Electronic and Optoelectronic Studies of

Organic Semiconductors
By
Dil Nawaz Khan

Supervised By
Prof. Dr. Muhammad Hassan Sayyad
A dissertation submitted to GIK Institute, in partial fulfilment of
Doctor of Philosophy in Engineering Sciences (Applied Physics)
(2014)
Faculty of Engineering Sciences

Ghulam Ishaq Khan Institute of Engineering Sciences & Technology

Topi, District Swabi, Khyber Pukhtoonkhwa, Pakistan

ii

Dedication
This dissertation is dedicated to:
my latE ParENtS,
Who always wanted me to acquire higher Education.
my wIfE ShaKIla Nawaz,
For her continued support and encouragement during my research.
&
my KIdS EShNa, maham aNd muhammad Ibadullah KhaN,
Their innocent smiles always gave me the courage to complete this
work.

iii

Acknowledgements
I thank Almighty Allah for giving me ability, courage, determination and guidance in
conducting this research work, despite all difficulties.
My tenure in the Faculty of Engineering Sciences, GIK Institute since 2007 as
graduate student has been enriched by the help of many people. Here I would like to take
this opportunity to thank the people who have in no small way made the research in this
dissertation possible.
First and foremost, I would like to gratefully and sincerely thank my supervisor
Prof. Dr. Muhammad Hassan Sayyad for his patience, understanding, guidance,
encouragement and advice during my graduate studies at the GIK Institute. His
mentorship was paramount in providing a well rounded experience consistent my longterm career goals. He encouraged me not only to grow as an experimentalist and a
Physicist but also as an instructor and an independent thinker. He always gave me the
courage to work and decide individuality and independently.
I would like to express my deep gratitude and respect to Prof. Dr. Jameel Un Nabi
(Dean FES) and Prof. Dr. S. Ikram A. Tirmizi (Ex. Dean FES) for their continued support
and encouragement 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.

It is an honor for me to acknowledge Prof. Dr. Dmitrii F. Perepichka, McGill
University, Montreal Canada for giving me the chance to learn under his supervision by
granting access to his labs and equipment. This dissertation would not have been possible
without his guidance and encouragement.
I am also thankful to all faculty members of FES and other staff for their
cooperation during my stay in GIK Institute.

iv

I would like to show my special gratitude to Fazal Wahab for lending his precious
time and extended co-operation in the lab and hostel.
I am forever indebted to my wife Shakila Nawaz for her understanding,
continuous support, encouragement, and endless patience during our whole life and
especially in the past 6 years of my studies. I am deeply grateful to my kids Eshna
Nawaz, Maham Nawaz and Muhammad Ibadullah Khan. They have lost a lot due to my
busy life during my research. I would like to thank my family members especially to my
brothers Akhtar Nawaz Khan and Arshad Nawaz Khan for their cooperation, support and
advice throughout my studies.
I am also thankful to Dr. Muhammad Yaseen, Dr. Munawar Ali Munawar, Dr. Mukhtar
Ali, Matthew Morantz and Dr. Q. Shuai (Steven) for synthesising the organic materials
which were used in this research work.
I am indebted to many of my colleagues and friends Dr. Muhammad Saleem, Dr.
Mutabar Shah, Dr. Zubair Ahmad, Dr. Shahid Mehmood Khan, Dr. Fakhra Aziz, Mr.
Muhammad Tahir and Mr. Aamir Ellahi for helping me to complete this dissertation. It
is a pleasure to thank Dr. Afshin Dadvand, Dr. Andrey Moiseev, Dr. Iryna Perepichka,
Mohini Ramkaran and Batrice Lego who made my research work possible at the
Chemistry Department, Otto Maas Building, McGill. I am also grateful to my apartment
fellows in Canada Yensy Oritz and David for facilitating me during my stay in Montreal.
I also want to acknowledge Prof. Ayub Awan, Prof. Munsif Khan, Prof. Ghulam
Rasool and Prof. Akhtar Pervaz, Prof. Muhammad Sajjad Khan (Principal GPGC
Abbottabad) for their encouragements and support during my graduate study.
The last but not least, I would like to acknowledge Higher Education Commission
of Pakistan (HEC) for providing me financial support through the 5000 Indigenous PhD
Fellowship Program and International Research Support Initiative program (IRSIP), and
Higher Education Department, Khyber Pakhtunkhwa for granting me study leave for this
period.
Dil Nawaz Khan

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
publications as follows:
Reviewed Journal papers:
1. Dil Nawaz Khan, Muhammad Hassan Sayyad, Fazal Wahab, Muhammad Tahir,
Muhammad Yaseen, Munawar Ali Munawar, Mukhtar Ali Temperature
dependant electrical properties of formyl-TIPPCu(II)/p-Si heterojunction diode
Modern Physics Letters B 28 (2014) 1450100 DOI:10.1142/S0217984914501000.
2. Dil Nawaz Khan, Muhammad Hassan Sayyad, Muhammad Tahir, Fazal Wahab
Muhammad Yaseen, Mukhtar Ali, Munawar Ali Munawar The sensing of
Humidity by surface type Ag/Formyl-TIPPCu(II)/Ag sensor for Environmental
Monitoring Surface Review and Letters 21 (2014) 1450048 DOI :
10.1142/S0218625X14500486.
3. Dil Nawaz Khan, Dmitrii F. Perepichka, Matthew Morantz, Qi Shuai
Muhammad Hassan Sayyad Study of Anthracenediimide Derivatives for nchannel Organic thin film transistors (Draft in preparation)

Conference papers
1. Dil Nawaz Khan, Muhammad Hassan Sayyad, Muhammad Yaseen, Munawar
Ali Munawar, Mukhtar Ali Application of Formyl-TIPPCu (II) for Temperature
and Light Sensing World Academy of Science, Engineering and Technology
51(2011) 210-212.

Dil Nawaz Khan

vi

Abstract
Organic semiconductors have made inroad into many area of devices which was
formally dominated by inorganic semiconductors because of their wide variety of
electronic and optoelectronic properties. They being low cost, light weight and low
temperature processing materials provide opportunities to fabricate the variety of devices,
such as, solar cells, field effect transistors, lasers, light emitting diodes, sensors, photo
detectors, smart windows, large area displays, e-paper, etc. The material manipulation,
low cost fabrication techniques and the emerging ideas are bringing about much
improved performances in the organic electronic devices. Most of the earlier studies have
been reported on the p-type organic semiconductors and little is known about n-types. In
the development of future organic electronic industry, all organic complementary circuits
are not possible without the availability of both p- and n-type organic semiconductors and
data is required on the junction properties and mobility studies of these materials. Plenty
of data is available on the junction diodes of p-type organic semiconductors but little is
known on the n-type organic semiconductors based junction devices and mobility
investigations. In this dissertation, the n-type organic semiconducting materials formylTIPPCu(II), N,N-di-n-heptyl-2,3:6,7-anthracenetetracarboxydiimide (ADCI7) and N,Ndi-n-octyl 2,3,6,7 anthracenetetracarboxydiimide (ADCI8) have been investigated as
active organic materials for their potential application in organic electronic devices.
Using organic semiconductor formyl-TIPPCu(II), junction diode, temperature, light and
humidity sensors have been fabricated, while ADCI7 and ADCI8 have been used for the
fabrication of n-channel organic thin film transistors.
To investigate junction properties of formyl-TIPPCu(II) organic semiconductor,
fabrication of Ag/formyl-TIPPCu(II)/p-Si heterojunction diode was undertaken and it
was made successfully. Its temperature dependent electrical properties are reported. The
values of series resistance, ideality factor, zero bias barrier height are observed strongly
dependent on temperature. The series resistance and ideality factor decease while the zero
bias barrier height increases with the rise in temperature.

vii

The surface type Ag/formyl-TIPPCu(II)/Ag humidity sensors has been fabricated

to study the effects of changing relative humidity on the electrical parameters and their
frequency dependant responses. The values of capacitance and resistance of the sensors
were measured at different humidity levels at frequencies of 1 kHz, 10 kHz and 100 kHz.
An increase in capacitance and decrease in resistance were observed during the rise of
relative humidity from 45 to 95% RH. The hysteresis response of these humidity sensors
was also studied at the frequency of 1 kHz.
Effects of temperature and light are studied on the capacitance and resistance of
the Au/formyl-TIPPCu(II)/Au device. The relative capacitance of the fabricated sensor
increased by 4.3 times by rising temperature from 27 to 1870C, while under illumination
up to 25000 lx, the capacitance of the Au/formyl-TIPPCu(II)/Au photo capacitive sensor
increased by 13.2 times as compared to dark conditions.
ADCI7 and ADCI8 were used to fabricate n-channel organic thin film transistors
(OTFTs) on oxidized silicon wafers. To get the high performance of the devices and to
avoid the trapping of charge carriers, the dielectric surface were modified by developing
the buffer layer of PMMA or by self assembly monolayer (SAM) of HMDS. The OTFTs
exhibited high charge mobility of the order of 10-2 cm2V-1S-1 (ADCI7) and 10-3 cm2V-1S1

(ADCI8) with the on/off ratio of the order of 104 showing the appreciable enhancement

in the field effect properties of these materials as compared to the previously reported
researches for the same family of materials. ADCI7 is introduced as new compound for
high mobility n-channel OTFTs.

viii

Table of Contents
Dedication .......................................................................................................................... iii
Acknowledgements ............................................................................................................ iv
Declaration ......................................................................................................................... vi
Abstract ............................................................................................................................. vii
List of Tables .................................................................................................................... xv
List of abbreviations ........................................................................................................ xvi

Chapter 1 ............................................................................................................................ 1
1.1

Introduction .......................................................................................................... 1

1.2

Motivation ............................................................................................................ 3

1.3

Objectives ............................................................................................................. 5

1.4

Outline of Dissertation ......................................................................................... 6

1.5

References ............................................................................................................ 8

Chapter 2 .......................................................................................................................... 11
Theory and Literature Review .......................................................................................... 11
2.1 Chemistry of Organic Semiconductors ................................................................... 12
2.2

Mechanism of Charge transport in organic materials ........................................ 13

2.2.1

Organic Thin Film Transistors ................................................................... 14

2.2.2

Factors limiting the mobility in OFETs ...................................................... 16

2.3 Operation of the organic transistors ........................................................................ 17

2.3.1

Threshold voltage........................................................................................ 19

2.3.2

On/Off ratio ................................................................................................. 19

2.3.3

Contact resistances ...................................................................................... 20

2.4

References .......................................................................................................... 21

Chapter 3 ........................................................................................................................... 23
Materials and Experimental Procedures ........................................................................... 23
3.1 Organic Materials.................................................................................................... 23
3.1.1 formyl-TIPPCu(II) ........................................................................................... 23
3.1.2

N,N-di-n-octyl-2,3:6,7-anthracenetetracarboxydiimide (ADCI8)............. 23

3.1.3 N,N-di-n-heptyl-2,3:6,7-anthracenetetracarboxydiimide (ADCI7)................ 24

3.1.4 Poly(methyl methacrylate) (PMMA) ............................................................... 24
ix

3.1.5 Hexamethyldisilazane (HMDS) ....................................................................... 25

3.2 Fabrication Techniques ........................................................................................... 26
3.2.1 Substrate Cleaning ........................................................................................... 26
3.2.2 Thin Films Depositions .................................................................................... 29
3.3

Atomic Force Microscopy.................................................................................. 33

3.4

Device Characterization Techniques .................................................................. 35

3.4.1

Electrical Characterization .......................................................................... 35

3.4.2

Current- Voltage (I-V) Characterization ..................................................... 36

3.5 Humidity dependent Characterization .................................................................... 37

3.6 Light and Temperature Dependence Measurements............................................... 38
3.7

References .......................................................................................................... 39

Chapter 4 .......................................................................................................................... 39
Temperature Dependant Electrical Properties of formyl-TIPPCu(II)/p-Si Heterojunction
Diode ................................................................................................................................. 40
4.1

Introduction ........................................................................................................ 40

4.2

Device Fabrication ............................................................................................. 41

4.3

Results and discussion........................................................................................ 42

4.4

Conclusions ........................................................................................................ 49

4.5

References .......................................................................................................... 49

Chapter 5 ........................................................................................................................... 52
The sensing of Humidity by surface type Ag/formyl-TIPPCu(II)/Ag sensor for
Environmental Monitoring................................................................................................ 52
5.1

Introduction ........................................................................................................ 52

5.2

Experimental ...................................................................................................... 54

5.3

Results and discussion........................................................................................ 55

5.3.1

Atomic Force Microscopy .......................................................................... 55

5.3.2

Capacitance Humidity Characteristics ........................................................ 56

5.3.3

Capacitance Frequency Characteristics ...................................................... 57

5.3.4 Resistance Humidity Characteristics ............................................................... 59

5.4
5.5

Conclusion ...................................................................................................... 60
References .......................................................................................................... 61

Chapter 6 ........................................................................................................................... 64
Application of formyl-TIPPCu(II) for temperature and light sensing .............................. 64
6.1 Introduction ............................................................................................................. 64
6.2

Experimental ...................................................................................................... 65
x

6.3

Results and Discussion ....................................................................................... 65

6.4

Conclusions ........................................................................................................ 68

6.5

References .......................................................................................................... 69

