOT:PSS) and (6,6)-phenyl C61 butyric acid methyl ester (PCBM). The substrates
and solvents employed during solution/wet processing techniques in the work
undertaken are ordinary microscope glass slides, indium tin oxide coated glass
substrates and chloroform.

3.1.1 VOPcPhO

The focus of this study is to use soluble vanadyl phthalocyanine derivatives, Vanadyl
2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine (VOPcPhO), as a thin film on a glass
substrate for characterization or as an active layer for the devices. VOPcPhO is an
aromatic macrocyclic compound which is a green-color dye. The four isoindole units

44
Chapter 3 Materials and Methods

surrounding the central-metal atom contribute to the heterocyclic structure of VOPcPhO.

The VOPcPhO has vanadyl as a central-metal atom in the core of macrocycle. Each
isoindole unit is connected to another by a nitrogen atom that forms a part of an internal
16-membered ring of alternate carbon and nitrogen atoms [1]. VOPcPhO with a
molecular formula of C56H32N8O5V was purchased from Sigma Aldrich, Inc. and used as
obtained. The molecular weight of the material is 947.85 g mol -1. The molecular
structure of VOPcPhO is shown in Figure 3.1.

Figure 3.1. A molecular structure of VOPcPhO.

Thin films of VOPcPhO have been prepared for the investigation of optical, structural
and morphological properties. Thermal annealing was carried out to investigate the
effect of thermal treatment on various properties of the VOPcPhO thin films. VOPcPhO

45
Chapter 3 Materials and Methods

has also been used as an active layer in various devices such as humidity sensors and
solar cells undertaken in this research.

3.1.2 PEDOT:PSS

Thin film of PEDOT:PSS has been spin coated on the patterned indium tin oxide (ITO)
coated glass substrates prior to the deposition of VOPcPhO as an active layer in the
organic solar cells. The water soluble PEDOT:PSS was obtained from the (H. C. Starck,
Baytron P VPAI 4033) in the solution form and was filtered with using a 0.45 μm filter.
PEDOT:PSS is used as a buffer layer which serves as an interfacial hole conducting
and electron blocking layer [2, 3]. The PEDOT:PSS layer is also incorporated to avoid
shortening of the device. Figure 3.2 shows the molecular structure of PEDOT:PSS:

Figure 3.2. A molecular structure of PEDOT:PSS. The “dot’’ and “plus’’ represent the
unpaired electron and positive charge on the PEDOT chain, respectively.

46
Chapter 3 Materials and Methods

3.1.3 PCBM

A fullerene derivative, PCBM is an electron transporting and electron accepting material

and is used to improve the performance of the device [4, 5]. PCBM has successfully
been employed to reduce the optical bandgap of the VOPcPhO. The molecular
structure of PCBM is presented in Figure 3.3.

Figure 3.3. A molecular structure of (PCBM)

47
Chapter 3 Materials and Methods

3.1.4 Solvent and Substrates

The chloroform was used as a solvent to get VOPcPhO conveniently dissolved. The
solution was prepared by dissolving 30 mg of VOPcPhO in 1 ml of chloroform. For
investigating a variety of properties the thin films and humidity properties plain glass
substrates were used. However, indium tin oxide (ITO) coated glass substrate was
employed for the fabrication of solar cells.

3.1.5 Substrate Cleaning Procedures

In the research work presented in this dissertation two types of substrates have been
used i.e. glass slides and ITO coated glass substrates. The glass slides have been used
for investigating properties of the VOPcPhO thin films VOPcPhO blends and humidity
sensors while the ITO coated glass slides were incorporated in the fabrication of organic
solar cells.

Substrate cleaning process is of prime importance prior to the thin film deposition or
device fabrication as it clears away oils and organic residues appearing on glass
surfaces. Cleaning of simple glass slides and patterning and cleaning of ITO coated
glass slides are given as under:

3.1.5.1 Cleaning Process for Glass Slides

The cleaning process, for microscopic glass slides, comprised of four steps:

48
Chapter 3 Materials and Methods

1. Deacon®
2. DI-water
3. Acetone
4. Methanol

Deacon® is a laboratory detergent used to remove organic compounds from the sample
surface. Microscope glass slides were effectively cleaned in a bath of soapy water or
Deacon®. The slides were then removed and rinsed in DI- water thoroughly in order to
wash away the residues of the detergent. Afterwards, a two-solvent method was applied
to remove organic substances like grease etc. After detergent-cleaning, the glass
substrates were first put into a beaker containing acetone and then in methanol. The
whole cleaning process was carried out in an ultrasonic supported bath for about 20
minutes using ultrasonic cleaner. As a final step, the glass substrates were blown dry
with nitrogen [6].

3.1.5.2 Patterning and Cleaning Process for ITO coated Glass

Slides

The wet chemical etching process was employed to pattern electrodes on the ITO
coated substrates. The parts of the ITO coated substrates, being used as the electrodes
during solar cell fabrication, were masked with ordinary nail enamel, which is non-
soluble in a diluted hydrochloric acid (HCl). The masked substrates were kept at room
temperature to let the nail enamel dry naturally. Later, the substrates were soaked in a
petri dish containing diluted Hydrochloric acid (HClconc : H2O = 1 : 10). The dish,
containing substrates, was placed on a hot plate at temperature of 80 oC for about half
an hour to fully remove the exposed parts of the ITO coating on the substrates. Then
the nail enamel was removed with acetone. Finally, the etched ITOs were cleaned using
the standard glass cleaning procedures.

49
Chapter 3 Materials and Methods

3.2 Fabrication Techniques

Two types of fabrication techniques have been adopted to deposit thin films in the
present work. The metal electrodes and VOPcPhO thin films for some applications have
been prepared by thermal evaporation. However, solution processing technique has
been employed to prepare thin film of VOPcPhO and VOPcPhO blends for film
characterization and devices investigated in this study.

3.2.1 Vacuum Thermal Evaporation

The most widely adopted method for preparation of thin films of metal is the thermal
evaporation. This method involves deposition of the source metal by evaporation or
sublimation into the gaseous state by heat under vacuum. The molecules travel from
the source to the substrate. In a high vacuum system, molecules move in straight lines
from the source to the substrate and the uniformity is controlled by the geometrical
configuration and rate of deposition.

The electrodes and organic thin films for different purposes have been thermally
evaporated using Edwards AUTO 306 vacuum evaporator with an online FTM5 crystal
thickness monitor, installed at the Faculty of Materials Science and Engineering
(FMSE), GIK Institute and at the clean room of Low dimensional Materials Research
Laboratory, University of Malaya. The equipment has the capability of accommodating
four sources at a time. The operational vacuum is 5x 10 -6 Torr and working current
ranges from 20-40 A. A photograph of the vacuum evaporator is specified in Figure 3.4.

50
Chapter 3 Materials and Methods

Figure 3.4. A photograph of Edward AUTO 306 Vacuum Evaporator.

Eventually, the metal electrodes were thermally deposited on the cleaned glass
substrates at the rate of 0.2-0.3 nm/s under a medium vacuum of 5x10-5 mbar.
However, thin films of VOPcPhO were thermally sublimed on the cleaned glass
substrates at the rate of 0.1-0.2 nm/s under the same pressure at room temperature.
The deposition process was carried out at a pressure of 10-5 mbar in order to produce
uniform film and avoid clusters. The thickness of the deposited VOPcPhO films was

51
Chapter 3 Materials and Methods

measured using FTM5 quartz-crystal thickness monitor installed inside the deposition
chamber. The schematics for thermal evaporation are presented in Figure 3.5.

Figure 3.5. A schematic diagram of thermal evaporator used in our labs.

52
Chapter 3 Materials and Methods

3.2.2 Spin-Coating Technique

A typical spin-coating process involves deposition of a small amount of solution onto the
substrate. Then the substrate is spun at high speed (typically around 3000 rpm). The
solution is caused to spread uniformly onto the substrate due to the uniform centripetal
acceleration. The nature of the solution determines the film thickness and other
properties of the thin films. Moreover, the properties (thickness and uniformity) of coated
films can be altered by the spin rate. A photograph of a small spin coating unit used for
the deposition of thin films is shown in Figure 3.6.

Figure 3.6. A photograph of WS-400B-6NPP-Lite spin coater used to deposite thin

films of VOPcPhO.

53
Chapter 3 Materials and Methods

The solution processed films have been fabricated by spin-coating technique employing
WS-400B-6NPP-Lite spin coater available at the clean room of Low dimensional
Materials Research Laboratory, University of Malaya. The prepared solutions of
PEDOT:PSS, VOPcPhO and VOPcPhO/PCBM were spun-cast on the specific substrate
to form the thin films for specialized purposes (either characterization or device
fabrication). The desirable thicknesses of the thin films were obtained by varying spin
speed of the spin coater. Figure 3.7 shows a photograph of WS-400B-6NPP-Lite spin
coater.

Figure 3.7. A schematic diagram of spin coating technique.

54
Chapter 3 Materials and Methods

3.2.3 Photolithography Technique

Photolithography is a three-step process comprising of deposition, uv-exposure and

development. A layer of photoresist is deposited on the already cleaned substrate by a
standard spin-casting method to produce a thin uniform layer. There are two types of
photoresist negative or positive. The choice of positive or negative photoresist depends
upon the desired area to be removed. The positive resist has become more popular due
to its better process controllability for small geometry features. Figure 3.8 shows the
positive and negative photoresist [7, 8].

Figure 3.8. Types of photoresist coating: (Positive and negative photoresist).

55
Chapter 3 Materials and Methods

Mask alignment is considered one of the most important steps in the photolithography
process. A mask, which is a glass plate with patterns (for device design) on one side, is
aligned with the substrate. The pattern is, then, transferred by exposing the photoresist
to an ultraviolet light through the pattern on the mask. Every successive patterned mask
should be aligned to the previous pattern. The three different exposure methods:
contact, proximity, and projection are shown in the Figure 3.9 [8]. Development is the
last step in the photolithography. In this step the photoresist is removed to acquire the
desired film patterns on the substrate.

Figure 3.9. Three different kinds of exposure methods.