Chapter 7 ........................................................................................................................... 71
Study of Anthracenediimide Derivatives for n-channel Organic thin film transistors ..... 71
7.1 Introduction ............................................................................................................. 71
7.2 Device Fabrication & Characterization .................................................................. 72
7.3 Thin-lm X-ray diffraction ..................................................................................... 73
7.4 Thin film morphology ............................................................................................. 74
7.5 Thin-lm transistor device characterization ........................................................... 76
7.6 Conclusion .............................................................................................................. 79
7.7

References .......................................................................................................... 79

Summary ....................................................................................................................... 82
Future Work .................................................................................................................. 83

xi

List of Figures
Fig. 1. 1: A broad range of electronic products for daily life use ....................................... 1
Fig. 1. 2: Bardeen and Walter first point contact transistor [7]. ......................................... 2
Fig. 2. 1: Comparison of conductivity of organic semiconductors. .................................. 11
Fig. 2. 2: Scheme of the orbitals of two sp2 hybridized carbon atoms ............................. 13
Fig. 2. 3: Schematic structures of bottom-gate OFETs: top-contact (left) and bottomcontact (right) .................................................................................................................... 15
Fig. 2. 4 Schematic drawings of top-gate OTFTs: top-gate/top-contact (left) and topgate/bottom-contact (right) ............................................................................................... 16
Fig. 2. 5 Transfer (a) and output (b) characteristics of PDIF-CN2 TFT[12] .................... 18
Fig.3. 1 Chemical structure of formyl-TIPPCu(II). .......................................................... 23
Fig.3. 2 The Molecular structure of ADCI8 ..................................................................... 24
Fig.3. 3 The synthesis procedure and chemical structure of ADCI7 ................................ 24
Fig.3. 4 Molecular structure of PMMA ............................................................................ 25
Fig.3. 5 Chemical structure of HMDS. ............................................................................. 25
Fig.3. 6 Chemical Hood for cleaning substrates ............................................................... 28
Fig.3. 7 Plasma cleaner PDC-32G .................................................................................... 28
Fig.3. 8 Inner view of PLASMIONIQUE EVD-400H thermal evaporating system ........ 30
Fig.3. 9 Sample Hoder in PLASMIONIQUE EVD-400H thermal evaporating system
(design by me)................................................................................................................... 30
Fig.3. 10 Edward Auto 306 vacuum thermal evaporator with thickness Monitor ............ 31
Fig.3. 11 PLASMIONIQUE EVD-400H thermal evaporating system............................. 32
Fig.3. 12 Schematic diagram of spin coating technique. .................................................. 33
Fig.3. 13 Spin coater Model WS-400B-6NPP/LITE ........................................................ 33
Fig.3. 14 Schematic diagram of AFM. ............................................................................. 34
Fig.3. 15 MM Multimode 8 AFM setup ........................................................................... 35
Fig.3. 16 Probe Station(KARL SUSS PM5) with keithley-196 System Digital
Multimeter and keithley-228A I-V source ....................................................................... 36
Fig.3. 17 Keithley 4200-SCS for characterization of OTFTs ........................................... 36
xii

Fig.3. 18 Inner view of Keithley 4200-SCS ..................................................................... 37

Fig.3. 19 Schematic of experimental setup for humidity characterization ....................... 37
Fig.3. 20 Schematic of experimental setup to study the effect of light ............................ 38
Fig.3. 21 Experimental setup to study the effects of temperature .................................... 39
Fig. 4. 1UV-Visible Spectrum of formyl-TIPPCu(II) ...................................................... 41
Fig. 4. 2 Mass Spectrum of Formyl-TIPPCu(II) ............................................................... 42
Fig. 4. 3 Cross-sectional view of Ag/formyl-TIPPCu(II)/p-Si diode. .............................. 42
Fig. 4. 4 I-V characteristics of formyl-TIPPCu(II)/p-Si diode at 299-339K. ................... 43
Fig. 4. 5 Semi-logarithmic (IV) characteristics of formyl-TIPPCu(II)/p-Si diode at
different temperatures. ...................................................................................................... 44
Fig. 4. 6 Reverse saturation current of formyl-TIPPCu(II)/p-Si diode at different
temperature. ...................................................................................................................... 45
Fig. 4. 7 Arrhenius plot of saturation current vs 1000/T for formyl-TIPPCu(II)/p-Si diode
........................................................................................................................................... 45
Fig. 4. 8 Forward bias semi-logarithmic plots of current-voltage characteristics of formylTIPPCu(II)/p-Si diode indicating the voltage drop V=IRs across the neutral region. ... 46
Fig. 4. 9 Series resistance-Temperature graph of fomyl-TIPPCu(II) diode. .................... 47
Fig. 4. 10 F(V) vs V plot of formyl-TIPPCu(II)/p-Si diode ............................................. 48
Fig. 4. 11 Variation of Zero bias barrier height and ideality factor of formylTIPPCu(II)/p-Si diode with temperature from 299-339K. ............................................... 49
Fig. 5. 1The cross-sectional view of surface type Ag/formyl-TIPPCu(II)/Ag humidity
sensor ................................................................................................................................ 54
Fig.5. 2AFM image of formyl-TIPPCu(II) on glass substrate. ......................................... 55
Fig.5. 33D AFM image of thin film of formyl-TIPPCu(II). ............................................. 56
Fig.5. 4Capacitance-relative humidity relationship of the Ag/formyl-TIPPCu(II)/Ag .... 56
Fig.5. 5Capacitance-frequency relationship of the Ag/formyl-TIPPCu(II)/Ag sensor at
65%, 75%, 85% and 95%RH. ........................................................................................... 58
Fig.5. 6Hysteresis-relative humidity relationship for Ag/formyl-TIPPCu(II)/Ag. ........... 59
Fig.5. 7Resistance-relative humidity relationship of Ag/formyl-TIPPCu(II)/Ag sensor at
1kHz and 10kHz. .............................................................................................................. 60
Fig.6. 1Cross-sectional view of the Au/formyl-TIPPCu(II)/Au organic sensor. .............. 65
xiii

Fig.6. 2Capacitance/resistance temperature relationships for the Au/formylTIPPCu(II)/Au organic sensor. ......................................................................................... 66
Fig.6. 3Hysteresis in the capacitive and resistive measurements of Au/formylTIPPCu(II)/Au organic sensor. ......................................................................................... 67
Fig.6. 4 Capacitance- illumination relationship for the Au/formyl-TIPPCu(II)/Au organic
sensor. ............................................................................................................................... 68
Fig. 7. 1 Schematic diagram of bottom gate/top contact n-channel OTFT of ADCI7 ..... 73
Fig. 7. 2 X-ray diffraction measurements of thin films of ADCI7 and ADCI8................ 74
Fig. 7. 3 AFM micrographs and the histogram of the height profile of thin films of ADI7
........................................................................................................................................... 75
Fig. 7. 4 AFM micrographs and the histogram of the height profile of thin films of
ADCI8 ............................................................................................................................... 75
Fig. 7. 5 Output characteristics of ADCI8 ........................................................................ 77
Fig. 7. 6 Transfer characteristics of ADCI8 ...................................................................... 78
Fig. 7. 7 Output characteristics of ADCI7 ........................................................................ 78
Fig. 7. 8 Transfer characteristics of ADCI7 ...................................................................... 79

xiv

List of Tables
Table 7.1 Comparison of electrical properties of ADCI7 and ADCI8

81

xv

List of abbreviations
ADCI7

N,N-di-n-heptyl-2,3:6,7-anthracenetetracarboxydiimide

ADCI8

N,N-di-n-octyl 2,3:6,7 anthracenetetracarboxydiimide

CP

Conjugated Polymer

CuTIPP

Cu(II) 5,10,15,20-tetrakis(4-isopropylphenyl) porphyrin

DI

De-ionized water

DOS

Density of states

EL

Electroluminescence

FET

Field effect transistor

FTM

Film Thickness Monitor

HMDS

Hexamethyldisilazane

HOMO

Highest occupied molecular orbital

ID

Identification

ITO

Indium tin oxide

I-V

Current-Voltage

LCDs

Liquid crystal displays

LCP

Liquid crystal polymer

LED

Light-emitting-diode

LEP

Light-emitting- polymer

LUMO

Lowest unoccupied molecular orbital

OFETs

Organic field-effect transistors

OLEDs

Organic light-emitting diodes

OP-TFTs

Organic polymer thin film transistors

xvi

OSCs

Organic semiconductors

OTFTs

Organic thin film transistors

PL

Photoluminescence

PMMA

Poly(methyl methacrylate)

RFT

Radio frequency tags

RH

Relative humidity

rpm

Revolution per minute

SAM

Self Assembly Monolayer

SCLC

Space-Charge-Limited Current

TCLC

Trapped Charge Limited Current

TIPP

5,10,15,20-tetrakis(4-isopropylphenyl) porphyrin

TOF

Time-of-flight

TPP

5,10,15,20-tetraphenylporphyrin

TSC

Thermally Stimulated Current

TSCLC

Trapping model with space charge limited current

TSL

Thermally stimulated luminescence

UPS

Ultraviolet photoemission spectroscopy

VETP

Vinyl-ethynyl-trimethyl-piperidole

XPS

X-ray photoelectron spectroscopy

XRD

X-ray diffraction

ZnTPP

5,10,15,20-tetraphenylporphyrin

ZnTIPP

Zn(II) 5,10,15,20-tetrakis(4-isopropylphenyl) porphyrin

xvii

Chapter 1
1.1 Introduction
In our daily life, we are enjoying with well-developed electronics. Nowadays, no
one can feel alone, colourful mobile phones and laptop keeping connection with family
and friends. Twenty first century brought technological advances in electronic industry
which have not only improved peoples lives in countless ways but also spurred
economic growth. Electronics products have become essential for our lives. Fig. 1.1
depicts a number of application domains of electronic technology in daily life.

Fig. 1. 1: A broad range of electronic products for daily life use

The stream of inventions in electronics was started in early 20th century. Before
this era, there was a little or almost no electronics in the day to day life of a common
man. The explanation of thunder and lighting by Franklin in 18th century is considered as
the beginning of electronics. Franklins idea was really a big mystery of that time; he
introduced the idea of charge flow and its consequences in the materials [1]. The idea of
resistance and conductance was introduced by George Simon Ohm which is helpful in
categorization of the materials [2].

The invention of thermionic diode by Ambrose Fleming signified the birth of

electronic devices.

It was initially used for rectification purposes and then for the

detection of weak signal produced by wireless telegraph [3]. Lee de Forest developed
amplifier vacuum tube triode by introducing a grid between the cathode and anode. Grid
acts as modulator of the electrons so it either stops them or makes them faster causing
current amplification. The triode played important role in the early growth of
communication systems by enabling long distance telephony and amplified radio
technology [4].
The electronic devices which were in daily use in early 20th century were based
on vacuum diodes and triode which were facing problems like high power consumption,
low reliability and needed cooling arrangements.

To overcome these problems, the

scientists tried alternatives of vacuum tubes; they turned their researches on solid state
devices. The tremendous development of PN junction diode by Russell Ohl opened new
era of research in the field of solid state electronic devices [5]. The discovery of transistor
effect by three American Physicists i.e. John Bardeen, William Shockley and Walter
Brattain opened the road of real electronics [6]. The photograph of first contact transistor
is shown in Fig. 1.2.

Fig. 1. 2: Bardeen and Walter first point contact transistor [7].

Historically, the study of conductivity in organic materials resulted the discovery

of photoconduction of solid anthracene in 1906, but then no appreciable research was
observed in next four decades. The discovery of conducting polymers in 1976 by Heeger,
Macdiarmid and Shirakawa opened the new ways of research in the field of organic
electronics [8, 9]. Inorganic semiconductors with wide range of applications in electronic
devices have some limitations due to their rigid crystalline nature. They need highly pure
materials and high temperature processing techniques so they are much expensive. To
overcome these limitations, the organic semiconductors have provided the alternative
opportunities to fabricate simple, inexpensive light weight, and flexible electronic
devices.

1.2 Motivation
The motivation of using organic semiconductors for the fabrication of electronic
devices arose from their structural flexibility and tunable electronics properties, cost
effectiveness, compatibility with roll to roll processing, easy and low temperature
fabrications, printable, flexible and large area applications due to their mechanically
flexibility and active matrix display backplanes [10, 11, 12], thus they have appealed for
a broad range of devices including junction diodes, sensors, transistors, light emitting
diodes, solar cells, memories, etc. The tunable charge mobility is another importance
property of organic semiconductors for the fabrication of more efficient organic field
effect transistors, solar cells and light emitting diodes [13, 14, 15, 16].
Most of the organic semiconductors can be processed easily at room temperature
in contrast to traditional silicon materials which need very high temperature of about
10000C. This can reduce the mismatches due to thermal expansion and allows OSCs
processing for larger area applications. The compatibility of OSCs with flexible
substrates due to their mechanical properties make them suitable for electronic paper,
smart windows, portable sensors, flat panel displays and RFID tags [17, 18]. Generally
the fabrication techniques for organic semiconductor devices are less complex and do not
require sophisticated photolithographic methods and high vacuum deposition processes
which make them less expensive as compare to traditional electronic technologies.

In earlier researches, the organic materials were not considered as reliable because
of their poor conductivity and fragility. These limitations of the organic semiconductors
can be significantly improved by their chemical and structural modification. The
performance of organic devices mostly depends on the surface morphology of the thin
films of molecular or polymeric semiconductors. Molecular orientation and packing can
be controlled by using post deposition processing [19].
By adding different functional groups, a variety of OSCs can synthesised and
tailored to tune their electronic and optoelectronic properties for different specific
applications. Currently the researchers are capable to control the material properties at
molecular level. The electronic properties of OSCs can also be enhanced by either their
doping or by making their composites with nanomaterials. Nanocomposite based organic
junction shows lower value of turn on voltage, ideality factor and reverse saturation
current while rise in charge carrier concentrations [20, 21].
Organic electronic is not only consumer electronics but it is also environmental
friendly technology which provides the best opportunity for renewable energy conversion
from the sun which is the most plentiful energy source. Earth receives solar energy at the
rate of 120 peta watts (1peta= 1015 watts), so the energy falling from the sun on earth in
one hour is sufficient for more than 20 years for the worldwide demands. The high
efficiency photovoltaic systems are mostly based on traditional inorganic materials, they
help to overcome the energy crises but they are not only much expensive but they may
also be harmful for the environment due the poisonous nature of the materials [22]. On
the other hand, the organic photovoltaics are low cost, lightweight, flexible and
environmental friendly [23].
Organic Field Effect transistors (OFETs) have gained great interest as a key
element for all organic electronic applications of the organic circuits; they are used as
switching pixels on/off, for adjusting the brightness level in displays and also in organic
sensors and in RFID tags. OFETs have other interesting applications in biosensors,
vapour sensors (e-nose) and intelligent textile [24].
The sensitivity of OSCs at ambient conditions is another important property
which has been used for the fabrication of various types of sensors. The OSCs are used as

active materials for detecting the effects of light, temperature, humidity, pressure and
gasses. They show high chemical stability and low hysteresis.

1.3 Objectives
The organic junction diode is the elementary building block of most of the
electronic and optoelectronic devices like light emitting diodes, solar cells, and OTFTs.
The study of junctions of organic-organic or organic-inorganic materials not only gives
enough knowledge about the interfaces of these materials but also it provides the
opportunities to enhance the performance of organic devices.
The main objective of this dissertation is to study the electronic and optoelectronic
properties of different organic semiconductors in order to find their suitability for the
fabrication of the organic electronic devices. Studies are carried out on the metallo
porphyrin

2-formyl-5,10,15,20-tetrakis(4-isopropylpheny)prophyrinatocopper(II)

or

formyl-TIPPCu(II), N,N-di-n-heptyl-2,3:6,7-anthracenetetracarboxydiimide (ADCI7)

and N,N-di-n-octyl-2,3:6,7-anthracenetetracarboxydiimide (ADCI8).
In phase-1, the copper based porphyrin formyl-TIPPCu(II) is chosen to study its
junction with inorganic semiconductor p-type silicon. As the macrocyclic organic
compounds porphyrins with largely conjugated structure have been extensively studied
over the past decades because of their wide range of applications in different electronic
devices. Porphyrins being tetrapyrrole derivatives show their charge transfer and light
harvesting functions in the photosynthesis. They show high chemical stability and their
structures can easily be synthetically manipulated [25, 26]. The study of effects of
temperature on electrical properties of junction diode is also one of the important
purposes of this research.
Another focus of this research is to explore the sensing abilities of formylTIPPCu(II) to develop inexpensive, reliable and accurate light, temperature and humidity
sensors for environmental monitoring. The morphological study of this organic material
shows the enough porosity for capturing water droplets at different humidity levels and
proves its suitability for detecting humidity.
Keeping in mind the importance of organic complementary circuits, the important
aim of this research is to study the n-type organic semiconductors to fabricate n-channel
5

organic thin film transistors. Mostly organic semiconductors are p-type; naturally n-type
OSCs are very rare. Miller et al has reported the linear acenedicarboximide cores as
electrochemically n-dopable. Then in another research work, ADI8 based organic thin
film transistor was reported as air stable [27, 28]. Therefore, the most important objective
of this research is to investigate the n-channel OTFT of N,N-di-n-octyl-2,3:6,7anthracenetetracarboxydiimide (ADCI8) and then to study the stable field effect
properties of newly synthesized N,N-di-n-heptyl-2,3:6,7-anthracenetetracarboxydiimide
(ADCI7).

1.4 Outline of Dissertation

This dissertation consists of eight chapters, the details are as under:

Chapter 2
The chapter consists of literature review, theory and basic properties of
conjugated organic materials and their devices. The brief description of organic thin film
transistors are also the part of this chapter.
.

Chapter 3
This chapter focuses on the molecular structure and important properties of
organic materials (used in this research) i.e formyl-TIPPCu(II), ADCI7 and ADCI8. It
also contains the details of devices fabrication and characterization techniques.

Chapter 4
Temperature

dependant

electrical

properties

of

formyl-TIPPCu(II)/p-Si

heterojunction diode are discussed in this chapter. The discussion consists of the
fabrication and characterization of formyl-TIPPCu(II)/p-Si diode and the effect of
temperature on important diode parameters like series resistance, reverse saturation
current, ideality factor and barrier height.

Chapter 5
The sensing of Humidity by surface type Ag/Formyl-TIPPCu(II)/Ag sensor for
environmental monitoring is described in chapter 5. It contains the details of fabrication
and characterization of formyl-TIPPCu(II) based organic humidity sensors. The
capacitive and resistive response of the fabricated sensors along with the possible
hysteresis has been explained.

Chapter 6
This chapter constitutes the investigation of light and temperature sensors
employing formyl-TIPPCu(II) as active sensing material. It contains the procedures of
fabrication and characterization of surface type organic sensors

Chapter 7
Chapter 7 deals with the investigation of ADCI7 and ADCI8 based n-channel
organic thin film transistors. It encompasses the fabrication and characterization of the
OTFTs and also contains the study of the surface morphologies of thin films of ADCI7
and ADCI8.

Summary and Future work

At the end of the thesis, summary of this research work have been reported along
with the suggested future work.

1.5 References
[1] P. Benjamin, A History of Electricity, NY: Wiley, 1898.
[2] R. A. Millikan and E. S. Bishop, Elements of Electricity, American Technical
Society, 1917.
[3] J. A. Fleming, "Instrument for converting Alternating electric currents into continous
current". US Patent 803,684, 7 Nov 1905.
[4] L. d. Forest, "Space Telegraphy". US Patent 879532 A, 18 Feb 1908.
[5] R. S. Ohl, "Light-sensitive electric device". US Patent 2,402,662, 25 June 1946.
[6] J. Bardeen and W. Brattain, "Three-Electrode Circuit Element Utilizing
Semiconductor Materials". US Patent 2,524,035, 3 Oct 1950.
[7] "1947 - Invention of the Point-Contact Transistor," Computer History Museum,
[Online]. Available: http://www.computerhistory.org/semiconductor/timeline/1947invention.html.
[8] H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang and A. J. Heeger,
"Synthesis of electrically conducting organic polymers: Halogen derivatives of
polyacetylene," J. Chem. Soc. Chem. Commun, pp. 578-580, 1977.
[9] C. K. Chiang, C. R. Fincher, Y. W. Park, A. J. Heeger, H. Shirakawa, E. J. Louis, S.
C. Gau and A. G. MacDiarmid, "Electrical conductivity in doped polyacetylene,"
Phys. Rev. Lett, vol. 39, pp. 1098-1101, 1977.
[10] A. C. Arias, J. D. MacKenzie, I. McCulloch, J. Rivnay and A. Salleo, "Materials and
Applications for Large Area Electronics: Solution-Based Approaches," Chem. Rev,
vol. 110, pp. 3-24, 2010.
[11] L. M. Yang and R. Pushpa, "Tuning electronic and optical properties of a new class
of covalent organic frameworks," J. Mater. Chem. C, vol. 2, pp. 2404-2416, 2014.
[12] O. Ostroverkhova, Handbook of organic materials for optical and (opto)electronic
devices, Cambridge, U.K: Woodhead Publishing, 2013.
[13] Y. Zhang, F. Zu, S. T. Lee, L. Liao, N. Zhao and B. Sun, "Heterojunction with

Organic Thin Layers on Silicon for Record Efficiency Hybrid Solar Cells,"
Advanced Energy Materials, vol. 4, p. DOI: 10.1002/aenm.201300923, 2013.
[14] D. Elkington, N. Cooling, W. Belcher, P. C. Dastoor and X. Zhou, "Organic ThinFilm Transistor (OTFT)-Based Sensors," Electronics, vol. 3, pp. 234-254, 2014.
[15] Y. Seino, H. Sasabe, Y. J. Pu and J. Kido, "High-Performance Blue Phosphorescent
OLEDs Using Energy Transfer from Exciplex," Advanced Materials, Vols. 16121616, p. 26, 2014.
[16] N. Kaur, M. Singh, D. Pathak, T. Wagner and J. M. Nunzi, "Organic materials for
photovoltaic applications: Review and mechanism," Synthetic Metals, vol. 190, pp.
20-26, 2014.
[17] T. Uchida, M. Shibasaki, T. Matsuzaki and Y. Nagata, "Glare-Tunable Transparent
Electrochemical Smart Window Coupled with Transparent Organic Light-Emitting
Diode," Applied Physics Express, vol. 6, p. doi:10.7567/APEX.6.041604, 2013.
[18] P. Wiltzius and M. Hill, "Organic electronics and e-paper," in Device Research
Conference, 2000. Conference Digest. 58th DRC, Denver, CO, USA, 2000.
[19] A. M. Hiszpanski and Y. L. Loo, "Directing the film structure of organic
semiconductors via post-deposition processing for transistor and solar cell
applications," Energy Environ. Sci, vol. 7, pp. 592-608, 2014.
[20] A. J. Heeger, J. R. Schriefer and W. P. Su, "Solitons in Conducting Polymers," Rev.
Mod. Phys, vol. 40, p. 3439, 1988.
[21] D. N. Khan, M. H. Sayyad, F. Wahab and M. Tahir, "Electrical Characteristics
Enhancement in a Polymer Nanocomposite based Organic/Inorganic Diode," in
ICECCO 2012, Ankara, Turkey, 2012.
[22] D. Elkington, N. Cooling, W. Belcher, P. C. Dastoor and X. Zhou, "Organic ThinFilm Transistor (OTFT)-Based Sensors," Electronics, vol. 3, pp. 234-254, 2014.
[23] Y. Chu and P. Meisen, "Review and Comparison of Different Solar Energy
Technologies," Global Energy Network Institute (GENI), 2011.
[24] A. Gupta and S. Sharma, "Organic solar cell A Renewable Energy Resource,"
International Journal of Environmental Science: Development and Monitoring, vol.

4, pp. 16-18, 2013.

[25] Y. He, T. Ye and E. Borguet, "Porphyrin self-assembly at electrochemical interfaces:
Role of potential modulated surface mobility," J. Am. Chem. Soc, vol. 124, pp.
11964-11970, 2002.
[26] R. Takahashi and Y. Kobuke, "Hexameric macroring of gable-porphyrins as a lightharvesting antenna mimic," J. Am. Chem. Soc, vol. 125, pp. 2372-2373, 2003.
[27] S. F. Rak, T. H. Jozefiak and L. L. Miller, "Electrochemistry and near-infrared
spectra of several imide or quinone groups," J. Org. Chem, vol. 55, pp. 4794-4801,
1999.
[28] Z. Wang, C. Kim, A. Facchetti and T. J. Marks, "Anthracenedicarboximides as AirStable N-Channel Semiconductors for Thin-Film Transistors with Remarkable
Current On-Off Ratios," J. Am. Chem. Soc, vol. 129, pp. 13362-13363, 2007.

10

Chapter 2
Theory and Literature Review
The conjugated organic materials exhibit semiconducting properties and their
conductivity lies between insulators and conductors ranging from 10-9 to 103 -1cm-1
(Fig. 2.1). But one of the superiority of organic semiconductors is the enhancement in
their conductivity. By different synthetic procedures the conductivity of these materials
can be tuned according to the requirements of different applications. The band gaps of
organic semiconductors lies between 1.2 to 3.5 eV in comparison to traditional elemental
semiconductors silicon with 1.2 eV and germanium 0.76 eV [1].

Organic Semiconductors
Insulators

10-12
Diamond

Semiconductors

10-8

10-4

Conductors

100

Silicon
Glass

Conductivity Scm-1

104
Germanium

108
Copper
Iron

Fig. 2. 1: Comparison of conductivity of organic semiconductors.

The invention of transistor was the enormous progress toward the modern
electronics which basically started the domination of inorganic semiconductors over the
metals and vacuum tube technologies. The end of the 20th century brought omnipresence
of semiconductor electronics in the daily life uses.

The emerging of organic

semiconductors in the beginning of the 21th century leaded the real revolution in the
electronics which made possible the fabrication of novel devices such as flexible solar
cells, e-paper, smart window, low cost printed circuits and large area flexible displays. In
contrast to inorganic semiconductors, the organic semiconductors are inexpensive, light
11

weight, soluble and flexible. Their electronic and optoelectronic properties can be
modified.
The organic semiconductors are further divided into two main classes, polymers
and small molecules or oligomers. Both have the same chemical properties but differ only
in their physical properties. Jacob Berzelius introduced the polymers in 1832 as long
chain carbon molecules. These molecules have higher melting points due to stronger
intermolecular forces, while the small molecules have low melting points [2, 3].