56
Chapter 3 Materials and Methods

3.3 Experimental Procedures

This section will cover experimental techniques employed for preparation of VOPcPhO
thin films and devices fabrication using VOPcPhO as an active layer.

3.3.1 Preparation of Stand-Alone Thin Films

For the spectroscopic, morphological, structural and post-thermal annealing

investigations solution processed thin films were prepared on cleaned glass slides. The
glass slides were cleaned according to the standard cleaning procedures. VOPcPhO
was conveniently dissolved in chloroform. The VOPcPhO solution concentration was
fixed at 30 mg/ml (3% weight) in chloroform. Then, the solution was spun-cast on the
cleaned glass slides. The spin speed was maintained at 3000 rpm to acquire a thin film
(~120 nm thickness) using a WS-400B-6NPP-Lite spin coater in the presence of
nitrogen flow.

The thermally evaporated thin films for the investigation of thermal annealing effect and
humidity sensors with symmetric electrodes were prepared in the following manner.
VOPcPhO was sublimed, at room temperatures, on carefully cleaned glass substrates.
The pressure during deposition process was maintained at 10-5 mbar. The thickness of
the deposited VOPcPhO films was measured using FTM5 quartz-crystal thickness
monitor. The thickness of the films for thermal annealing investigation was 150 nm,
which was acieved by holding deposition rate at 0.1-0.2 nm/s. For humidity sensors
three different thicknesses i.e. 50 nm, 100 nm and 150 nm were obtained.

57
Chapter 3 Materials and Methods

PCBM was also purchased from Sigma-Aldrich and used as provided without any
further purification. The blends of VOPcPhO and PCBM with three different
concentrations (i.e. 25, 50 and 75 % of PCBM), were prepared in chloroform. In order
to obtain homogeneous solution, the prepared blends were stirred for about 48 hours.
The thin films of VOPcPhO:PCBM blends were spun-cast on the cleaned substrates at
a spin rate of 1500 rpm using a WS-400B-6NPP-Lite spin coater as introduced earlier.

For the investigation of thermal annealing effect, thin films of VOPcPhO were produced
by spin coating the VOPcPhO on the glass substrates in the presence of nitrogen. The
speed of the spin-coater was maintained at 3000 rpm for 20 s to produce VOPcPhO thin
films resulting in the thickness of 140±5 nm. Immediately after spin-coating, the
deposited films were subjected to post-annealing procedure. The annealing treatment
was carried out for three samples on hot plates at temperatures of 95, 125 and 155 oC
for 20 min in ambient air. The as-cast and annealed films were then investigated for
their optical and morphological properties.

3.3.2 Fabrication of VOPcPhO-thin-film Based Devices

The Ag/VOPcPhO/Ag surface-type humidity sensors were fabricated on cleaned glass

substrates with dimensions 25x25x1 mm3. Silver electrodes of thickness ~100 nm, with
a gap of 40 µm, were thermally deposited on the substrates at the rate of 0.2-0.3 nm/s
under vacuum of 5x10-5 mbar. The substrates were plasma cleaned prior to the
deposition of electrodes. The 40 µm gap was achieved by using a shadow mask. Thin
films of VOPcPhO were thermally sublimed on the gap between the Ag electrodes at the
rate of 0.2 nm/s under vacuum of 5 x 10-5 mbar. The devices were fabricated with three
different thicknesses of VOPcPhO films i.e. 50 nm, 100 nm and 150 nm. The cross

58
Chapter 3 Materials and Methods

sectional view of the fabricated capacitive-type humidity sensors is shown in Figure

3.10.

Figure 3.10. Cross-sectional view of Ag/VOPcPhO/Ag capacitive-type humidity sensor.

For the fabrication of the Al/VOPcPhO/Pt co-planar humidity sensor the substrate was
cleaned using standard cleaning process. The procedure opted for the preparation of
asymmetric metal electrodes using photolithographic technique is shown in the
schematic diagram of Figure 3.11. The electrodes were deposited in two different steps:
A 5-6 m thick layer of photoresist was spin coated on a glass substrate using Clarient
AZ 4620 spin-coater. The shape of the first electrode (Aluminum) was defined by
photolithography steps shown in Figure 3.11 (a-c) Then, sputtering technique was used
to form thin-film electrode of aluminum at a nominal thickness of 300 nm from an
aluminum target at a constant current of 30 mA Figure 3.11d. The sputtering of the
electrodes of the sensor was performed by Baltec SCD005 sputter coater. The
electrode was patterned by a lift-off process of the photoresist Figure 3.11e. The
photoresist is stripped off by putting the sample in acetone, isopropyl alcohol and de-
ionized water subsequently. A second photolithographic step consists of patterning of
platinum electrode (electrode-2). On the patterned Al-electrode a photoresist layer was

59
Chapter 3 Materials and Methods

deposited again through the spin coating method. The exposure/development steps
presented in Figure 3.11 (f-h) were applied to define the Pt-electrode (electrode-2).
Later on, a 330 nm thick film of platinum was deposited through sputtering from a
platinum target followed by a lift-off process Figure 3.11 (i-j). The sensing area between
the two asymmetric electrodes was 17 μm.

60
Chapter 3 Materials and Methods

Figure 3.1. The steps employed in the photolithography for the fabrication of the
asymmetric sputtered metal-electrodes for humidity sensors; (a,f) mask,
(b,g) exposure to light, (c,h) development, (d,i) Au/Pt sputtering, (e,j)
photoresist lift-off.

61
Chapter 3 Materials and Methods

.A thin film of 120 nm was deposited on the pre-patterned asymmetric electrodes The
device structure is illustrated in Figure 3.12.

Figure 3.12. A 3-D device structure of a co-planar humidity sensor.

The organic solar cell reported in this work was prepared on the glass substrates coated
with ITO (230 nm thick and resistivity 7 Ω/cm2). The device preparation steps are as
follows: ITO substrate was initially etched with HCl. Afterwards the substrate was
thoroughly cleaned. The whole cleaning process was carried out in an ultrasonic
supported bath for about 20 minutes. Before the deposition of VOPcPhO, a water-
based solution of poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate)
(PEDOT:PSS), was deposited onto the ITO substrate. The solution of PEDOT:PSS was

62
Chapter 3 Materials and Methods

spin-coated at 7000 rpm for 20 s, resulting in 24 nm buffer layer on the ITO substrate.
Then, the sample was baked on a hotplate for 30 minutes at 120 oC. Later, the
VOPcPhO solution was spin coated on the baked sample. The spin rate was maintained
at 3000 rpm. The thin films of VOPcPhO coated on glass substrate for optical
examination and a fabricated solar cell are shown in the photograph of Figure 3.13.

Figure 3.13. A photograph of the thin films of VOPcPhO coated on glass substrates for
optical studies and a fabricated solar cell.

As a final step, an aluminum cathode of thickness ~55 nm with a growth rate of 0.1-0.3
nm/s was deposited on spin coated VOPcPhO thin film employing an Edward AUTO
306 thermal evaporator at a pressure of 2.4 x 10-5 mbar. The evaporation process was
performed through a shadow mask to yield ITO/PEDOT:PSS/VOPcPhO/Al type of
devices with an active area of 0.2 cm2. The preparation of VOPcPhO thin films and the
fabrication of VOPcPhO organic solar cell were carried out in the clean room
atmosphere. The device structure for VOPcPhO based solar cell is depicted in Figure
3.14.

63
Chapter 3 Materials and Methods

Figure 3.14. A device structure for single layer VOPcPhO based solar cell.

64
Chapter 3 Materials and Methods

3.4 Characterization Techniques

The characterization techniques of UV/Vis absorption, AFM and XRD have been
employed to investigate the optical and structural properties of the thin films and the
fabricated devices. Capacitance versus %RH, resistance versus %RH and
response/recovery versus time measurements were made on the sensors. Current-
Voltage measurements have been performed on the organic solar cells.

3.4.1 Surface Profilometer

The P-6 Stylus profiler is capable of measuring step heights and surface roughness of
the deposited thin films. It can also measure step heights and surface structure on thick
films. All thickness measurements have been performed on the films coated on glass
substrates using a KLA Tencor P-6 surface profilometer. Figure 3.15 shows a
photograph of a KLA Tencor P-6 surface profilometer.

65
Chapter 3 Materials and Methods

Figure 3.15. A photograph of KLA Tencor P-6 surface profilometer capable of

measuring film thickness.

66
Chapter 3 Materials and Methods

3.4.2 UV-Vis-NIR Spectrophotometery

In the present research, the Jasco V-570 spectrophotometer has been employed to
obtain the absorption spectra of various films. It is capable of measuring transmission,
reflectance and absorbance spectra of the thin films. The optical parameters such as
absorption coefficient, optical energy gap and other related features were calculated
from the absorbance spectra of the thin films, at room temperautre. The Jasco V-570
UV/Vis/NIR spectrophotometer is shown in Figure 3.16.

Figure 3.16. A photograph of Jasco V-570 UV/Vis/NIR spectrophotometer used for UV-
Vis spectra measurements.

67
Chapter 3 Materials and Methods

3.4.3 Atomic Force Microscopy (AFM)

Characterization

The AFM micrographs were obtained in a tapping mode using Digital Instruments Veeco
D3000 microscope. The AFM cantilever was provided by App Nano, Inc.The normal
spring constant of the cantilever was 0.03 N/m and the radius of the tip was less than 10
nm. The 2-D and 3-D AFM images of the thin films were used to estimate numerous
parameters such as grain size, surface roughness and section analysis. The images of
Digital Instruments Veeco D3000 atomic force microscope are given in Figure 3.17 and
Figure 3.18 below.

Figure 3.17. A Veeco D3000 microscope AFM system used in the characterization.

68
Chapter 3 Materials and Methods

Figure 3.18. AFM close-up view, showing the sample chuck and scanner.

3.4.4 X-Ray Diffractometery

The X-ray diffractograms were recorded using a Siemens D5000 diffractometer. XRD
experiments were carried out on the samples at room temperature. The radiation was
monochromatized Cu-Kα beam of average wavelength 0.154056 nm. A photograph is
shown in Figure 3.19.

69
Chapter 3 Materials and Methods

Figure 3.19. A photograph of Siemens D5000 Diffractometer used in the work reported
in this dissertaton.

70
Chapter 3 Materials and Methods

3.4.5 Humidity Measurements

The in-situ capacitance and resistance versus relative humidity response of the humidity
sensor, at ambient temperature (25°C+0.5), were carried out by placing the device in a
home- made hermetically sealed humidity chamber capable of providing a humidity
range of 0-95 % RH. The commercial digital humidity and LCR meters were employed
to record the data. The capacitive and resistance measurements were performed at a
frequency of 1 KHz with an ESCORT ELC-133A LCR meter, while the relative humidity
measurements were carried out by CEM DT-8860 digital humidity/temperature meter.
The relative humidity (RH) inside the chamber was varied between 0 and 95 % RH, with
a step size of 5 % RH, using dry and wet air. The test chamber provides different
humidity levels for the sensor. The device is fixed in the humidity chamber and is
exposed to humid ambience. The adsorption of water vapors at the surface occurs
when the relative humidity within the sealed chamber starts rising, leading to a drastic
change in the dielectric constant of the sensing element. The increase in the dielectric
constant of the sensing material raises the capacitance, which is recorded against
increasing relative humidity. The photograph of the humidity measurements setup is
shown in Figure 3.20.

71
Chapter 3 Materials and Methods

Figure 3.20. A photograph of the experimental setup for humidity measurements

prepared at Organic Electronics Lab, FES, GIK Institute.

72
Chapter 3 Materials and Methods

3.4.6 Current-Voltage Measurements (I-V) in Devices

Current-voltage (I-V) measurements refer to d.c. characterizations of devices which are

used to extract parameters and analyze the performance of the devices. For the
organic solar cells the current voltage (I-V) measurements were performed using
Keithley 236 source meter, shown in Figure 3.21, under the AM1.5G-filtered irradiation
(100 mW/cm2) from an Oriel 67005 solar simulator shown in Figure 3.22 in at the
LDMRC, University Malaya. The applied voltage was scanned between -0.5 and 1 V in
steps of 0.1 V at room temperature in the dark as well as under light irradiation.

73
Chapter 3 Materials and Methods

Figure 3.21. A photograph of Keithley 236 source meter used for characterization of
solar cell reported in this dissertation.

74
Chapter 3 Materials and Methods

Figure 3.22. A photograph of Oriel 67005 solar simulator used for measuring the
response of solar cell made from the organic materials reported in the
dissertation.

All the materials and methods given in this chapter have been used to fabricate and fully
characterize thin films and devices reported in the dissertation.

75
Chapter 3 Materials and Methods

3.5 References

[1] Y. Rio, M. S. Rodríguez-Morgade, and T. Torres, "Modulating the electronic

properties of porphyrinoids: a voyage from the violet to the infrared regions of the
electromagnetic spectrum," Organic & Biomolecular Chemistry, vol. 6, pp. 1877-
1894, 2008.
[2] A. Hübler, B. Trnovec, T. Zillger, M. Ali, N. Wetzold, M. Mingebach, A.
Wagenpfahl, C. Deibel, and V. Dyakonov, "Printed Paper Photovoltaic Cells,"
Advanced Energy Materials, 2011.
[3] M. D. Irwin, D. B. Buchholz, A. W. Hains, R. P. H. Chang, and T. J. Marks, "p-
Type semiconducting nickel oxide as an efficiency-enhancing anode interfacial
layer in polymer bulk-heterojunction solar cells," Proceedings of the National
Academy of Sciences, vol. 105, p. 2783, 2008.
[4] S. E. Shaheen, C. J. Brabec, N. S. Sariciftci, F. Padinger, T. Fromherz, and J. C.
Hummelen, "2.5% efficient organic plastic solar cells," Applied Physics Letters,
vol. 78, p. 841, 2001.
[5] M. Reyes-Reyes, K. Kim, and D. L. Carroll, "High-efficiency photovoltaic devices
based on annealed poly (3-hexylthiophene) and 1-(3-methoxycarbonyl)-propyl-1-
phenyl-(6, 6) C blends," Applied Physics Letters, vol. 87, p. 083506, 2005.
[6] G. J. Shugar, J. T. Ballinger, and L. M. Dawkins, Chemical technicians' ready
reference handbook: McGraw-Hill Professional, 1996.
[7] L. Mosher, C. M. Waits, B. Morgan, and R. Ghodssi, "Double-exposure grayscale
photolithography," Microelectromechanical Systems, Journal of, vol. 18, pp. 308-
315, 2009.
[8] http://www.ece.gatech.edu/research/labs/vc/theory/photolith.html

76
Chapter 4 Characterization of VOPcPhO based thin films

4 Characterization of VOPcPhO based

Thin Films

There is an interest in widening the absorption band of phthalocyanines into the near
infrared region for the potential applications in optical data storage and security printing
[1]. Various MPcs such as magnesium phthalocyanine, copper phthalocyanine, tin
phthalocyanine, etc., have been investigated for their optical properties [2-4]. For the
past few decades, MPcs are known for their potential use in inks, photoconductors,
solar cells, and a variety of sensors. The structural and electrical properties of VOPc
and VOPc derivative based devices have been explored [5, 6]. Previous investigations
on VOPc thin films have reported a relatively high carrier mobility (~1cm2/Vs) [7]. Due to
this particular feature, VOPcPhO is considered as a potential candidate for the
development of future optoelectronic devices.

To explore the potentially interesting properties of the materials, structural and

morphological characterization is thus considered as a prerequisite for a deep insight
and knowledge of the material. These structural properties mostly depend on the
deposition technique, the heat-treatment temperature and the conditions during film
deposition. Annealing process is a broadly employed method to enhance the quality of
the crystal and exploit structural defects in the material. During thermal annealing, the
morphology and structural properties of the material change. For semiconductor devices
like light emitting diodes and photovoltaic cells, the structural properties are very
important, therefore, it is essential to investigate how thermal annealing process affects
these properties [8]. The effect of thermal annealing process on the surface morphology
and structural properties of cobalt phthalocyanine, tin phthalocyanine [9, 10] have been

77
Chapter 4 Characterization of VOPcPhO based thin films

studied. Ye et al. have investigated the effect of different annealing temperatures on the
structural and optical properties of fluorinated copper phthalocyanine/α-sexithiophene
heterojunction thin films [11].

As mentioned earlier, in the present work, thin films of VOPcPhO have been fabricated
on glass substrates by vacuum deposition and solution processing techniques. A
detailed study on the effects of film-thickness, doping concentration and post fabrication
thermal annealing on the surface morphology and structural and optical properties have
been performed by various characterization techniques. Hence, the focus of our work is
to optimize VOPcPhO based thin films for their potential in the respective applications.

4.1 Optical and Spectroscopic Studies

In this section the spectroscopic studies of VOPcPhO thin film are presented. The effect
of thickness and doping concentration on the absorption coefficient is also discussed.
Optical energy band-gap has also been extracted from the optical data.

4.1.1 Absorption spectra of VOPcPhO

The photo-absorption measurements made on the spin coated film of VOPcPhO are
shown in Figure 4.1 [12].It is observed that VOPcPhO exhibits two predominant bands
in the absorption spectra. The Q-band, which is a well-known band of a phthalocyanine
molecule, exists in the visible region between 630 nm and 750 nm, while the Soret-band
(B-band) is observed in the ultra-violet (UV) region from 270 to 410 nm.

78
Chapter 4 Characterization of VOPcPhO based thin films

Figure 4.1. Absorption spectra of spin coated VOPcPhO thin film on glass.

It is generally considered that the aromatic cyclic conjugated 18-π electrons system is
responsible for the spectral properties of the phthalocyanines [13]. The UV and visible
spectra for the metal phthalocyanines emerge from (i) the molecular orbitals contained
in the 18-π electrons system and (ii) the overlapping orbitals on the metal atom, present

79
Chapter 4 Characterization of VOPcPhO based thin films

in the center of the ring [14] . A close look at the absorption spectra of VOPcPhO thin
film reveals that the Q-band splits out in two characteristic peaks. The higher energy
peak (strong peak) occurs at 666 nm and the low energy peak (shoulder) appears at
715 nm in the visible region. However, the Soret-band or B-band possesses two peaks
with one shoulder in the UV region of the absorption spectrum. The high energy peaks
are observed at 290 nm and 344 nm while the shoulder exists at 408 nm [15-17].

We attribute both Q-band and Soret-band to the two lowest singlet–singlet electronic
transitions of the conjugated system [18, 19]. The previous studies have reported that
the Q-band, which is quite sensitive to the environment of the molecule, is strongly
localized on the Pc-ring [20]. In the visible region (Q-band) the excitation takes place
from the ground state a1u (π) highest occupied molecular orbital (HOMO) to eg (π*)
lowest unoccupied molecular orbital (LUMO) of the phthalocyanine ring, which can be
interpreted as a transition between bonding and anti-bonding molecular orbitals [15]. In
the visible spectral region, the higher energy peak appearing at 1.88 eV is associated
with the first π–π* transition on the phthalocyanine macro-cycle, while the low energy
shoulder occurring at 1.73 eV may be attributed to the presence of second π–π*
transition, excitonic transition, vibrational interval or surface state [15, 21, 22].
Nevertheless, the characteristic splitting (Davydov splitting), which results due to the
vibronic coupling in the excited state, is observed in the Q-band region. The energy
separation due to the Davydov splitting was found to be 0.15 eV. This value is close to
the values reported previously for the other phthalocyanine molecules [15, 23]. The
differences in the relative orientation of molecules are considered to be an important
factor for the extent of the Davydov splitting. In the near UV region of the spectrum, the
B band or Soret band may arise due to a2u (π) highest occupied molecular orbital
(HOMO) to eg (π*) lowest unoccupied molecular orbital (LUMO) transition.

80
Chapter 4 Characterization of VOPcPhO based thin films

The following equation [24] has been employed to calculate the absorption coefficient
for the as-cast and thermally annealed films of VOPcPhO:

4.1

where 2.303 is a conversion factor, ‘A’ is the measured absorbance of the annealed thin
film samples and ‘d’ is the thickness of the film.