2.1 Chemistry of Organic Semiconductors

The carbon atoms are the basic building block of Organic semiconductors. The
atomic number of carbon is 6 and its electronic configuration is 1s22s22p2. In chemical
bonding configuration, it forms sp, sp2 and sp3 hybridized orbitals which are the mixing
of atomic orbitals.
The organic semiconductors are -conjugated materials and are formed by sp2
hybridization which forms three hybrids, each containing one electron having orientation
of an angle of 1200 to one another. The unhybridized pz orbital which is perpendicular to
the plane of sp2 hybridized orbital contains the remaining electron. The overlapping of
two sp2 orbitals results in the formation of s-bond which basically provides the structure
stability to the organic materials, while the bond appears due to the pz orbitals and is
responsible for the conductivity of the materials (Fig. 2.2).

The electrons are

delocalized and have the ability to move freely within the chain. The appearance of
delocalized -orbitals results as the lowest unoccupied molecular orbital (LUMO) and the
highest occupied molecular orbital (HOMO). The smaller energetic difference between
these orbitals provides the materials as semiconducting properties.

12

pz- orbital

-bond

pz- orbital

-bond

Plane of the

-bond

sp2 orbitals
Fig. 2. 2: Scheme of the orbitals of two sp2 hybridized carbon atoms

2.2 Mechanism of Charge transport in organic

materials
The HOMO-LUMO energy gap of organic semiconductors lies between 1-4 eV
which is an indication of insulating behavior of the organic materials [4]. But the
opportunities of the generation and conduction of charge carriers can be produced by
using different methods including the creation of electron-hole pair by optical excitation,
chemical/electrostatic doping or the injection of charge carriers by metallic electrodes.
The organic semiconductors can be found in different states i.e. amorphous,
polycrystalline or single crystal, so the charge transport in these materials can have
different mechanisms. Organic semiconductors can be described on the basis of the
energy band theory of inorganic semiconductors. According to this theory, the charge
transport mechanism in organic materials is considered to be the same as in the extended
states of the valence and conduction bands of single crystal inorganic semiconductors.
The molecules in organic materials are weakly bonded by van der Waals and dipoledipole attractions, which causes the lesser intermolecular orbital overlap that results a
narrower band width and a short mean free path in contrast to the inorganic
semiconductors. According to band theory, the mobility of the materials is influenced by
13

the scattering of phonons, impurities and the temperature. The charge mobility is
described by the relation [5]

(2.1)

Where T represents the absolute temperature and n depends on the scattering

mechanism. In naphthalene single crystals at ambient temperature, the hole FET mobility
was observed about 20-35 cm2/Vs while for same material mobility at cryo-temperatures
of several Kelvin was found of about 102 cm2/Vs by Time-Of-Flight (TOF) experiments
[6, 7]. A phonon-assisted hopping mechanism of charge transport in the amorphous and
polycrystalline materials is due to thermally activated charge mobility.

In this

mechanism, the variation in the mobility with temperature is resulted by the thermally
activated

hopping between localized sites.

Then the activation energy E can be

described with the following [8]

~

exp

exp (2

) (2.2)

where E is the energy difference between two hopping sites, VP is the lattice frequency, T
is the absolute temperature and k is Boltzmanns constant. The probability of the
localized hopping electron transferring to the next site at an energy E above the initial
one is represented by VP exp(-E/KT). The overlap of the wave-functions between adjacent
hopping sites is described by the term exp 2R where is the decay rate of the wavefunction and R is the separation between sites.
The tight inter-molecular -stacking in the packed molecular films results the
higher charge carrier mobilities. Then the charge transport in organic semiconductors
mostly depends on the transfer integral and the reorganization energy which relate with
the packing of organic semiconductors.
.

2.2.1

Organic Thin Film Transistors

Organic thin film transistor (OTFT) is three terminal device which is the

fundamental unit of organic electronic and optoelectronic devices. Without a bulk contact
it resembles with the Si MOSFET. All three types of materials i.e. conductor, insulator
and semiconductor are simultaneously used in organic transistors. It consists of thin films
14

of organic semiconductor, dielectric and three electrodes i.e. source, drain and gate. The
source and drain play the role of flow of charges and are directly connected with the
semiconducting thin film while the gate is used for the modulation of voltage or current.
OFETs are mainly prepared in one of following four different:
1. Bottom gate/top contact
2. Bottom gate/bottom contact
3. top-gate/bottom-contact
4. top-gate/top-contact
The first two configurations are depicted in Fig. 2.3. In first structure, the gate and
dielectric are deposited first on the substrate then both drain and source are deposited on
the top of the thin film of OSCs while in the second configuration, the drain and source
are directly developed on the gate and dielectric then OSCs film covers the whole device
[9].

Source

Drain
Organic semiconductor

+++++++++++++++

Organic semiconductor

Source

+++++++++++++++

Gate Dielectric

Drain

Gate Dielectric

Gate
Substrate

Gate
Substrate

Fig. 2. 3: Schematic structures of bottom-gate OFETs: top-contact (left) and

bottom-contact (right)

The top-contact transistors exhibit better performance with higher field effect
mobility, which may be attributed due to direct contact of source and drain electrodes
with the semiconducting thin film. But one important drawback of this structure is
possible damage of semiconducting film because the electrodes are usually deposited by
thermal evaporation through the shadow mask instead of lithographic processes.
In bottom-contact OFETs, the crystalline semiconducting material can influence the
charge transport and the prior existence of the metal electrodes can affect the growth of
organic film on the dielectric.
15

In other two OFET structures, the gate is developed on the top. In the topgate/bottom-contact geometry, the drain and source are patterned on the top of the
substrate, followed by the deposition of semiconductor thin film and then the gate
dielectric and finally the gate electrode are developed. In the top-gate/top-contact
structure the organic film is first deposited on the substrate, and then the source and drain
electrodes, the gate dielectric and finally gate electrode are deposited. The degradation in
the structure by ambient atmosphere can be prevented by using a polymeric dielectric.

Gate

Gate

Gate Dielectric

Source +++++++++++++++

Gate Dielectric

Drain

Organic semiconductor

+++++++++++++++
Source Organic semiconductor

Substrate

Drain

Substrate

Fig. 2. 4 Schematic drawings of top-gate OTFTs: top-gate/top-contact (left) and topgate/bottom-contact (right)

2.2.2Factors limiting the mobility in OFETs

The charge mobility is an important parameter of the organic semiconductors
which can be found by different methods like SCLC, Time of flight and by OFETs. The
finding of mobility by OFETs is the best one. The value of mobility depends on the
organic materials nature. The single crystal materials have higher mobility, but the
growth of single crystal of organic semiconductor is very difficult task. The
polycrystalline organic material posses the smaller value of mobility as compared to
single crystal because of different types of defects in the material like grain boundaries,
dislocation, stacking etc. These defects trap the charge carriers causing the decrease in
the mobility of the organic semiconductors [10].

16

2.3 Operation of the organic transistors

The organic semiconductors have the low charge carrier density so the gate field
not affects the bulk semiconductor, the charge transport can take place only in thin layer
close to the interface of the dielectric. OFETs can only function in accumulation mode.
When the gate and drain of a p-type OFET are negatively biased and VDSVG, a linear
current regime can be observed. By making VDS more negative, the linear rise in the
current IDS can be observed which is basically caused by the decrease in the density of
accumulated charges from the source to the drain (Figure 2.5). When the potential of
drain is more negative than the potential of the gate, the current tends to saturate and a
zone of depletion appears close to the drain (pinching of the channel).
The relation between drain source current and voltage i.e. (IDS & VDS) at fixed gate
voltage (VG) represents the output characteristic while the transfer characteristics give the
relation between IDS and VG at fixed VDS. The same information by the OFET
measurements is obtained when sufficient numbers of drain voltages (gate voltages) are
scanned as transfer (output) characteristics. The linear and saturation regime can be
obtained by transfer characteristics at two fixed VDS: one value as much smaller than the
maximum scanning gate voltage and the other VDS value is set larger than the maximum
scanning VG. Various important parameters like the field effect mobility (FET), the on/off
ratio and the threshold voltage can be extracted from the transfer characteristics of the
OFET. The model developed for Metal Oxide Semiconductor Field Effect Transistor
(MOSFET) can be used for the characterization of the OFET. According to the standard
MOSFET model, the n-channel device is described by the standard current equation [11].
In the linear region (VDS< VG-Vth):
=

(2.3)

But for saturation operational region (VDSVG-Vth):

=

(2.4)

Both equations show that FET is a proportional factor that relates the IDS to the
VDS, VG, the length L and width W of channel, threshold voltage Vth. and the gate
capacitance per unit area Ci.
17

The measured values of the FET in the saturation and linear regions of operation
have much difference, so they are referred as FET,sat and FET,lin . In this research work
FET is measured in the saturation region.

Fig. 2. 5 Transfer (a) and output (b) characteristics of PDIF-CN2 TFT[12]

18

The mobility in OFETs is field-dependent and it may be limited by the existing

traps and by metal/organic contact (Schottky barrier). Therefore, to get the high value of
mobility remedies should be followed to minimize the effect of these factors. By
increasing the bias magnitude, OFETs can be operated away from the injection-limited
regime. This can be achieved by slightly increasing the values of IDS with VDS [13].

2.3.1Threshold voltage
The gate voltage at which the conduction channel starts to appear is called the
threshold voltage. The charge transport mechanism in OFET is different from MISFETs
i.e. Metal Insulator Semiconductor Field Effect Transistors which are silicon based. It
operates in accumulation region; the conduction channel is not isolated from the substrate
due to absence of depletion layer [14]. Ideally, Vth should be zero for an organic transistor
operating in accumulation mode, but the real Vth is not equal to zero due to various
factors [15]. The appearance of non-ohmic injection barrier at the interface of metal and
semiconductor causes the misalignment of the energy levels of the metal contacts with
the LUMO of n-type materials and HOMO of p-type.
The value of threshold voltage (Vth) can be found by either the measurements by
plotting IDS versus VG for saturation region or by extrapolating the linear region of the
IDS (VGS) curve to IDS = 0.

2.3.2On/Off ratio
The ratio between the currents in the OFET in on and off states is referred as the
on/off ratio. The channel in organic transistors is not isolated from the other portion of
semiconductor, Then the total current is the sum of an ohmic current IDS, the conduction
current IDS in the channel (as both currents are parallel). The total current is:
I

=I

+I

and the ratio is

,
,

(1.5)

This ratio exhibits the ability of a transistor to use as a switch from the on state to the off
state. The transistors with on/off ratio of the order of 106 can be used in logic circuits
[16]. This ratio can be increased by different methods. The modification of transistor
19

geometry causes the appreciable rise in the value of the on/off ratio. The ratio of channel
width and length (W/L) has direct influence on the value of the drain-source current IDS
in the saturation region. Thus either by increasing the channel width or decreasing its
length, the value of the on/off ratio can be increased [17]. Another effective way to
increase the on/off ratio is to minimize the off-current. Which can be reduced either by
the purification of organic semiconductors or reducing leaks and noise interferences by
patterning active organic layer.

2.3.3Contact resistances
The device performance is also influenced by the channel and contact resistances.
The total resistance of the OFET device (Rtotal) is the net value of the contact resistance
(Rc) and the channel resistance (Rch) i.e.
Rtotal =Rc + Rch

while

Rc= Rsource+ Rdrain

(1.6)

The contact resistance which depends on the nature of electrodes i.e. the metals
work function and on the geometry of the transistor, is actually the sum of source and
drain resistances. The increase in gate voltage results in the rise in charge carrier density
in the channel which minimizes the contact resistance. In the bottom contact
configuration the contact resistance is high as compared to the top contact structure and it
depends on the drain voltage. The differences exist due to different reasons. In top
contact geometry, the injection surface is larger while in bottom contact the non-uniform
or disturbed growth of organic material by triple interfaces causes the increase in
resistance. Generally the faster response time for OFETs can be achieved by decreasing
the channel length and increasing . The interface modification by using Self-Assembled
Monolayer (SAM) can also reduce the contact resistance.