4.1.2 Effect of thickness on the absorption spectra

The thickness of the VOPcPhO active layer has been varied by manipulating spin-rate
of the spin-coater while keeping the concentration and the solvent the same. The
measured thicknesses are tabulated in Table 4.1 It is evident from the Table 4.1, that the
higher the spin rate the thinner is the active layer.

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Chapter 4 Characterization of VOPcPhO based thin films

Table 4.1: Spin rates and thicknesses

Spin Rate (rpm) 1000 2000 3000 4000

Film Thickness ( 0.1 ) (nm) 210.1 184 146.9 116.3

UV/Vis/NIR absorption spectra of the spin-coated VOPcPhO thin films on glass

substrates for four different spin rates are presented in Figure 4.2. The absorption
spectra reveals that the absorption coefficient of the spin coated films of VOPcPhO
tends to increase with increasing spin rates.

82
Chapter 4 Characterization of VOPcPhO based thin films

Figure 4.2. Absorption spectra of spin coated VOPcPhO thin films on glass at different
spin rates.

83
Chapter 4 Characterization of VOPcPhO based thin films

4.1.3 Effect of doping of Fullerene derivative on the

absorption spectra

The effect of doping concentration of PCBM on absorption spectra is shown in Figure

4.3. It can be observed that the doping concentration has a considerable effect on the
absorption coefficient of the investigated films. The absorption coefficient of the samples
seems to increase with increasing concentration of PCBM. The intensity of the bands in
the absorption spectrum strongly depends on the concentration of the dopant, which
could be ascribed to the doping and charge transfer complexes between the VOPcPhO
and PCBM. The VOPcPhO acts as electron donor while PCBM acts as electron
acceptor. This feature makes the VOPcPhO:PCBM blend suitable for photovoltaic
applications, where the efficiency strongly depends on dissociation of the exciton and
charge separation [25].

84
Chapter 4 Characterization of VOPcPhO based thin films

Figure 4.3. Optical absorption spectrum of VOPcPhO:PCBM blend for different dopant
concentrations.

85
Chapter 4 Characterization of VOPcPhO based thin films

4.2 Optical Energy Band gap

The optical energy gaps Eg, evaluated using absorption spectroscopy, for the as-
deposited VOPcPhO and the PCBM doped VOPcPhO films are shown in Figure 4.4.
The information about direct and indirect inter-band transitions can be acquired through
one-electron theory [26]. The absorption edge data of phthalocyanines have been
analyzed.

86
Chapter 4 Characterization of VOPcPhO based thin films

Figure 4.4. The variation of the absorption coefficient (α) as a function of photon
energy for different dopant concentrations, (1) 0 %; (2) 25 %; (3) 50 % and
(4) 75 %, showing reduction in band-gap with increasing dopant
concentration.

87
Chapter 4 Characterization of VOPcPhO based thin films

by this theory [27]. The relation between absorption coefficient and photon energy is
given as below [26]:

4.2

Where α0 is a constant, E is the energy gap (bandgap) and r is the factor used to
evaluate the type of transitions. The value of r equals 2 for direct allowed, 1/2 for
indirect allowed, 2/3 for direct forbidden and 1/3 for indirect forbidden transitions. The
Eq. (4.2) is manipulated and used to plot a graph between photon energy and
d[ln(αhν)]/d[hν] in order to obtain the value of ‘r’. The transition determining factor ‘r’ is
calculated to be equal to 2 showing direct inter--band allowed transitions, which is
consistent with band to band transition in other phthalocyanines [28-30].

The energy gap for undoped VOPcPhO and VOPcPhO:PCBM blend of different
concentrations are determined from the plot of (αhν)2 and photon energy. Extrapolating
the linear portion of the plot to the x-axis at 0, the optical gap was evaluated from the
intercept as shown in Figure 4.4. The optical band gap of the film decreases from 3.32
to 3.26 eV for increasing doping concentrations of PCBM in the blend films.

The energy gap for undoped VOPcPhO is 3.32 eV while the optical energy gap for the
doped VOPcPhO with PCBM concentration of 25, 50 and 75 % are 3.30 eV, 3.28 eV
and 3.26 eV, respectively. It is evident from the statistics that the optical energy gap
decreases with increasing doping levels of PCBM. The decrease in the energy band

88
Chapter 4 Characterization of VOPcPhO based thin films

gap may be ascribed to the intermolecular interactions between VOPcPhO and PCBM.
It may also be inferred that the conjugated chain lengths may also enhance. Another
possible reason for this decrease in the optical band gap may be attributed to the fact
that the increasing PCBM concentration induces considerable structural changes in the
films. The characteristics of the energy gap states can be determined by the empty π
states in the conduction band and filled π states in the valence band [31].

Figure 4.5 shows that a red shift occurs as a result of the doping concentration of PCBM
in the absorption spectra of VOPcPhO:PCBM blend films. The red shift in the blend
films can be attributed to the decrease in the energy gap with doping contents [32]. With
the help of this doping process the energy gap has successfully been reduced from 3.32
eV to 3.26 eV.

89
Chapter 4 Characterization of VOPcPhO based thin films

Figure 4.5. The variation of the absorption coefficient (α) as a function of photon
energy for different dopant concentrations (1) 25 %; (2) 50 % and (3) 75
% indicating red-shift along the absorption edge.

90
Chapter 4 Characterization of VOPcPhO based thin films

4.3 Morphological and Structural Studies

This section covers the morphological and structural studies carried out on the thin films
of VOPcPhO.

4.3.1 Atomic Force Microscopy

The 2-D and 3-D AFM micrographs along with section analysis, obtained in tapping
mode at room temperature are presented in Figure 4.6, with a scan size area of 5 um.
The grain size can be determined from the 2-D micrograph while 3-D AFM image can
help in understanding the orientation of the grains. The average grain size obtained
from the images of the spun-cast VOPcPhO film is around 651 nm2. The measured root-
mean-square (rms) roughness of the VOPcPhO film is 0.286 nm.

91
Chapter 4 Characterization of VOPcPhO based thin films

Figure 4.6. AFM micrographs for spin coated thin film of VOPcPhO employed for
humidity sensor: (a) 3-D micrograph, (b) 2-D micrograph and (c) section
analysis.

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Chapter 4 Characterization of VOPcPhO based thin films

The surface roughness can be measured in terms of various parameters such as

average roughness, line roughness and root mean square roughness (R rms). The rms
roughness can be calculated by using the formula given below [33]:

4.3

Where ‘L’ is the cut off length and Z2(x) is the height deviation of the profile.

It can be observed from Figure 4.6 that the VOPcPhO film shows a relatively smooth
surface with some rough and sharp peaks. The results obtained here can be helpful in
better understanding of the underlying relationship between the morphology of the
semiconducting layer and the adsorption of water molecules. It may be suggested that
the rougher the surface the greater are the absorption sites available. Moreover, with
the increased roughness the sensitivity of the film increases remarkably. However, in the
present study the film appears to be slightly rough but the roughness of the surface can
be enhanced by a number of methods e.g. thermal annealing, controlled growth rate
and solvent treatment etc. which ensure the improved device performance and its
efficiency [34-38].

93
Chapter 4 Characterization of VOPcPhO based thin films

4.3.2 X-Ray Diffraction

The X-ray diffraction pattern of the VOPcPhO film is shown in Figure 4.7, which has
been obtained at room temperature. The X-ray diffractometer is used to investigate the
nature of the film. The absence of significant peaks in the curve of Figure 4.7 suggests
lack of crystallinity in the sample film. Moreover, the x-ray pattern shows a
characteristics hump which indicates amorphous and foggy nature of the VOPcPhO thin
film [33].

Figure 4.7. XRD spectra of a spin-coated thin film of VOPcPhO for humidity sensor

94
Chapter 4 Characterization of VOPcPhO based thin films

4.4 Influence of Thermal Annealing on the

Optical, Morphological and Structural
Properties of VOPcPhO

This section focuses on the optical studies, structure and morphology of VOPcPhO
pristine and annealed thin films for photo-devices application.

4.4.1 UV/Vis Absorption Spectra Measurements

Figure 4.8 shows the UV/Vis absorption spectra for the as-cast and annealed films
thermally treated at temperatures 95, 125 and 155 oC for a period of 20 minutes in
atmosphere. A change in the intensities of the absorption coefficient of the VOPcPhO
films after thermal treatment is observed in the curves of Figure 4.8. It is evident that the
annealing temperature affects the absorption coefficient and the amount of Davydov
splitting. The intensities of the absorption peaks in the lower energy band (Q-band) tend
to increase with increasing temperature see Figure 4.8. The spectra of the as-cast and
annealed samples reveal no distinguishable shift before and after annealing. The
increase in the intensities of the absorption peaks in the UV spectral region (Soret band)

95
Chapter 4 Characterization of VOPcPhO based thin films

Figure 4.8. Optical absorption spectrum of the VOPcPhO thin films in the Q-band
region before and after thermal annealing. Inset shows a spectrum before
and after annealing in the Soret-band region.

is exhibited in the inset of Figure 4.8. The variation in the maximum absorption
coefficient for both Q-band and Soret-band against the annealing temperature of the
spin-coated VOPcPhO thin films is presented in Figure 4.9. The increment in the
absorption coefficient may be ascribed to better molecular arrangement in the annealed
VOPcPhO films as compared to the as-cast sample. The films annealed at 155 oC
causes reduction in the absorption coefficient. This abrupt drop in the absorption

96
Chapter 4 Characterization of VOPcPhO based thin films

coefficient suggests that the VOPcPhO molecules have been disrupted at such high
temperatures of 155 oC (and 170 oC, result not shown) in the presence of oxygen (as
the films are annealed in air). The results shown in Figure 4.8 and Figure 4.9 indicate
that in order to achieve the maximum light absorption within the photoactive layer, the
VOPcPhO film needs to be annealed at optimum temperature of about 125 oC.

Figure 4.9. Relation between absorption spectra and temperature for UV and visible
spectrum regions.

Information concerning the optical band gap of materials is important for practical
considerations especially in the optoelectronic device fabrication. The optical absorption
spectra play a vital role in studying the energy band structure and the type of optical

97
Chapter 4 Characterization of VOPcPhO based thin films

transitions. The absorption coefficient (α) can be correlated to the photon energy (hν)
according to relationship shown in Eq. 4.2.

In order to ascertain the direct or indirect optical band gap, we rearrange Eq. 4.2 by
taking natural logarithm and derivative as follows:

4.4

The curve of d{ln(αhν)}/d{hν} versus hν is plotted in Figure 4.10. The energy value for
which a peak is observed on the curve presents approximately the optical energy gap
(Eg). This particular value of Eg helps determining the value of r. From the slope of
ln(αhν) versus ln(hν- Eg) shown in the inset of Figure 4.10, the value of r ~ 2 was
observed, which indicates the presence of direct allowed optical transitions between the
intermolecular energy bands in the VOPcPhO thin films.

98
Chapter 4 Characterization of VOPcPhO based thin films

Figure 4.10. Plot of dln(αhν)/dhν versus hν for the as-cast sample. Inset shows a plot of
ln(αhν) versus ln(hν –Eg) to determine the type of transition.

To find out the accurate energy band gaps in the lower energy and higher energy
regions of the absorption spectra, a graph between (αE)2 and photon energy (E) was
plotted as shown in Figure 4.11. The x-axis intercepts, resulting from the extrapolation of
the linear absorption, are exploited to obtain the direct energy band gaps for the as-cast

99
Chapter 4 Characterization of VOPcPhO based thin films

Figure 4.11. The variation of the absorption coefficient (α) as a function of photon
energy before and after annealing of the films in the Soret-band region.
Inset shows a Q-band region.

and the sample annealed at 125 oC. It is evident from the results that the energy gap is
reduced for the annealed sample in the Q-band region while in the Soret-band (B-band)
the energy gaps for the as-cast and the annealed thin films are almost the same.

100
Chapter 4 Characterization of VOPcPhO based thin films

4.4.2 AFM Images

The AFM images for VOPcPhO spin-coated films on glass substrates have been
examined for the as-cast film and films annealed at different temperatures in order to
obtain a deep understanding of the structural changes that result within the organic
material by thermal annealing process.

The 2-D and 3-D AFM images of the VOPcPhO thin films in tapping mode are depicted
in Figure 4.12. The different surface topographies of the as-cast and thermally annealed
films are clearly illustrated in the figure. The morphology of the as-cast film (with no
thermal treatment) exhibits rather a smooth and uniform surface without distinct
features, suggesting some small-sized clusters. The root-mean-square (rms) roughness
of the as-cast film is 0.286 nm, showing a quite smooth surface. The samples that have
undergone thermal treatment at 95 and 125 oC showed the rms roughness equal to
0.369 nm and 0.500 nm, respectively. The surface of the thin films becomes rougher
and non-uniform as the annealing temperature increases from 95 to 125 oC [39].

101
Chapter 4 Characterization of VOPcPhO based thin films

Figure 4.12. AFM images (2D and 3D ) of VOPcPhO thin films spun-cast on glass
substrates; scan size is 5 µm x 5 µm: (a) as-cast and annealed at (b) 95
o
C, (c) 125 oC, (d) 155 oC: (e) Relation between grain size and different
annealing temperatures.

102
Chapter 4 Characterization of VOPcPhO based thin films

The 3-D AFM micrographs show a considerable change in the texture of the film after
thermal treatment at various temperatures. The film in Figure 4.12c not only suggests
that the film has greater roughness but also a much coarser texture with sharp peak-like
features as compared to the other two films. It can be observed from Figure 4.12d that
upon further increasing the annealing temperature to 155 oC and above, the VOPcPhO
surface starts deteriorating and shows the evaporation of some parts of the film due to
degradation. The AFM image in Figure 4.12d verifies that the sudden drop in the
intensity of the absorption spectra of the film annealed at 155 oC is the outcome of
degraded films due to the high temperature effect. The best surface morphological
characteristic is achieved by annealing the VOPcPhO thin film at 125 oC with surface
roughness almost doubled as compared to the as-cast film, which is in agreement with
the results obtained from optical absorption spectrum. In order to confirm our results
some of the films were annealed at other temperatures such as 110, 140 and 170 oC.
However, the results are not presented here but the samples undergoing thermal
treatment at 110 and 140 oC showed smooth and uniform surfaces as compared to the
film annealed at 125 oC. The film annealed at 170 oC, results not shown, testifies the
degradation of the film at temperatures 155 oC and above. Hence, it can be concluded
that annealing beyond 155 oC is quite unsafe.

The rough and non-uniform morphology of the VOPcPhO thin films suggests the
formation of interpenetrating VOPcPhO molecular network. The coarse and rough
surface, obtained by thermal annealing, enhances the ordered structure formation in the
thin film. The relation between the device performance and the surface roughness of the
films has been studied and it has been reported that the higher roughness of the film
results in higher efficiency device [38, 39].

The 2-D micrographs in Figure 4.12 are used to estimate the grain size of the thin films
of VOPcPhO. The as-cast VOPcPhO thin film consists of small grains and has an

103
Chapter 4 Characterization of VOPcPhO based thin films

average grain size of about 651 nm2. On the contrary, the films annealed at
temperatures 95 and 125 oC show large grain size of 1088 nm2 and 1433 nm2,
respectively. It is observed that in our samples the grain size of the films increases with
increasing annealing temperatures. The observed increase in the grain size with
elevating temperature may be attributed to the fact that atoms move across the grown
surface to the sites of low energy. As a result, the grain size of the films increases and
has a subsequent influence on the surface roughness [33]. It may also be assumed that
some adjacent grains in the non-annealed film join together during thermal annealing
process [40].

The graph of Figure 4.12e shows the influence of annealing temperature on the average
grain size (obtained from the AFM images data) of VOPcPhO thin films. We found that
the grain size of VOPcPhO films can be enlarged by increasing the annealing
temperature. Thus, we anticipate that this process can be exploited to improve the film
surface morphology thereby enhancing the charge transport properties as well. Other
researchers have discovered that charge transport can be raised by annealing, which in
turn gives a better device performance [41, 42]. It is generally believed that some films
posses increased carrier transport efficiency due to well-ordered structure and/or large
grain size. However, the grain size of the degraded films (annealed at 155 and 170 oC)
is quite large which is unable to be recorded on the graph of Figure 4.12e.

104
Chapter 4 Characterization of VOPcPhO based thin films

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Chapter 4 Characterization of VOPcPhO based thin films

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Chapter 4 Characterization of VOPcPhO based thin films

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"Thermally evaporated ZnPc thin films--band gap dependence on thickness,"
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Chapter 4 Characterization of VOPcPhO based thin films

[27] S. Ambily and C. S. Menon, "Electrical conductivity studies and optical absorption
studies in copper phthalocyanine thin films," Solid State Communications, vol.
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[28] R. A. Collins, A. Krier, and A. K. Abass, "Optical properties of lead phthalocyanine
(PbPc) thin films," Thin Solid Films, vol. 229, pp. 113-118, 1993.
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properties of monoclinic lead phthalocyanine thin films," Advanced Materials for
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Chapter 4 Characterization of VOPcPhO based thin films

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Chapter 5 VOPcPhO-Thin-film based devices

5 VOPcPhO-Thin-Film Based Devices

The characterization of organic semiconductors is receiving great attention because of

the increased activity in their potential use in wide range electronic and photonic
devices such as junction diodes [1], organic field effect transistors (OFETs) [2], solar
cells [3], organic light emitting diodes (OLEDs) [4] and sensors [5]. Some of the organic
semiconductors have shown high sensitivity to humidity [6, 7], temperature [8, 9] and
different types of gases [10]. Therefore, investigation of properties of organic
semiconductors under different conditions is a very promising field for the development
of various sensors. Humidity is one of the most common constituent present in the
environment; therefore, humidity sensors are required for the measurement and control
of humidity in many fields such as industrial production, human comfort, medical and
agriculture etc.

Humidity sensors using organic materials are generally divided into two categories i.e.
resistive and capacitive types. The capacitive-type humidity sensors are popular due to
low power consumption [11]. They show better linearity and good stability at higher
temperature and higher humidity level as compared to their counterpart resistive-type
sensors [12-15]. The studies on VOPcPhO have been undertaken for its potential use
as an active material in the fabrication of organic electric, electronic and photonic
devices. As far as we know, VOPcPhO based humidity sensors have not been
investigated. In the present study, characterization of surface-type humidity sensors has
been reported.

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Chapter 5 VOPcPhO-Thin-film based devices

Humidity is among the most commonly measured quantities in measurement science.

The measurement of water vapors in atmosphere, which is called hygrometry, is very
complex [16] and in fact there is no one solution which can meet the entire requisite in
all conditions [17]. Some organic compounds show high sensitivity to humidity but these
compounds easily get dissolved in water [18, 19]. Phthalocyanines and porphyrins have
been used as humidity sensors because these organic materials are insoluble in water
[20]. The VOPc and its derivatives belong to the class of p-type organic semiconductors
[21, 22]. The Vanadyl Phthalocyanine derivative VOPcPhO is insoluble in water, so it
seems reasonable to investigate humidity sensing properties.

Organic semiconductor based solar cells have gained considerable attraction due to
their potential advantages such as low cost, light weight and ease of fabrication on
flexible substrates as compared to their inorganic counterparts [23]. The active layers
of the organic solar cells are mostly grown by vacuum evaporator, however, this
technique may produce non-uniform film-thickness over large area of substrate and the
material deposited on the wall of the evaporator chamber may contaminate deposition
afterward. Other alternative, an easier method to fabricate the organic thin film, is spin
coating method, in which the material used is very minimal for the solution preparation.
The bulk-heterojunction device structure which is possible only with wet-processing
method, resulted in higher efficiency as compared to single layer and bi-layer structures
[24].