20

2.4 References
[1] D. Yon, H. Wang and B. Du, Introduction to Organic Semiconductr Heterojunctions,
Singapore: John Wiley & sons, 2010.
[2] J. Berzelius, Jahres-Bericht ber die Fortschritte der physischen Wissenschaften,
Eilfter Jahrgang, 1832.
[3] R. Farchioni and G. Grosso, Organic Electronic Materials, Berlin: Springer, 2001.
[4] M. Pope and C. E. Swenberg, Electronic Processes in Organic Crystals and
Polymers, 2nd ed, New York: Oxford University Press, 1999.
[5] J. G. Laquindanum, H. E. Katz, A. J. Lovinger and A. Dodabalapur,
"Benzodithiophene rings as semiconductor building blocks," Adv Mater, vol. 9, pp.
36-39, 1997.
[6] E. Menard, V. Podzorov, S. H. Hur, A. Gaur, M. E. Gershenson and J. A. Rogers,
"High-performance n- and p-type single-crystal organic transistors with free-space
gate dielectrics," Adv Mater, vol. 16, pp. 2097-2101, 2004.
[7] W. Warta and K. Norbert, "Hot holes in naphthalene: High, electric-field-dependent
mobilities," Phys. Rev. B, vol. 32, pp. 1172-1182, 1985.
[8] Y. Olivier, V. Lemaur, J. L. Bredas and J. Cornil, "Charge hopping in organic
semiconductors: Influence of molecular parameters on macroscopic mobilities in
model one-dimensional stacks," J. Phys. Chem. A, vol. 110, pp. 6356-6364, 2006.
[9] Y. Y. Lin, D. J. Gundlach and T. N. Jackson, "Contact dependence of alphasexithienyl thin film transistor characteristics," Electrical, Optical, and Magnetic
Properties of Organic Solid State Materials, vol. 413, pp. 413-418, 1996.
[10] H. E. Katz, Z. N. Bao and S. L. Gilat, "Synthetic chemistry for ultrapure,
processable, and high-mobility organic transistor semiconductors," Accounts Chem
Res, vol. 34, pp. 359-369, 2001.
[11] J. Soeda, T. Uemura, Y. Mizuno, A. Nakao, Y. Nakazawa, A. Facchetti and J.
Takeya, "High Electron Mobility in Air for N,N
1H,1HPerfluorobutyldicyanoperylene Carboxydi-imide SolutionCrystallized ThinFilm Transistors on Hydrophobic Surfaces," Adv. Mater, vol. 23, p. 36813685,
21

2011.
[12] C. D. Dimitrakopoulos and P. R. L. Malenfant, "Organic thin film transistors for
large area electronics," Adv Mater, vol. 14, pp. 99-117, 2002.
[13] A. Dodabalapur, L. A. Wang, D. Fine and D. Basu, "Electric-field-dependent charge
transport in organic thin-film transistors," J Appl Phys, vol. 101, p. 054515, 2007.
[14] G. Horowitz, R. Hajlaoui, H. Bouchriha, R. Bourguiga and M. Hajlaoui, "The
concept of "threshold voltage" in organic field-effect transistors," Adv Mater, vol.
10, pp. 923-927, 1998.
[15] G. Horowitz, P. Lang, M. Mottaghi and H. Aubin, "Extracting parameters from the
current-voltage characteristics of field-effect transistors," Adv Funct Mater, vol. 14,
pp. 1069-1074, 2004.
[16] J. Wang, H. Wang, J. Zhang, X. Yan and D. Yan, "Organic thin-film transistors with
improved characteristics using lutetium bisphthalocyanine as a buffer layer," J. Appl.
Phys, vol. 97, p. 026106, 2005.
[17] T. P. Saragi, T. Fuhrmann-Lieker and J. Salbeck, "High ON/OFF ratio and stability
of amorphous organic field-effect transistors based on spiro-linked compounds,"
Synthetic Met, vol. 148, pp. 267-270, 2005.

22

Chapter 3
Materials and Experimental Procedures
3.1 Organic Materials
In this research the organic semiconducting materials (i) 2-formyl-5,10,15,20-tetrakis(4isopropylpheny)prophyrinatocopper(II)

or

formyl-TIPPCu(II),

(ii)

N,N-di-n-heptyl-2,3:6,7-

anthracenetetracarboxydiimide (ADCI7) and (iii) N,N-di-n-octyl 2,3:6,7 anthracenetetracarboxydiimide

(ADCI8) have been used for the fabrication of devices.

3.1.1 formyl-TIPPCu(II)
formyl-TIPPCu(II)

with

full

chemical

name

2-formyl-5,10,15,20-tetrakis(4-

isopropylpheny)prophyrinatocopper(II) is carbon based metalloporphyrin. Its molecular structure is shown

in Fig. 3.1.1. The organic semiconductor formyl-TIPPCu(II) was synthesised by Yaseen et al [1].

Fig.3. 1 Chemical structure of formyl-TIPPCu(II).

3.1.2N,N-di-n-octyl-2,3:6,7-anthracenetetracarboxydiimide (ADCI8)
The

ADCI8

is

n-type

organic

material

which

belongs

to

the

family

of

anthracenetetracarboxydiimide and has an optical energy band gap of 2.95 eV. This material is very

23

suitable for fabrication of organic thin film transistors. Its optical and photoluminescence wavelengths in
Dichloromethane (DCM) are 419 and 423 nm. The molecular structure of ADCI8 is depicted in Fig. 3.2.

Fig.3. 2 The Molecular structure of ADCI8

3.1.3 N,N-di-n-heptyl-2,3:6,7-anthracenetetracarboxydiimide (ADCI7)

The

ADCI7

is

also

n-type

organic

semiconductor

belonging

to

the

family

of

anthracenetetracarboxydiimide. Its chemical formula is given in Fig. 3.3. This material has been first time
used for the fabrication of n-channel OTFTs.
O
O

O
+

H2N R

1. CHCl3, RT

Br
Br2, hv
CCl4

N R

2. NaOAc, Ac2O,
reflux

O
1, R = n-C7H15
2, R = n-C8H17
Br

Br
Br

O
Br
Br

Br

1 or 2, NaI
N, N-dimethylacetamide

Br
3

R N

N R

O
4 (ADI7), R = n-C7H15
5 (ADI8), R = n-C8H17

Fig.3. 3 The synthesis procedure and chemical structure of ADCI7

3.1.4 Poly(methyl methacrylate) (PMMA)

The synthetic polymer Poly(methyl methacrylate) (PMMA) with molecular formula (C5O2H8)n is
used as buffer layer on dielectric SiO2 to enhance the air stability of n-channel OTFTs [2]. The Molecular
24

structure of PMMA is given in Fig. 3.4. In this research, the commercially available
available PMMA w
was used. It
forms a stable film because of having high melting point [3].

Fig.3. 4 Molecular structure of PMMA

3.1.5 Hexamethyldisilazane (HMDS)

The

organosilicon

compound

Hexamethyldisilazane

(HMDS)

with

chemical

formula

[(CH3)3Si]2NH is low density compound [4].. Being adhesion promoter it is used as self assembly
monolayer for the fabrication of stable n-channel
n channel OTFTs. Fig. 3.5 shows its chemical structure. The
commercially available HMDS is used in this research.

Fig.3. 5 Chemical structure of HMDS.

25

3.2 Fabrication Techniques

This section is composed of the general fabrication methods which have been employed in this
research work to fabricate the junction diodes, organic sensors and organic thin film transistors. These
include the pre-deposition preparation of substrates (glass and silicon wafer) and the material deposition
techniques.

3.2.1 Substrate Cleaning

The performance of organic devices depends on uniform growth of organic thin films on the
substrates. The adhesion and growth of organic material on the substrate is directly influenced by the
topography and cleanliness of the substrate structure. So the removal of contamination from the substrate
structure before any deposition is very necessary.
The procedures for cleaning the substrates depend on the nature of substrate. In this research work,
the silicon and glass substrates have been used for the fabrication of junction diodes, n-channel OTFTs and
organic sensors, respectively. Their cleaning procedures are illustrated here.
3.2.1.1 Glass substrates cleaning
For the detection of light, temperature and humidity, the surface type organic sensors have been
fabricated in this research work. The organic films were deposited on the thin glass slides which are
commercially available for medical purposes. Prior to the deposition, all substrates were cleaned by
following these steps
Detergent- to remove large surface contamination or possible oil droplets
Sonication-to remove surface particles- using distilled water in ultrasonic bath
Drying in dust free environment
Plasma cleaning to remove organic contaminations in thermal evaporator
3.2.1.2 Silicon Substrate Cleaning
In this dissertation, two different types of organic devices have been fabricated by using
silicon substrates. The p-type silicon has been used to form its junction diode with organic material, while
SiO2 covered n-type silicon wafers were used as gate electrode to fabricate the n-channel OTFTs. The
procedure of cleaning of silicon substrates is slightly different for both cases.
26

3.2.1.2.1 Cleaning of silicon substrate for junction diodes

To fabricate the formyl-TIPPCu(II)/p-Si, the silicon substrates were cleaned by adopting following
procedures.

Sonication- to remove large surface particles- using acetone in ultrasonic bath

Drying- by using nitrogen gas

Plasma cleaning- to remove the organic particles in plasma cleaner

3.2.1.2.2 Cleaning of silicon substrate for OTFTs

The n-type organic materials are very sensitive and react with water droplets to form hydroxyl ions
which become the traps for electrons. To minimize this effect, the silicon surface is cleaned to avoid
any contaminations. Therefore, the substrates were cleaned by using following steps:

Sonication- using acetone in ultrasonic bath- to remove

surface particles

Sonication- using 2-propanol in ultrasonic both- to remove

surface particles

Piranha cleaning- solution of 96% H2SO4 and 32% H2O2 in 2:1 volume ratio
to remove all possible contaminations

Sonication- in deionized water

Drying- in nitrogen gas

Plasma cleaning

The substrates were cleaned by using acetone, 2-propanol and Piranha in chemical hood.
Fig. 3.6 shows the Hood for cleaning substrates.

27

Fig.3. 6 Chemical Hood for cleaning substrates

In this research work, for OTFTs the substrates were plasma cleaned in Plasma cleaner PDC-32G (Fig.
3.7).

Fig.3. 7 Plasma cleaner PDC-32G

28

3.2.2 Thin Films Depositions

In this research, thin films of the materials were grown on the substrates by using two different
techniques.
1. Vacuum Thermal Evaporation
2. Spin coating
3.2.2.1 Vacuum thermal deposition technique
Vacuum thermal sublimation is one of the most popular techniques for the growth of thin layers of
different material in the range of angstroms to microns. Historically it is a very old technique which can
be traced to the formation of thin metallic film by Michael Faraday by exploding the metallic wire in
vacuum.
This technique consists of three major steps.

1. Generation of vapor
The cloud of vapours is created by heating the solid material (source) in
Vacuum chamber
2. Vapor Transpotation
The vapour are transported from source to target (Substrate)
3. Film growth
The vapor which strikes the substrate sticks with its surface causing the film growth
The organic semiconductors specially the small molecules are deposited by using this technique.
The organic material/metal is loaded in resistively heated crucible/boat. The substrates are placed in sample
holder whose temperature can also be controlled. Both are sealed in vacuum chamber having inside
pressures of ~10-6 mbar. The deposition rate and the thickness of the film can be controlled by the quartz
crystal and oscillator (crystal sensor) monitor. The evaporation can be adjusted to the desired value by
changing the orientation of shutter. The inner view of the vacuum evaporator is shown in Fig. 3.8, with the
sample holder (Fig. 3.9).

29

Fig.3. 8 Inner view of PLASMIONIQUE EVD-400H thermal evaporating system

Fig.3. 9 Sample Hoder in PLASMIONIQUE EVD-400H thermal evaporating system.

In this research work, for the fabrication of junction diodes, organic sensors and OTFTs, the thin
films of metal electrodes and organic materials were formed by thermal evaporation techniques. Both
30

metals (Gold & Silver) and organic material formyl-TIPPCu(II) were deposited on the substrates by using
thermal evaporator AUTO 306 having FTM5 film as thickness monitor in the Faculty of Material and
Manufacturing, GIKI (Fig. 3.10) while the n-channel OTFTs of ADCI7 and ADCI8 were fabricated by
depositing the thin film of organic materials and metals (Gold) on the n-Si substrates by PLASMIONIQUE
EVD-400H thermal evaporating system (Fig. 3.11).

Fig.3. 10 Edward Auto 306 vacuum thermal evaporator with thickness Monitor

31

Fig.3. 11 PLASMIONIQUE EVD-400H thermal evaporating system

3.2.2.2 Spin Coating

Spin coating has been used for many years for developing thin films, and the technique is
still effective for solution processable organic materials. In this technique a liquid or a suspension is
dispensed by a pipette onto the center of a substrate which rotates with uniform angular speed. The
thickness of the material is controlled by spinning speed. The spinning time, surface tension,
viscosity and volatility of a solvent and the amount of solid content present in suspension also affect
the thickness of the film. The schematic diagram of spin coating is shown in Fig. 3.12.

32

Fig.3. 12 Schematic diagram of spin coating technique.

In this research, the thin films of PMMA as buffer layers were deposited on the top of SiO2
dielectric layers for preventing the absorption of water droplets and to increase the mobility of nchannel OTFTs. The films were grown at the spinning speed of 2500 rpm using spin coater Model
WS-400B-6NPP/LITE which is shown in Fig. 3.13.

Fig.3. 13 Spin coater Model WS-400B-6NPP/LITE

3.3 Atomic Force Microscopy

The performance of organic devices is directly influenced by the nature of organic films. The
charge mobility in OTFTs depends on the thin films growth. The surface morphologies of organic thin
films of OTFTs can easily be monitored by Atomic Force Microscopy. By using this tool, the irregularities
and any type of degradation in the thin layers can be studied.
33

A cantilever with a sharp tip of radius of curvature (~10-50 nm) is used to scan the surface
of sample. Then the Van der Waal interaction (~ 1nN) emerges between the neutral atoms of the cantilever
and surface which deflects the cantilever and the laser beam from the laser diode. A photodetector records
these deflections. The schematic diagram of AFM is shown in Fig. 3.14.

Laser

Photodetector

Cantilever

Fig.3. 14 Schematic diagram of AFM.