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5.1 Humidity Sensors

The dielectric property of a material can be investigated by means of its capacitance as

the permittivity of the material varies proportionally with capacitance. The non-linear
behavior as a function of relative humidity exhibited by capacitive sensors can be
explained by the following equation [11]:

5.1

where the dielectric constant in wet state, the permittivity of the dielectric in a dry

state and n is the morphological factor of the dielectric material.

Essentially the capacitance variation with relative humidity could be attributed to various
aspects 1) dielectric constant of water, 2) porosity of active thin film, 3) contact area,
gap between electrodes and relative permittivity of sensing material and 4) polarizability
of organic material [25].

The relative permittivity of water is ~ 80 [26, 27], which is quite higher than that of
macrocyclic compounds [28]. The water molecules adsorbed by the active layer

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increase with rising relative humidity, which in turn tends to enhance capacitance of the
sensor. The VOPcPhO based surface type capacitive humidity sensor is made possible
to probe humidity variation due to large difference between relative permittivity of water
and that of vanadyl phthalocyanine derivative.

The adsorption of water molecule, which is a kind of polar molecule, on solid surface
could be categorized as chemisorption and physisorption. The formation of a molecule
layer of chemisorption at low humidity level and layers of physisorption at increasing
humidity levels can best describe the adsorption process of water. The water molecules
in the chemisorption layer and the first layer of phsisorption are doubly bonded and
unable to move freely. While molecules present in other physisorption layers are singly
bonded due to which they can be polarized easily. Hence the eminent increase in
relative permittivity and capacitance would be inevitable [27].

Another factor responsible for an increase in capacitance with relative humidity may be
the porosity of the active film. At higher relative humidity levels and greater film
thicknesses variation in capacitance become less conspicuous because the pores of the
film are being filled with water molecules. This results in decreased sensitivity towards
humidity [12]. The increased vapor contact area would increase physisorption of water
molecules and dielectric constant of the sensing material [26]. On the other hand
reduced gap plays an important role in enhancing the capacitance.

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5.1.1 Humidity Sensing Studies of VOPcPhO Film Using

Symmetric Electrodes

Results of measured capacitance (C) versus relative humidity (% RH) for the surface-
type Ag/VOPcPhO/Ag capacitive sensors with different thicknesses of the VOPcPhO
thin films are shown in Figure 5.1. In these measurements the capacitive response of
the sensors was studied over the range of 0-95 % RH and the relative humidity was
increased in steps of 5 % RH. In each step the humidity was held for sufficient time to
allow the sensors to respond fully and stabilize.

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Figure 5.1. Capcitance versus relative humidity relationship for the Ag/VOPcPhO/Ag
capacitive sensors for the VOPcPhO thicknesses equal to (1) 50nm, (2)
100nm, (3) 150nm.

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It is observed that the capacitance of the samples increases to 250, 225 and 110 times
for VOPcPhO films having thicknesses of 50 nm, 100 nm and 150 nm, respectively, for
the relative humidity being varied over the 0-95 % RH range. This indicates the
decrease of sensitivity with increasing thickness in the range studied and is in
agreement with capacitance versus % RH studies for the polyimide films reported by
Harrey et al [29].

It can be seen from Figure 5.1 that the sensors are insensitive in the range of 0-55 %
RH and after 55 % RH there is an exponential increase in the capacitance of the
devices due to the fact that the coverage of water vapors at the surface is not
continuous and only a few molecules are adsorbed. However, when one or several
water layers are formed, the increase in the capacitance becomes sharp and linear [30].
It may further hold the argument that the range 55-75 % RH might be the transition
humidity range for which the water molecule adsorption mode changes from single layer
physisorption to multilayer physisorption [31]. The phenomenon in Figure 5.1 might be
caused by adsorption of water vapors in the pores of thin films and presence of charge
transfer complexes [28, 30]. The dielectric constant changes with the increasing
adsorption of water vapors, hence the capacitance of the sensor increases.

Figure 5.2 shows relative capacitance-thickness relationship for Ag/VOPcPhO/Ag

sensors at different levels of humidity i.e. 70, 80 and 90 % RH. It is seen that at 50 nm
VOPcPhO thick film, the sensor gives highest performance. The sensor with thinner
VOPcPhO film is more sensitive towards humidity. In the case of thin film with thickness
of 50nm greater capacitance was achieved due to the acquisition of high concentration
of water molecules in VOPcPhO layer as compared to the other samples of
thicknesses100 nm and 150 nm.

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Figure 5.2. VOPcPhO film thickness relationships for Ag/VOPcPhO/Ag capacitive

sensor at relative humidity of 70%(1), 80%(2), 90%(3).

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The fact that capacitance increases with an increase in relative humidity can be best
explained by considering various probabilities. The polarization of the material can
describe the state of a dielectric which is related to the capacitance of the material. The
polarization and polarizabilities are co-related by the following relation [32].

5.2

where P is polarization, α is polarizability and E is electric field.

There are several causes of polarizabilities, which are ultimately responsible for the
relative change in the capacitance of the dielectric material. Various types of
polarizabilities are electronic polarizability ( αe ), ionic polarizability ( αi ) and dipolar
polarizability ( αdip ). The electronic polarizability arises due to the displacement of the
electron cloud of an atom/ion/molecule with respect to the nucleous. Ionic polarization
occurs due to change in distance between the positive and negative ions of a dipole.
There are certain permanent dipoles also present in a dielectric material which are
arranged in a random fashion. These dipoles change their orientation with the
application of electric field, thus giving rise to dipolar polarization or orientational
polarization. The electronic polarization and ionic polarization are induced polarizations.
The effect of electronic polarization is very negligible, however it is universally present in
all materials. Ionic polarization occurs in polar materials in which a molecule contains a
net positive and a net negative charge [32].

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There may be present internal charge transfer complexes [12, 28] in VOPcPhO,
therefore it can be assumed that ionic polarization takes place in this organic
semiconducting material along with the electronic polarization. At low frequency (1KHz)
measurements, the electronic and ionic polarizabilities are probably considered to affect
the capacitance of the material. Due to the presence of dipoles of water molecules
adsorbed by vanadyl phthalocyanine, the dipolar polarization also exists and it seems to
play a vital role in humidity-capacitance measurements of the material. In earlier
studies, it has been investigated that the polarizability due to transfer of charge carriers
as electrons and holes occurs in normal and humid environment [33].

If we take all the polarizabilities into account, we can write the net polarizabilty ( α n )
under normal conditions as:

5.3

when the sensor is placed in humid environment, then the total polarizability (α h) may be
the following:

5.4

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Chapter 5 VOPcPhO-Thin-film based devices

where αth is polarizability due to the transfer of electron/holes as charge carriers under
humid environment. Here we consider that concentration of charge carriers and total
polarizability (α h) are humidity variant.

The Clausius-Mossotti equation gives relation among macroscopic property (relative

dielectric constant) εr , microscopic property (polarizability of material) α and
concentration of molecules N, (or Nd as concentration of the charges in dry air) in the
material [32].

5.5

where εd is the relative permittivity and εo is permittivity of free space.

On the basis of this equation, the following expression has been derived [34, 35]:

5.6

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Chapter 5 VOPcPhO-Thin-film based devices

where Ch is capacitance in humid conditions, Cо is capacitance in dry air, k is humidity

capacitive factor and H is the relative humidity level. In this case the value of k is
1.099×10-4 (RH)-1. The value of relative permittivity, εd of the material is taken as 4 and
that of a morphological factor n is 2. This relation can be used for simulation of
capacitance-humidity relationship. Figure 5.3 shows the comparison between the
experimental and simulated relative capacitance-humidity results for the
Ag/VOPcPhO/Ag capacitive type sensor. The simulated results are found well in
agreement with experimental ones.

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Chapter 5 VOPcPhO-Thin-film based devices

Figure 5.3. Capacitance-relative humidity relationship for Ag/VOPcPhO/Ag capacitive

sensor with film thickness of 150nm: (1) experimental (2) Simulated .

Figure 5.4 shows current versus voltage relationship for the humidity sensor at two
different values of humidity levels (40 and 60 % RH). It is seen that at any certain
voltages the current increases with an increase in humidity level. This may be due to

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increase in the conductivity of the film with increasing humidity level. The drop in
resistance with the increase in humidity level can be due to several reasons [19, 30]: 1)
electronic and ionic conduction, 2) polar molecules of water may also increase the
conductivity of the thin film due to increase in proton concentration. 3) there may be
some physical phenomena behind all this, such as the effect of absorbed water
molecule as a dipole and impurity.

Figure 5.4. Current-Voltage characteristics of the device under two different humidity
levels (40 and 60 % RH).

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Chapter 5 VOPcPhO-Thin-film based devices

5.1.2 Humidity Sensing Studies of VOPcPhO Film Using

Asymmetric Electrodes

The platinum and aluminum have been selected for the electrodes because of very
large difference in their work functions (5.65 eV for Pt and 4.28 eV for Al). This
enormous difference in the work functions can create the electric field in the organic
semiconductor which in turn result in the formation of depletion region [36]. Having high
resistance depletion region makes the device very sensitive to the effect of dopants
(impurities), in our case water molecules serve as dopants. A few water molecules can
decrease the resistance of the samples remarkably, which has been observed in the
experimental results. Another benefit of the platinum electrode is its less blocking
capacity at the interface [37].

Results of capacitance (C)-relative humidity (RH) relationships for the Al/VOPcPhO/Pt

co-planar humidity sensor are shown in Figure 5.5. The capacitance of the humidity
sensor enhances 100-folds with increasing humidity. In each step, the humidity was
held for sufficient time to allow the sensors to respond fully and stabilize. It can be
observed that there is an exponential increase in the capacitance of the device in the
range 0 % RH to 90 % RH. Initially, only a few water molecules seem to be adsorbed on
the surface of VOPcPhO thin film and the coverage of water vapors is not continuous
throughout the surface of the sample showing that the sample is insensitive to humidity
below a certain level, in the beginning. Later, when one or several water layers get
stacked on the surface, the increase in the capacitance becomes sharp and linear [12].
It may further hold the argument that the range in which the change in capacitance is
significant i.e. ~60-90 %RH, might be the transition humidity range for which the water

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molecule adsorption mode changes from single layer physisorption to multilayer

physisorption [27]. The phenomenon in Figure 5.5 might be caused by adsorption of
water vapors in the pores of thin films and presence of charge transfer complexes [12,
28].

Figure 5.5. Capacitance versus relative humidity relationship for the Al/VOPcPhO/Pt
co-planar humidity sensor.

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Chapter 5 VOPcPhO-Thin-film based devices

The following approach may be used to explain the Ch/C0 versus relative humidity curve
shown in Figure 5.5. It is well known that the value of capacitance depends upon the
polarizability of the material [38]. Basically there are several sources of polarizability
such as dipolar αdip polarizability, ionic αi polarizability and electronic αe polarizability,
which cause relative change in the capacitance of the active sensing material. As the
VOPcPhO may comprise of internal charge-transfer complexes, it can be assumed that
the ionic polarizability also occurs in this organic semiconductor material. The
concentration of dipoles resulting from water molecules, VOPcPhO and water charge
transfer complexes might be a cause of change in capacitance of the sensor. Moreover,
the humidity might also cause change in the concentration of ions (which may be
produced by dissociation of water molecules), electrons and holes (if water acts as
impurity for the VOPcPhO) in VOPcPhO, which in turn increase the polarization [19] and
hence the capacitance. In earlier studies, it has been investigated that the polarizability
due to transfer of charge carriers as electrons and holes, occurs in normal and humid
environment [33].

In the beginning the pores of VOPcPhO thin film contain only dry air and have no water
molecules at all. When the sample is exposed to humid environment two barely
distinguishable processes, physical and chemical adsorption, take place. It seems very
probable that the hydroxyl groups may be formed by dissociation mechanism when
water vapor chemisorbs on the surface of the thin film. The first physisorption layer of
water molecules is immobile due to hydrogen bonding on the hydroxylated surface.
Subsequently, water vapors increase in number and the vapor pressure raises due to
which physisorption monolayer changes to multilayer and the resulting layer of
molecules become mobile. Eventually, the dielectric constant changes with the
increasing adsorption of water vapors and hence the capacitance of the co-planar
Al/VOPcPhO/Pt sensor increases, which is in line with the our previous results [39] and

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those reported by Ahmad et al [30]. This may imply that initially when there are less
hydroxyl groups available on the surface, the water molecules are more free to rotate.
Later on, as more hydroxyl groups are accumulated on the surface, the adsorbed water
molecules cannot move and rotate freely. It may be reasonable to assume that various
interfaces occur at the surface of the film, at the same time, after exposing the sample
to humidity environment. Prior to the exposure to humidity, only two interfaces existed,
i.e. film-air and substrate-film. After being revealed to humidity a few more interfaces
appear such as film-humid air, film-water, substrate-humid air, substrate-water and film
with changed dielectric constant-humid air/water [40].

It has been reported in literature that there exists another very important polarization
mechanism which is probably due to the electrochemical interaction of the humidity with
the grains’ surface at the interfaces between the organic layer and the electrodes. Water
has freely rotating dipoles which are organized differently from the water molecules.
Moreover, they are set up in a manner that might be explained by the interfacial
polarization [37, 41-43]. The water molecules can also participate in the formation of
double-layer at the interface between the organic layer and electrodes [44]. The
capacitance at the interfaces is also affected by the adsorption of water molecules. As
the concentration of the water molecules increases the polarization increases which in
turn enhances the capacitance [45].

For amorphous films, capillary condensation also results at higher humidity levels [40].
In porous films, the capillary condensation causes the value of capacitance to increase
with the increase in RH, which results in the change of dielectric constant [46]. This is

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consistent with the results obtained in our present study, as considerable change is
observed in the capacitance; we believe that capillary condensation leads to
appreciable variation in dielectric constant in this case.

Taking into account the shape of the experimental capacitance-humidity relationship, we

can assume that this graph may be simulated by the following function:

5.7

where, C and Co are the capacitances of the sensor at higher humidity level and initial
level, respectively; K is the capacitive-humidity factor. Assuming that maximum change
start at 60 %RH, Therefore the value of capacitance at 60 %RH is assumed to be the
value of ‘K’. A is the fitting parameter.

Figure 5.6 shows a relationship between humidity and resistance within the range 0 to
90 %RH. As can be seen, the resistance decreases with increasing humidity exhibiting
the sensitivity to humidity in the studied range. The electronic device characteristics are
considerably affected by adsorption of water molecules on the surface of the active
layer [47]. It has been reported that the holes can be generated in the surroundings of
the semiconducting active layer due to large dipole moment of water molecules after
adsorption of water vapors on the surface of the thin film [48]. The evidence in Figure
5.6 points to the likelihood that decrease in resistance with increasing humidity may be

128
Chapter 5 VOPcPhO-Thin-film based devices

associated with enhancement of the charge carrier density due to relatively large dipole
momentum of water molecules adsorbed on the surface of VOPcPhO. This results in
promotion of carrier conduction in the semiconducting active layer.

Figure 5.6. Resistance versus relative humidity relationship for the Al/VOPc/Pt co-
planar humidity sensor.

In general it can be assumed that average pore size for the materials with smaller grain
sizes is lower. The pore size plays a vital role in the charge conduction upon water

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Chapter 5 VOPcPhO-Thin-film based devices

absorption. The smaller pores get easily filled by water adsorbed and hence contribute
to the increase in the conductivity of the material which in turn reduces the resistance of
the device. However, the larger pores would not contribute to the conduction path as
only the walls of such pores are filled with the water adsorbed. Therefore, it may be
thought that smaller pores are necessary for higher humidity sensitivity in the lower
humidity regime in this case [49]. Sakai et al has reported that at high water content the
adsorbed water molecule on the surface of the semiconducting material support ion
dissociation which can enhance the conductivity of the material [50]. The absorbed
water also seem to introduce an increase in mobility of water [51]. The existence of
double layer at the electrodes-interface tends to modify the value of resistance as well.
With the increased concentration of water molecules, the resistance reduces due to
increased displacement currents of bound charges[45]. Humidity enhances significantly
the conduction process due to the reduction in the resistance after the formation of the
double layer at the interfaces between the electrodes and the active thin film [41].The
resistance of the organic semiconducting material decreased from 2.9 GΩ to 2.1 MΩ
when exposed to the humid environment from as low as 0 %RH to as high as 90 %RH,
showing high sensitivity.

The measured response and recovery characteristics of the Al/VOPcPhO/Pt co-planar

humidity sensor are presented in Figure 5.7. The response or recovery time can be
explained as the time required by the device to achieve 90 % of the total capacitance
change [48]. The response and recovery time for the sensor were measured by
increasing the humidity from 30 %RH to 90 %RH (absorption) and decreasing the
humidity from 90 %RH back to 30 %RH (desorption). For evaluating sensor response
time, the variation of capacitance at fixed value of relative humidity (90 %RH) is noted
with time and is plotted as portion ab in Figure 5.7. For recovery time similar
observations are taken during desorption and are plotted as portion bc in Figure 5.7.

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The response time and recovery time of the sensing material are found to be 20s each.
The capacitance versus time corresponding to the same humidity was tested several
times.

Figure 5.7. Response recovery versus time relationship for the Al/VOPcPhO/Pt co-
planar humidity sensor.

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5.1.3 Photovoltaic Studies of VOPcPhO Film Based Cell

Organic solar cell has become an attractive proposition due to the availability of a
variety of inexpensive materials which possess tunable properties and can be easily
incorporated in the solution based fabrication procedure [52-54]. However, the quest
for a material, which will solve the problems of low efficiency, poor reliability and
instability, is still an active research area [55, 56]. Even though there are several
studies on I-V characteristics of organic semiconducting materials [57-59], the I-V
curves of dark and illuminated VOPcPhO-based solar cells have not been studied in
detail. VOPcPhO can be conveniently utilized in solution processing techniques, as it
forms homogeneous solution in chloroform in almost no time. Soluble VOPc derivative
has been employed to form a solar cell by spin casting method.

Here the investigation is reported on the optical and electrical properties of VOPcPhO-
based device, sandwiched between aluminum and ITO electrodes. It is well known that
aluminum serves as a low work function electrode when it is coupled with a higher work
function electrode of ITO for being used in the applications of Schottky contacts and
heterojunction structure devices. The performance and reliability of the devices depend
on numerous properties of the metal-organic semiconductor interface. The thin films of
VOPcPhO were prepared for spectroscopic studies.

Since VOPcPhO behaves as p-type organic semiconductor so the holes are the
dominant carriers in the devices. Thus, the measured photocurrent in the thinner active
layer can be attributed mainly to the ability of charge carrier to travel to the external
electrodes without being recombined [60]. Recombination of holes and electrons may
occur in the thicker layer. Although, the efficiency shown here is very low but this is

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common in single layered solar cell structure. The lower efficiency can be attributed to
the fact that the single layer VOPcPhO is a hole transport material which has a low
electron mobility. The efficiency of the device may be enhanced by introducing the bulk
heterojunction structure which is a blend of donor and acceptor materials [61].

The effect of post thermal annealing on the spin coated films of the VOPcPhO has also
been undertaken in the present research work. It has been found that the quality of the
thin film was very much enhanced at the temperature equal to 125 oC. Therefore, the
active layer of VOPcPhO in the solar cell was annealed at 125 oC prior to the deposition
of the top (Al) electrode.

The current density-voltage (J-V) characteristics of the single-layer device fabricated

with VOPcPhO as an active layer in dark and under illumination are measured using
Keithley source meter. The J-V relationship of the ITO/PEDOT:PSS/VOPcPhO/Al device
in dark are shown in Figure 5.8. The J-V characteristics taken at room temperature are
non-linear and asymmetric, revealing the rectification effect. The rectification ratio at
±0.5V has been calculated and is around 3.12. The rectifying phenomenon can be
assigned to the significant charge injection from the ITO electrode to the PEDOT:PSS
and VOPcPhO active layer.

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Chapter 5 VOPcPhO-Thin-film based devices

Figure 5.8. Current-voltage characteristics of VOPc-based single-layer device in dark

and under illumination.