AFM can function in the following three different modes:

1. Static or contact mode
2. Semicontact or tapping (Intermittent contact) mode
3.

Non contact mode

In this research work, surface morphologies of the thin films of the organic materials which were
grown for the fabrication of organic sensors and OTFTs were investigated in tapping mode (NSC 35
Micromasch cantilevers) by using MM Multimode AFM setup (Fig. 3.15). For the surface morphologies of
the thin films for OTFTs, ScanAsyst-Air (Bruker) silicon nitride levers with a nominal spring constant of 0.4
N/m, nominal resonant frequency of 70 kHz and tip radius < 5nm has been used.

34

Fig.3. 15 MM Multimode 8 AFM setup

3.4 Device Characterization Techniques

3.4.1Electrical Characterization
The current-voltage studies of the junction diode and OTFTs were carried out using the facilities
available at the Faculty of Engineering Sciences, GIK Institute and SCS at Perepichka lab McGill
University, Canada, respectively. These systems are briefly described here.

35

3.4.2Current- Voltage (I-V) Characterization

The current-voltage measurements of the junction diode were carried out on Probe Station (KARL
SUSS PM5) at temperature range of 229-339K, equipped with keithley-196 System Digital Multimeter and
keithley-228A I-V source. Fig. 3.16 depicts the I-V characterization set up.

Fig.3. 16 Probe Station(KARL SUSS PM5) with keithley-196 System Digital Multimeter and
keithley-228A I-V source
While the electrical measurements of n-channel OTFTs were obtained by Keithley 4200-SCS in
vacuum at ambient atmosphere (Fig. 3.17). The inner view of the apparatus is shown in Fig. 3.18.

Fig.3. 17 Keithley 4200-SCS for characterization of OTFTs

36

Fig.3. 18 Inner view of Keithley 4200-SCS

3.5 Humidity dependent Characterization

Humidity dependent measurements i.e. capacitance and resistance of the fabricated humidity
sensors were investigated in self-assembled humidity setup

connected with LCR and digital humidity

meter CEM DT-8860. The schematic diagram of the setup is shown in Fig. 3.19. By flowing the wet and
dry nitrogen in the chamber, the humidity level was changed.
801.2

LCR
meter

Exhaust
check valve

Dry N2
Ag/formyl-TIPPCu(II) /Ag

Distilled
water

Sensor

Humidity
Chamber
Sensor
Holder

95.7

Humidity
meter

Fig.3. 19 Schematic of experimental setup for humidity characterization

37

3.6 Light and Temperature Dependence Measurements

By changing the distance between fabricated sensor and light source the light dependent
measurements were carried out by using CEM DT-1300 light meter. The experimental setup is depicted in
Fig. 3.20
Movable light source

Light sensor

CEM DT-1300 light

meter

Fig.3. 20 Schematic of experimental setup to study the effect of light

The Temprotic Corporations thermo-chuck Alpha series probe station (KARL SUSS PM5) model
TP0315A-TS-2 of USA has been used to study the effect of changing temperature from 27 to 1870C on the
organic temperature sensor. Fig. 3.21 represents the experimental setup to study the effects of temperature.

38

Fig.3. 21 Experimental setup to study the effects of temperature

3.7 References

[1] M. Yaseen, Mukhtar Ali, Muhammad NajeebUllah, Munawar Ali

Munawar, Irshad Khokhar,
[2] J. Heterocyclic Chem., vol. 46, pp. 251-255, 2009.
"Poly(methyl methacrylate)," Wikipedia, [Online]. Available:
http://en.wikipedia.org/wiki/Poly(methyl_methacrylate). [Accessed 07 May 2014].
[3] W. F. Smith and J. Hashemi, Foundations of Materials Science and Engineering (4th ed.), McGrawHill, 2006.
[4] "Bis(trimethylsilyl)amine," Wikipedia, [Online]. Available:
http://en.wikipedia.org/wiki/Bis(trimethylsilyl)amine. [Accessed 07 May 2014].

39

Chapter 4
Temperature Dependant Electrical Properties of formylTIPPCu(II)/p-Si Heterojunction Diode
4.1 Introduction
Organic electronic is a commercially emerging field which constantly introducing more efficient
and stable commercial appliances like the active matrix display, complementary circuits, RFID tags and
sensors by using varieties of organic materials including small molecule and polymers by exploring their
unique electronic and optoelectronic properties [1-3]. It enables the designing of more eco-friendly and
affordable devices than silicon-based electronics. The organic semiconductors promise more accessible,
innovative and sustainable electronic technologies.

The tunebility

in the properties of organic

semiconductors either by alteration in chemical structure or by improving their surface morphology make
them special for fabricating a variety of devices with high efficiency and stability. The electrical properties
of conjugated organic materials can be studied by making their junction with inorganic semiconductors [4,
5]. The I-V measurements of organic devices are unable to provide much more information about the
device characteristics at room temperature [6], so the current-voltage characteristics at wide range of
provide useful information about electronic parameters of the devices. Among the small molecules,
porphyrins are more suitable for electronic conduction because of having large -electron frameworks.
Porphyrin and metalloporphyrin being field responsive materials have been used for fabrication of
electronic and optoelectronic devices [7, 8]. Thin films of porphyrin which are formed by thermal
evaporation or solution methods are of crystalline natures which enhance the different features of organic
devices.
In this research work, the temperature dependent electrical properties of copper based porphyrin i.e.
2-formyl-5,10,15,20-tetrakis(4-isopropylpheny)prophyrinatocopper(II) or formyl-TIPPCu(II) have been
investigated by fabricating its junction with p-type silicon to explore more information about this material.

40

4.2 Device Fabrication

The temperature dependent behavior of copper based porphyrin i.e. 2-formyl-5,10,15,20-tetrakis(4isopropylpheny)prophyrinatocopper(II) or formyl-TIPPCu(II) has been studied by fabricating its junction
diodes with p-type silicon substrates. The synthesis procedure of formyl-TIPPCu(II) has already been
reported elsewhere [10].
Due to presence of carbonyl group in formyl-TIPPCu(II), its FTIR spectrum shows a strong
absorption at 1670 cm-1. In chloroform, its UV-Visible spectrum exhibits a B band or Soret absorption at
430 nm along with 550 and 595 nm as two Q-band absorptions (Fig. 4.1). At 872, the mass spectrum of
formyl-TIPPCu(II) depicts a molecular ion peak of 3% intensity with a base peak at 349 (Fig. 4.2).
UV-Visible Spectrum of formyl-TIPPCu(II)

Absorbance

0
400 420 440 460 480 500 520 540 560 580 600 620 640

Wavelength (nm)
Fig. 4. 1UV-Visible Spectrum of formyl-TIPPCu(II)

41

Fig. 4. 2 Mass Spectrum of Formyl-TIPPCu(II)

For the fabrication of formyl-TIPPCu(II)/p-Si junction diodes, the p-type silicon substrates with
orientation (100) were cleaned with acetone in ultrasonic bath for 15 minutes. After drying these substrates
by nitrogen gas, these were plasma cleaned for 10 minutes to remove different contaminations. The film of
formyl-TIPPCu(II) with thickness 140 nm was thermally grown on the substrate in the Auto 306 vacuum
coater with diffusion pumping system (Edward). The chamber pressure was kept as 5.5 10-5 mbar. The
thickness of formyl-TIPPCu(II) was measured by an FTM5 crystal controlled thickness monitor. The crosssectional view of the fabricated Ag/formyl-TIPPCu(II)/p-Si junction diode is shown in Fig. 4.3. The crosssectional view of the fabricated Ag/formyl-TIPPCu(II)/p-Si junction diode is depicted in Fig. 4.3. The
temperature dependant I-V measurements were carried out on thermo chunk Alpha series probe station
(Karl Suss PM5) with Keithley SMU system 237.

Ag

p-Silicon

formylTIPPCu(II)

Fig. 4. 3 Cross-sectional view of Ag/formyl-TIPPCu(II)/p-Si diode.

4.3 Results and discussion

The I-V characteristics of formyl-TIPPCu(II)/p-Si junction at temperatures (299-339K with 10 K intervals)
are presented in Fig. 4.4.
42

-6

2.5x10

-6

2.0x10

299
309
319
329
339

-6

Current (A)

1.5x10

-6

1.0x10

-7

5.0x10

0.0
-8

-6

-4

-2

Voltage (V)

Fig. 4. 4 I-V characteristics of formyl-TIPPCu(II)/p-Si diode at 299-339K.

The I-V curves exhibit weak voltage dependence for reverse current but these show exponential
response at low forward voltage and then deviate at high voltage which may be caused by the domination
of series resistance and interfacial layers. These graphs show the rectifying nature which is clearly caused
by the formation of organic/inorganic diodes. These diodes have much smaller value of turn on voltage ~
0.5V which are suitable for different applications. The current increases with the increase in temperature
which suggests a negative resistance coefficient of the diode. At the low applied voltage, the thermionic
emission (TE) theory can be used to analyse the I-V characteristics at low applied voltage [11, 12], the
current and voltage are related by the equation by using this theory (for q(V-IRs) > kT).

q V IRs
I I 0 exp
1
nkT

(4.1)

Where voltage across the junction is represented by V, the Boltzmann constant by k, the electronic
charge by q, the temperature in Kelvin by T, the forward current by I and the diode quality factor by n
which describes the disagreement between experiment and simple theory at forward bias of the diode, and
the voltage drop across the parasitic series resistance (Rs) is IRs, the reverse saturation current (I0) can be
measured by semilog forward I-V plot (Fig. 4.5) at zero applied voltage, which can be represented as:

q
I 0 AA*T 2 exp b
kT

(4.2)
43

Wherethe effective diode area is represented by A, the effective Richardson constant by A*which
has the values 32 A/cm2K2 for p-Si [13], b is the zero bias barrier height..

-13

299
309
319
329
339

-14
-15

ln I (A)

-16
-17
-18
-19
-20
-21
-8

-6

-4

-2

Voltage (V)

Fig. 4. 5 Semi-logarithmic (IV) characteristics of formyl-TIPPCu(II)/p-Si diode at different

temperatures.
The decreasing response of the reverse saturation current with decrease in temperature can be seen
in Fig. 4.6. The low value of reverse saturation current i.e. 1.19 10-8 A at 299K indicates the good quality
of fabricated junction diode. The changing values of saturation current at different temperature can also be
used to find the activation energy (Ea) of carrier conduction by using Arrhenius plot of logI0 verses 1000/T
with the help of following relation
E
I 0 exp a
kT

(4.3)

The value of Ea from this plot (Fig. 4.7) is determined as 0.59V.

44

-8

1.6x10

-8

1.6x10

-8

1.5x10

-8

1.4x10

-8

I0(A)

1.4x10

-8

1.3x10

-8

1.3x10

-8

1.3x10

-8

1.2x10

-8

1.1x10

300

310

320

330

340

Temperature (K)

Fig. 4. 6 Reverse saturation current of formyl-TIPPCu(II)/p-Si diode at different temperature.

-17.95
-18.00

logI0 (A)

-18.05
-18.10
-18.15
-18.20
-18.25
2.9

3.0

3.1

3.2

3.3

3.4

-1

1000/T (K )

Fig. 4. 7 Arrhenius plot of saturation current vs 1000/T for formyl-TIPPCu(II)/p-Si diode

The slope of the linear region of the semi-log I-V curve is used to extract the ideality factor of the
device at different temperatures (Fig. 4.5) by applying the expression:

45

q
kT

dV

d ln I

(4.4)

The values of ideality factor are greater than unity which may be possibly caused by different
factors such as inhomogeneities of film thickness, series resistance, interface states, secondary mechanisms
and non uniformity distribution of interfacial charges [14, 15]. It is also observed from the experimental
curves that the rise in temperature causes a decrease in the values of ideality factor. The series resistance
which plays the parasitic role in the diode can also be found by semi-logrithmic plot of forward I-V
characteristics. For high forward voltage, I-V curves deviate from linearity indicating the presence of series
resistance (Fig. 4.8). The voltage drop across the neutral region in semi-log curve V=IRs is obtained by the
horizontal displacement between the extrapolated linear part and the actual curve, can be used for finding
the values of series resistance (Rs) at different temperatures [16].

-13.0

299
309
319
329
339

-13.5
-14.0
-14.5

ln I (A)

-15.0
-15.5
-16.0
-16.5
-17.0
-17.5
-18.0

Voltage (V)

Fig. 4. 8 Forward bias semi-logarithmic plots of current-voltage characteristics of formylTIPPCu(II)/p-Si diode indicating the voltage drop V=IRs across the neutral region.

The variation of series resistance of formyl-TIPPCu(II)/p-Si junction diode with change in

temperature is depicted in Fig 4.9. The rise in temperature results the decrease in the values of Rs which
actually causes the decrease in diodes ideality factor. The values of zero bias barrier height at different
temperatures have been calculated by using well known Norde method for extraction of electronic
parameters [17]. According to this method the Norde function F(V) is calculated by following relation
46

F V

kT I V
ln

q AAT 2

(4.5)

Where is the first integer which is greater than n. The plot of F(V) vs Voltage is given in Fig. 4.10.
At the minimum point of F(V), the values of barrier height at different temperature are calculated from the
equation:

b F (V0 )

V0

kT
q

(4.6)

5.5

Series Resistance ()

5.0
4.5
4.0
3.5
3.0
2.5
2.0
1.5
300

310

320

330

340

Temperature (K)

Fig. 4. 9 Series resistance-Temperature graph of fomyl-TIPPCu(II) diode.