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Chapter 5 VOPcPhO-Thin-film based devices

The J-V characteristics of the organic solar cell based on VOPcPhO under illumination
are also shown in Figure 5.8. The device characterization was carried out under
simulated 100mW/cm2 AM 1.5 white light illumination. The performance parameters for
the cell have been extracted. The short circuit current (JSC) and open circuit voltage
(VOC) for the single layer VOPcPhO-based solar cell were measured as 5.26 x 10-6
A/cm2 and 0.62121V, respectively. The fill factor FF was obtained as 0.33. The power
conversion efficiency of the organic solar cell is calculated and it turned out to be equal
to 1.08 x 10-3 %.

The power conversion efficiency for the single-layer device fabricated using the
VOPcPhO, however, is low compared to the other organic solar cells reported in the
literature. The reasons for the lower efficiency may also be low carrier mobility, poor
interface morphology and lack of optimization of fabrication procedure.

In order to meet the growing energy requirements, it is essential to explore the materials
which are convenient to be used in the fabrication of the solar devices. The use of
VOPcPhO for photovoltaic applications is particularly attractive due to its high solubility
in a variety of organic solvents. The photovoltaic response, demonstrated for single-
layer organic solar device with the VOPcPhO, has shown the potential of this material to
play an important role in fabricating simple, easy and inexpensive devices.

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Chapter 5 VOPcPhO-Thin-film based devices

The I-V characteristics of a single-layer solar, in semi-log scale at room temperature,

are presented in Figure 5.9. It is presumed that the forward bias current results due to
thermionic emission current when a metal is brought in contact with a semiconductor

Figure 5.9. Current-Voltage characteristics of VOPc–based solar cell in semi log

scale.

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Chapter 5 VOPcPhO-Thin-film based devices

And it is given as [62, 63].

5.8

The reverse saturation current Io is given by the equation given below:

5.9

where Øb0 is the barrier height at zero bias, V is the forward bias voltage, k is the
Boltzman constant, T is the temperature in Kelvin, A* is the effective Richardson
constant and is equal to 10-2 A/cm2 K2 for semiconductor [64]. A is the active area of the
diode, n is the ideality factor, which can be obtained by taking a slope of the straight line
region in the semi-log I-V characteristics of the device. The saturation current was
determined from the semi-log plot of Figure 5.9 and was found equal to 0.3 nA. The
ideality factor n is defined as:

5.10

The barrier height Øb0 can be determined by the following expression:

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Chapter 5 VOPcPhO-Thin-film based devices

5.11

The current–voltage characteristics are extremely useful to provide important

information about the junction properties such as ideality factor, reverse saturation
current, zero bias barrier height and specially transport mechanism responsible for
conduction. The ideality factor ‘n’ and the barrier height at zero bias ‘Ø b0’ are determined
from the y-axis intercept and the slope of the linear region of the semi-log plot of the
experimental I-V characteristics data in the forward bias region. The values of n and Ø b0
were found to be 2.69 and 0.416 eV. In our case, the ideality factor, which should be
closer to unity, deviates from the ideal value. The n value beyond ‘2’ is highly suggestive
of the fact that the prevalent current in single layer photovoltaic device is due to
recombination [65].

The series resistance (Rs) and shunt resistance (Rsh) are determined from the graph of
the junction resistance (R) versus voltage (V) shown in Figure 5.10. The values of Rs
and Rsh obtained from the plot of Figure 5.10 are 930 KΩ and 49 MΩ, respectively.

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Chapter 5 VOPcPhO-Thin-film based devices

Figure 5.10. The junction resistance versus applied voltage for single layer solar cell.

The detailed information about the conduction processes through the VOPcPhO active
layer has been extracted from the analysis of forward bias I-V characteristics presented
in the double log scale in Figure 5.11. The plot exhibits three discrete regions of slope.
For low voltages, the slope of region I in Figure 5.11 equals 1, which specifies that the
governing charge transport mechanism in this region is ohmic conduction. The space
charge limited current SCLC with discrete trapping level appears to be quite dominant in
the second region (region II) as the value of the slope in this region is 1.7. The slope

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Chapter 5 VOPcPhO-Thin-film based devices

equal to 3 in region III, corresponds to the dominance of trapped-charge-limited current

TCLC in the device.

Figure 5.11. Current–Voltage characteristics of the solar cell in Log (I)–Log (V)
representation.

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Chapter 5 VOPcPhO-Thin-film based devices

Another method to determine the barrier height is the Norde’s method [66]. The Norde’s
function is given as:

5.12

where is a dimensionless quantity having a first integral value greater than ‘n’. The

value of in this case is ‘3’. A graph of and , shown in Figure 5.12 , is plotted to
obtain the minima on x and y axes. The barrier height can be calculated by the following
expression:

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Chapter 5 VOPcPhO-Thin-film based devices

Figure 5.12. F(V) versus voltage plot of VOPcPhO based cell.

5.13

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Chapter 5 VOPcPhO-Thin-film based devices

where is the minimum voltage and is the corresponding minimum value of

. The barrier height calculated by Norde’s method is 0.39 eV, which is in

agreement with the value obtained by conventional I-V method.

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Chapter 5 VOPcPhO-Thin-film based devices

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Chapter 6______________________________________Conclusions and Future Work

6 Conclusions and Future Work

6.1 Conclusions

It has been observed from the optical studies that VOPcPhO possesses two bands B-
band and Q-band in the spectral region like many other MPcs. The stand-alone thin film
of VOPcPhO were used for XRD characterization and the films are found to be
amorphous. The optical examination of VOPcPhO dissolved in chloroform and spin
coated on glass substrates showed that the material is sensitive to light in the UV region
between 290 nm and 344 nm as well as in the visible spectrum within the range of 665
nm and 710 nm.

The films of undoped VOPcPhO and VOPcPhO doped with PCBM for three different
concentrations 25, 50 and 75 % have been fabricated on commercially available glass
slides by spin coating process. The absorption spectrum has been employed to
determine the energy gap for doped and undoped samples. The spectroscopic studies
reveal that the energy gap decreases from 3.32 eV to 3.26 eV with increasing doping
levels. The red shift appears in the absorption spectrum which can be attributed to the
reduction in optical band gap.

The optical properties, surface morphology and structure of solution processed

VOPcPhO thin films are significantly influenced by the port-deposition thermal annealing
process. With an increase in annealing temperature, the absorption intensities in both
the regions (UV and visible) of the film annealed at 125 oC has increased, due to the
increased number of absorption sites, as compared to the as-cast film. However,

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increasing the temperature beyond 155 oC has disrupted the film formation, thereby
reducing the light absorption. It has been observed from the topographic images
obtained by AFM that the annealing process considerably enhances the rms roughness
and the grain size of the VOPcPhO film at annealing temperatures approaching 125 oC.
It can be concluded that by conducting this simple thermal annealing process, the
features of light absorption and surface morphology of the films can be improved. This
study may find suitability of VOPcPhO for developing low cost organic solar cells or
photodiodes, where such features play a key role in the device performance.

Surface-type Ag/VOPcPhO/Ag capacitive humidity sensors have also been successfully

fabricated. The investigation made on the samples of different thicknesses leads to the
fact that the capacitance of the sensors increase with rise in humidity levels. In general,
such capacitance response is attributed to polarization due to adsorption of water
molecules and transfer of charge carriers. The performance of Ag/VOPcPhO/Ag sensor
has been found to be dependent on the thickness of VOPcPhO film. Experimental
results showed that the lesser the thickness the higher the sensitivity. The highest
capacitance response was observed for the 50 nm VOPcPhO thick film. It is also
observed from the I-V curves that at any certain voltages the current increases with an
increase in humidity level. This may be attributed to an increase in the conductivity of
the film with increasing humidity level. The considerable features of the surface-type
humidity sensors are the economical cost, simplicity and ease of fabrication. It may be
possible to exploit the high sensitivity and better stability of the sensor in commercial
applications.

In the present work, the effect of the humid environment on a co-planar humidity sensor
based on VOPcPhO thin film coated on asymmetric electrodes has also been
investigated. Prior to deposition two asymmetric metal-electrodes (aluminum and
platinum) have been successfully grown on the glass substrate by photolithography

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technique in the co-planar structure with a gap of 17 um. It is found that the capacitance
increases while the resistance decreases with increasing level of relative humidity. The
increase in the capacitance can be attributed to the enhanced dielectric constant of the
active layer due to water vapors adsorbed. On the other hand the resistance is greatly
affected by the change in the dipole moment due dissociation of water molecules
adsorbed on the surface. The humidity sensor presented here shows enough sensitivity,
good selectivity, linearity and reasonable response and recovery times.

The electrical properties of ITO/PEDOT:PSS/VOPcPhO/Al solar cell device were

investigated in dark and under illumination. The rectification behavior has been
observed for the device in the dark. The device showed photovoltaic effect. The open
circuit voltage, short circuit current density and fill factor were found to be equal to 5.26
x 10-6 A/cm2, 0.62121 V and 0.33, respectively. The electronic parameters of the cell
from I-V characteristics in dark have also been extracted by using conventional forward
bias I–V method and Norde’s method. The calculated values of the ideality factor and
barrier height were 2.69 and 0.416 eV, respectively.

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6.2 Future Work

The investigations carried out in this dissertation can provide fundamental

understanding of VOPcPhO, which can be employed to further improve the film quality
and enhance the device performance. In this regard some of the future work has been
suggested:

1. Usually, absorption spectroscopy is considered the most reliable and

comprehensive methods to obtain the useful information required to optical
properties of the material. The spectrum of the VOPcPhO can be broadened by
the addition of fullerene derivatives and thiophenes such as PCBM and P3HT.

2. The gap between the electrodes of the co-planar structure of humidity sensors
play key role in the sensitivity of the sensor. To increase the sensitivity, the
humidity sensors with nano-scale gap between the electrodes can be developed.

3. The efficiency may be improved by introducing a donor material to form bulk

heterojunction solar cell in the future studies. A bi-layer and bulk heterojunction
solar cells based on VOPcPhO, PCBM and P3HT can be prepared.

155