47

0.88

299K
309K
319K
329K
339K

0.86

F(V) (Volt)

0.84
0.82
0.80
0.78
0.76
0.74
0.72
0

V (Volt)

Fig. 4. 10 F(V) vs V plot of formyl-TIPPCu(II)/p-Si diode

Fig. 4.11 shows that, the rising temperature of diode, decrease the ideality factor while increases the
barrier height. The non ideal behaviour and variation in barrier height of formyl-TIPPCu(II)/p-Si junction
diode at different temperatures indicate the presence of barrier inhomogeneity and/or other mechanism of
electron transport. At lower temperature, the flow of current is mostly through the region of lower barrier
height. The significantly larger value of ideality factor at room temperature may be caused by different
reasons. The higher values of ideality factors are attributed due to secondary mechanisms, oxide layer
between organic material and silicon substrate [18].

48

40
38

0.250

34

0.245

Ideality factor (n)

32
30

0.240

28
26

0.235

24
22

Barrier Heigh b0 (eV)

36

0.230

20
18

0.225
300

310

320

330

340

Temperature (K)

Fig. 4. 11 Variation of Zero bias barrier height and ideality factor of formyl-TIPPCu(II)/p-Si diode
with temperature from 299-339K.

4.4 Conclusions
The thin films of formyl-TIPPCu(II) were grown on the p-type silicon substrates by thermal
evaporation

technique to fabricate formyl-TIPPCu(II)/p-Si heterojunction diodes. The variation in

electrical characteristics of the fabricated device has been investigated in the temperature range of 299-339
K. The important parameters of diode like series resistance, ideality factor, reverse saturation current and
zero bias barrier height were extracted from I-V data. The parameters are strongly temperature dependent.

4.5 References

[1] Y. Karzazi, "Organic Light Emitting Diodes: Devices and applications," J. Mater. Environ. Sci, vol.
5(1), pp. 1-12, 2014.
[2] H. Klauk, U. Zschieschang, J. Pflaum and M. Halik, "Ultralow-power organic complementary
circuits," Nature, vol. 445, pp. 745-748, 2007.
[3] F. Aziz, M. H. Sayyad, K. Sulaiman, B. H. Majlis, K. S. Karimov, Z. Ahmad and G. Sugandi,
49

"Influence of humidity conditions on the capacitive and resistive response of an Al/VOPc/Pt co-planar
humidity sensor," Measurement Science and Technology, vol. 23(1), p. 014001, 2012.
[4] M. Tahir, M. H. Sayyad, F. Wahab, D. N. Khan and F. Aziz, "The electrical characterization of
Ag/PTCDA/PEDOT:PSS/p-Si Schottky diode by currentvoltage characteristics," Physica B, vol. 415,
pp. 77-81, 2013.
[5] D. N. Khan and M. H. Sayyad, "Extraction of Electronic Parameters ofPEDOT:PSS-PVA/n-Si
Heterojunction Diode," in Second International Conference on Computer Research and Development,
Kaula Lampur, 2010.
[6] F. E. Cimilli, M. Salam, H. Efeolu and A. Trt, "Temperature-dependent currentvoltage
characteristics of the Au/n-InP diodes with inhomogeneous Schottky barrier height," Physica B, vol.
404, no. 8-11, pp. 1558-1562, 2009.
[7] L. L. Li and E. W. G. Diau, "Porphyrin-sensitized solar cells," Chemical Society Reviews, vol. 42, pp.
291-304, 2013.
[8] H. X. Wei, Z. X. Bo, S. J. Yong, Z. J. Wen, Z. Y. Di and S. Zongbao, "Colorimetric Artificial Nose for
Monitoring Traditional Solid State Fermentation Process of Vinegar Pei," J Food Processing &
Beverages, vol. 1, pp. 1-6, 2013.
[9] D. N. Khan, M. H. Sayyad, M. Yaseen, M. A. Munawar and M. Ali, "Application of Formyl-TIPPCu
(II) for Temperature and Light Sensing," World Academy of Science, Engineering and Technology,
vol. 51, pp. 210-212, 2011.
[10] M. Yaseen, M. Ali, M. NajeebUllah, M. A. Munawar and I. Khokhar, "Microwave-Assisted Synthesis,
Metallation, and Duff Formylation of Porphyrins," J. Heterocyclic Chem., vol. 46, pp. 251-255, 2009.
[11] E. H. Rhoderick and R. H. Williams, Metal Semiconductor Contacts, 2nd ed., Oxford: Clarendon
Press, 1988.
[12] S. M. Sze, Physics of Semiconductor Devices, 2nd ed., New York: Wiley, 1981.
[13] S. M. Sze, Physics of Semiconductor Devices, 2nd ed, John Wiley & sons, 2004.
[14] C. T. Sah, R. N. Noyce and W. Shockley, "Carrier generation and recombination in pn-junctions and
pn-junction characteristics," Proc. IRE, vol. 45, p. 1228, 1957.
[15] S. Gildenblat, S. Cohen and G. Sh., Metal-Semiconducteur Contacts and Devices, VLSI Electronics,
New York: Academic, 1986.
[16] M. N. Borah, S. Chaliha, P. C. Sarmah and A. Rahman, "Studies on current-voltage characteristics of
50

ITO/(n)CdSe-Al heterojunctions," J. Optoelectron. Adv. Mater., vol. 10, pp. 2793-2799, 2008.
[17] H. Norde, "A modified forward IV plot for Schottky diodes with high series resistance," J. appl.
Phys., vol. 50, p. 5052, 1979.
[18] M. Soylu, I. S. Yahia, F. Yakuphanoglu and W. A. Farooq, "Modification of electrical properties of
Al/p-Si Schottky barrier device based on 2'-7'-dichlorofluorescein," J. Appl. Phys., vol. 110, pp.
074514-9, 2011.

51

Chapter 5
The sensing of Humidity by surface type Ag/formylTIPPCu(II)/Ag sensor for Environmental Monitoring
5.1 Introduction
Water which is present everywhere in the form of liquid, vapours or ice is essential for all forms of
life. It can be adsorbed on all surfaces as moisture and present in air as humidity. Its existence in air is
important for all living species. The relative humidity is one of the important factors which determine the
level of comfort. The sensing of humidity and moisture have great economic importance for prediction of
floods, preserving and processing of foodstuffs, for plants protection, for the maintenance of the optimum
conditions in manufacturing processes specially in electronic industries and for weather telemetry
applications [1]. It is important tool to control the climate indoors and to predict the climate outdoors for
monitoring environmental changes.
Effective humidity sensors have certain significant factors such as long term physical and chemical
stability, accuracy and repeatability, fast response time and cost effectiveness [2]. It is detected indirectly
from its effects on the materials. The sensing mechanism for humidity is either resistive or capacitive. In
the capacitive sensor, the change in relative humidity is detected by the variation in capacitance which is
caused by the change in dielectric constant due to water adsorption of sensing material while in the
resistive sensor, the variation occurs in the resistance of the material [3]. The capacitive technique is
considered as the most favorable for miniaturised humidity sensors [4]. There are varieties of materials
which can be used as active humidity sensing elements including ceramic, inorganic and organic
semiconductors [5, 6]. The organic materials exhibit excellent sensing behaviour due to their porous nature
as compared to inorganic which shows poor performance with respect to sensitivity, stability and
selectivity. The electrical properties like conductivity and dielectric constant of organic semiconductors
changes with the change in humidity and temperature. The Conventional humidity sensors are mostly based
on ceramic and inorganic semiconductors which have certain drawbacks. The ceramic based humidity
sensors show week humidity detective response and degradation in their sensitivity at high humidity due to
52

their pores widening which is caused by the diffusion of adsorbed water [7, 8]. They also need the periodic
regeneration of heat cleaning to wash out moistures to recover their humidity sensitive properties [9].
While the organic semiconductor based humidity sensors work efficiently in whole humidity levels. Porous
Si is also favourable semiconducting humidity sensing material but it gets contamination by its
environment due to reactivity [10]. The nonlinearilty, lack of reproducibility and temperature sensitivity are
others main limitations of porous Si based sensors [11]. The conventional humidity sensors are not only
much expensive than organic counterparts but also need high temperature fabrication procedures. While the
fabrication processes of organic sensors are not only simple but they also show low hysteresis. Due to
flexible nature of the organic materials, these sensors can be used for large area applications. Organic
sensors also need no heat cleaning process [12].
Organic materials are basically classified as polymers and small molecules. Organic Polymers have
attracted tremendous attention as active sensing materials due to their high sensitivity to humidity due to
their porous nature [13]. Conducting polymers are another important class of the organic materials which
have been used to monitor high humidity levels. Mostly the organic semiconductors are used in capacitive
type humidity sensors [14, 15].
Porphyrins which are basically macrocyclic compounds have high chemical and thermal stability.
They exhibit emission, absorption, charge transfer and complexing properties due to their characteristic
ring structure [16]. Porphyrins exhibit aromaticity because of having 22 electrons with 18 electrons in
direct conjugation [17]. For achieving certain specific properties, the metalloporphyrins are formed by
placing the metal ions into the central hole of the porphyrin ring. The copper based porphyrin i.e. formylTIPPCu(II) or 2-formyl-5,10,15,20-tetrakis(4-isopropylpheny)prophyrinatocopper(II) has been synthesised
by fitting copper ions into the central porphyrin ring. Its synthesis procedure has already been described
elsewhere [18]. The formyl-TIPPCu(II) has already been investigated for the sensing for temperature and
light [19].
Humidity is an important parameter which directly influence the environment so in this research
work formyl-TIPPCu(II) has been first time used as active sensing material for detecting humidity. The
purpose of this research is to explore the efficient sensing organic materials which can be used to fabricate
the humidity sensors for environmental monitoring in domestic or industrial processes. To avoid the
damages in the active layer and shortening in the device, the surface type sensor is fabricated instead of
sandwich configuration.
53

5.2 Experimental
To detect the variation in Relative humidity, the organic semiconductor formyl-TIPPCu(II) was used as
sensing material to fabricate its surface type sensors with silver electrodes. The title compoundformylTIPPCu(II) was synthesized by the method described by Yaseen et al[20] by placing the copper in central
vacant site of porphyrin and was purified by column chromatography.
The commercially available glass microscope slides were used as substrates. To avoid the different type
of contamination, the substrates were cleaned for 15 minutes in distilled water in ultrasonic bath, after
drying in dust free environment, the substrates were plasma cleaned for 8 minutes in thermal evaporator.
The silver electrodes with thickness of 100 nm were deposited on the substrates by Edward Auto 306
thermal evaporator with the deposition rate of 0.1nm/s by keeping inside pressure of the chamber at 10-5
mbar maintaining the uniformity in the metallic films. The gap of 40 m was produced between the
electrodes by masking technique. The thin films of formyl-TIPPCu(II) (thickness ~ 140nm) were grown on
the electrodes in same thermal evaporator under same deposition rate and chamber pressure. The schematic
diagram of the fabricated device is shown in Fig. 5.1.
Ag

formyl-TIPPCu(II)
Glass

Ag

Fig. 5. 1The cross-sectional view of surface type Ag/formyl-TIPPCu(II)/Ag humidity sensor

The surface morphology of the vacuum sublimated thin film of formyl-TIPPCu(II) was studied by
Atomic Force Microscopy ((NSC 35 Micromasch cantilevers) in the standard tapping mode (Fig. 5.2). The
capacitive and resistive measurements of the fabricated sensors were carried out by placing them in a
sealed chamber using digital hygrometer and LCR meter at the frequencies of 1kHz and 10kHz and
100kHz. The level of humidity in the chamber was controlled by injecting the Nitrogen gas after passing
through the water vessel. The measurements were carried out at room temperature (250C).

54

Fig.5. 2AFM image of formyl-TIPPCu(II) on glass substrate.

5.3 Results and discussion

5.3.1Atomic Force Microscopy
In the capacitive type humidity sensor, the dielectric constant of the active sensing material changes due to
adsorption of water which basically depends on the porosity of the material structure [21]. The voids which
appear during the growth of thin film provide rooms for tiny water droplets. The 3D AFM image (Fig. 5.3)
of the thin film of formyl-TIPPCu(II) shows that there are enough adsorption sites for water molecules due
to roughness of the film.

55

Fig.5. 33D AFM image of thin film of formyl-TIPPCu(II).

5.3.2Capacitance Humidity Characteristics

The capacitance - relative humidity relationship of Ag/formyl-TIPPCu(II)/Ag humidity sensor at different
frequencies of 1kHz, 10kHZ and 100kHz, is shown in Fig. 5.4.

1000

1kHz
10kHz
100kHz

Capacitance (pF)

800

600

400

200

0
40

50

60

70

80

90

100

RH%

Fig.5. 4Capacitance-relative humidity relationship of the Ag/formyl-TIPPCu(II)/Ag

56

The experimental results describe the increase in capacitance with the rise of relative humidity of the
device from 45% to 95% RH. There is sharp increase in capacitance of the sensor from 65% to 95% RH of
about 9.4 times at 1kHz, 4.6 times at 10kHz and 2.1 time at 100kHz of AC signal frequency of applied
voltage. The dielectric constant of the organic material increases due to adsorption of enough water
molecules which results in the rise of the capacitance of the sensor. Normally the dielectric constant of
organic materials is low i.e. lying between 4 to 8 [22, 23] but of water is high of about 80 [24]. So with the
adsorption of water the dielectric constant of the sensing material also increases. The adsorption of the
water depends on the porosity and the attractive forces between the surface of active organic material and
water molecules. AFM image shows that there is high degree of porosity in the formyl-TIPPCu(II)
structure. The increase in relative humidity results in the rise of adsorption of water molecules in the pores
of the film which increase the dielectric permittivity of the organic film. The dielectric permittivity of the
film is related with capacitance by following expression [25].

C S C0 w
d

(5.1)

Where d and w are the dielectric permittivities of the thin film of formyl-TIPPCu(II) at dry and wet
conditions and C0, CS are corresponding values of capacitance and n is the morphological factor.
Polarization of the organic material under the influence of external electric field is another factor for
the variation of capacitance [26]. The organic semiconductors like formyl-TIPPCu(II) acts as dielectric
having no free electrons. With the application of external electric field the bounded charges slightly
displace from their position causing the formation of dipoles in the organic material [27]. In humidity
sensor there are additional dipole formation (H+, OH-) in adsorbed water molecules which results the rise in
capacitance of sensor.

5.3.3Capacitance Frequency Characteristics

Fig. 5.5. exhibits the capacitance frequency relationships for four distinct humidity levels of 65%, 75%,
85% and 95%RH. There is no significant variation in the capacitance at high frequency of 100kHz as
compared to lower frequency of 1kHz of AC signal. At 95%RH, the capacitance of the sensor at 1kHz
frequency is 48.5 times greater than at 100kHz of the AC signal of the applied voltage, proving the fact of
unsuitability of organic semiconductors for high frequency electronic applications [28].

Organic
57

semiconductors have low mobility so they have insufficient time response of applied AC signals at higher
frequencies. At low frequency, the net polarization of material increases due to easier hoping of electrons
which results the increase in the capacitance of sensor. While at higher frequencies, the relaxation of charge
carrier is not as rapid as the time variation of the electric field which causes the decease in the capacitance
of the sensor [29, 30].

%95RH
%85RH
%75RH
%65RH

Capacitance(pF)

800

600

400

200

0
0

20

40

60

80

100

Frequency (kHz)

Fig.5. 5Capacitance-frequency relationship of the Ag/formyl-TIPPCu(II)/Ag sensor at 65%, 75%,

85% and 95%RH.

During the adsorption and desorption of water molecules, one of the important challenges faced by
humidity sensors is hysteresis which cannot be avoided completely because the rate of adsorption and
desorption is never same. The electrical parameters like capacitance and resistance of humidity sensors are
measured due to high porosity and moderate polarity of the organic thin film. The water molecules and
organic material are bounded together with hydrogen bonding and Van der Waal force [31, 32]. Desorption
of water starts when ambient air is drying down causing the destruction of physical bonds which results the
hysteresis at high level of humidity. Porosity of the film is another cause of hysteresis as it supports the
adsorption of water vapours but make difficult the rapid desorption [33]. The hysteresis property of the
humidity sensor of forlmyl-TIPPCu(II) was also studied at higher frequency of 1kHz and it was found
58

about 7% (Fig. 5.6). M. H. Sayyad et al [34] reported 9% hysteresis in capacitive measurements of surface
type Ag/ZnTIPP/Ag (Zn based porphyrin) humidity sensor at 1 kHz, Zubair et al [35] found 12%
repeatability in organic inorganic composite based humidity (Ag/Cu2O-PEPC-NiPC/Ag) sensor.

Capacitance (pF)

800

600

400

200

0
40

50

60

70

80

90

100

RH%

Fig.5. 6Hysteresis-relative humidity relationship for Ag/formyl-TIPPCu(II)/Ag.

5.3.4 Resistance Humidity Characteristics

Resistance relative humidity curves of Ag/formyl-TIPPCu(II)/Ag humidity sensor at 1kHz and
10kHz are shown in Fig. 5.7. The resistance of the fabricated sensor decreases with increase in relative
humidity from 45% to 95%RH. There is abrupt decrease in the resistance of the sensor from 45% to
80%RH. With the adsorption of water, the conductivity of the film increases which causes the decrease in
resistance with rise of humidity level. The electrical response of the sensor is due to proton hoping between
the chemisorbed hydroxyl groups at lower RH values [100]. The sensitivity of the humidity sensor is found
by the relation [101]

R0
% RH

(5.2)

59

Where R0 is starting resistance, R is the change in resistance R=Rmax-R0, and (%RH) is change
in relative humidity. The sensitivity of formyl-TIPPCu(II) is found 0.0196%RH.

1kHz
10kHz

Resistance(M

5
4
3
2
1
0
40

50

60

70

80

90

100

RH%

Fig.5. 7Resistance-relative humidity relationship of Ag/formyl-TIPPCu(II)/Ag sensor at 1kHz and

10kHz.

The long term stability of the fabricated sensor at room temperature (250C) has been experimentally
observed in the laboratory. The good stability of the sensor has been confirmed after 200 cycles at low/high
humidity (45%RH/95%RH) at a temperature of 250C. The reproducibility of the sensing material formylTIPPCu(II) based sensors have been checked by characterizing a number of devices of same structure and
dimension. The repeatability of the sensor is determined by hysteresis which depends on the temperature,
exposure time and total span of humidity cycles. Ag/formyl-TIPPCu(II)/Ag humidity sensor shows an
acceptable values of hysteresis which proves the repeatability of the device.

5.4 Conclusion
In this study, the humidity sensing capabilities of formly-TIPPCu(II) has been investigated by
fabricating surface type Ag/formyl-TIPPCu(II)/Ag humidity sensor. The variations in capacitance and
resistance of the sensor as function of relative humidity (45%-95%RH) have been observed. The fabricated

60

sensor exhibited the adequate sensorial properties and good stability. An acceptable value of hysteresis (~
7%RH) has been found. The film of formyl-TIPPCu(II) showed sensitivity of about 0.0196%RH.

5.5 References
[1]

J. Fraden, Handbook of Modern Sensors Physics, Designs, and Applications, New York: Springer,
2010.

[2]

C. Y. Lee and G. B. Lee, "Humidity sensors: A review," Sens. Lett, vol. 3, pp. 1-15, 2005.

[3]

Y. Sakai, Y. Sadaoka and M. Matsuguchi, "Humidity sensors based on polymer thin films," Sensors
& Actuators B, vol. 85, pp. 35-36, 1996.

[4]

Z. M. Rittersma, "Recent achievements in minitiarised humidity sensors-a review of transduction

techniques," Sensors and Actuators A, vol. 96, pp. 196-210, 2002.

[5]

B. Ertug, T. Boyraz and O. Addemir, "Investigation of the Electrical Conductivity and Humidity
Sensitivity Characterristics of BaTiO3 Ceramics with PMMA Additive," Archives of Metallurgy and
Materials , vol. 57, no. 2, pp. DOI: 10.2478/v10172-012-0043-2, 2012.

[6]

F. Aziz, M. H. Sayyad, K. Sulaiman, B. Majlis, K. S. Karimov, Z. Ahmad and G. Sugandi,

"Influence of humidity conditions on the capacitive and resistive response of an Al/VOPc/Pt coplanar humidity sensor," Meas. Sci. Technol, Vols. 23, 014001, 2012.

[7]

S. Chakraborty, K. Nemoto, K. Hara and P. T. Lai, "Moisture sensitive field effect transistors using
SiO2/Si3N4/Al2O3 gate structure," Smart Materials and Structures, vol. 8, p. 274, 1999.

[8]

R. K. Nahar, "Study of the performance degradation of thin film aluminum oxide sensor at high
humidity," Sens Actuators B, vol. 63, pp. 49-54, 2000.

[9]

E. Traversa, "Ceramic sensors for humidity detection: the state of the art and future development,"
Sensors & Actuators B, vol. 23, pp. 135-156, 1995.

[10]

J. N. Chazalviel and F. Ozanam, Surface modification of porous silicon, in Properties of Porous

Silicon, INSPEC, London, UK: L. Canham, ed., 1997.

[11]

H. Saha, "Porous Silicon Sensors- Elusive and Erudite," International Journal on Smart Sensing and
Intelligent Systems, vol. 1, pp. 34-56, 2008.
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[12]

T. Zhang, X. Tian, B. Xu, W. Dong, L. Sun, S. Xiang and D. Gao, "A polymer sensitive to humidity
and its electrical properties analysis," Journal of Materials Science Letters, vol. 19, pp. 1419-1422,
2000.

[13]

T. Fei, H. Zhao, K. Jiang, X. Zhou and T. Zhang, J. Appl. Polym. Sci. vol. 130, pp. 2056-2061,
2013.

[14]

B. Adhikari and S. Majumdar, "Polymers in sensor applications," Progress in Polymer Science, vol.
29, pp. 699-766, 2004.

[15]

Z. Ahmad, Q. Zafar, K. Sulaiman, R. Akram and K. S. Karimov, "A Humidity Sensing OrganicInorganic Composite for Environmental Monitoring," Sensors, vol. 13, pp. 3615-3624, 2013.

[16]

A. Rest, J. D. Coyle, R. R. Hill and D. R. Roberts(Eds.), Light, Chemical Change and Life: A
Source Book of Photochemistry, Walton Hall: The Open University Press, 1982.

[17]

M. Gouterman, The Porphyrins Vol.111, Part A, Physical Chemistry, New York: D. Dolphin (Ed.)
Academic, 1978.

[18]

M. Yaseen, M. Ali, M. Najeebullah, M. A. Munawar and I. Khokhar, "Microwave-Assisted

Synthesis, Metallation and Duff Formylation of Porphyrins," J. Heterocyclic Chem, vol. 46, pp. 251255, 2009.

[19]

D. N. Khan, M. H. Sayyad, M. Yaseen, M. A. Munawar and M. Ali, "Application of FormylTIPPCu (II) for Temperature and Light Sensing," World Academy of Science, Engineering and
Technology, vol. 51, pp. 210-212, 2011.

[20]

I. Sakai, Y. Sadaoka and M. Matsaguchi, "Humidity sensors based on polymer thin films," Sens.
Actuators B, Vols. 35-36, pp. 85-89, 1996.

[21]

F. Gutmann and L. E. Lyons, Organic Semiconductors, Part A, Florida, USA: Krieger Robert E.
Publishing Company, Malabar, 1981.

[22]

V. A. Kargin, Organic Semiconductors, Moscow: Nauka, 1968.

[23]

M. Bjorkqvist, J. Salonen, J. Paski and E. Laine, "Characterization of thermally carbonized porous

silicon humidity sensor," Sens. Actuators A, vol. 112, pp. 244-247, 2004.

[24]

J. G. Korvink, L. Chandran, T. Boltshauser and H. Baltes, "Accurate 3D Capacitance evaluation in

Integrated Capacitance Humidity Sensors," Sens. Mater, vol. 4, pp. 323-335, 1993.
62

[25]

M. A. Omar, Elementary Solid State Physics: Principles and Applications, MA, USA: AddisonWesley:Reading, 1975.

[26]

P. Lorrain and D. R. Corson, Electromagnetism: Principles and Applications, New York: Freeman,
1997.

[27]

K. J. Baeg, A. Facchetti and Y. Y. Noh, "Effects of gate dielectrics and their solvent on
characteristics of printed n-channel polymer field-effect transistors," J. Mater. Chem, vol. 22, p.
21138, 2012.

[28]

P. Bergo, W. M. Pontuschka, J. M. Prison, C. C. Motta and J. R. Martinelli, "Dielectric properties of

barium phosphate glasses doped with transition metal oxides," J Non-Cryst Solids, vol. 348, pp. 8489, 2004.

[29]

R. S. Kumar and K. Hariharan, "AC conductivity and electrical relaxation studies on 10CuI60AgI
30V," Mat Chem Phys, vol. 60(1), p. 28, 1999.

[30]

Y. Diamant, G. Marom and L. A. Broutman, "The effects of network structure on moisture

absorption of epoxy resins," J. Appl. Polym. Sci, vol. 26, pp. 3015-3025, 1981.

[31]

P. S. Anderson, "Mechanism for the behavior of hydroactive materials used in humidity sensors," J.
Atoms. Oceanic Technol, vol. 12, pp. 662-667, 1995.

[32]

A. Sun, Z. Li, T. Wei, Y. Li and P. Cui, "Highly sensitive humidity sensor at low humidity based on
the quaternized polypyrrole composite film," Sensors and Actuators B, vol. 142, pp. 197-203, 2009.

[33]

M. H. Sayyad, M. Saleem, K. S. Karimov, M. Yaseen, M. Ali, K. Y. Cheong, F. Ahmad and M.

Noor, "Synthesis of Zn(II) 5,10,15,20-tetrakis(4-isopropylphenyl) porphyrin and its use as a thin
film sensor," Appl Phys A, vol. 98, pp. 103-109, 2010.

[34]

N. Guermat, A. Bellel, S. Sahli, Y. Segui and P. Raynaud, "Electrical and structural characterisation
of plasma-polymerized TEOS thin films as humidity sensors," M. J. Condensed Matter, vol. 12, pp.
208-211, 2010.

[35]

Q. Y. Tang and Y. C. Chan, "Fast-response Polyimide/multiwall Carbon Nanotube Composite

Films," in 12th Electronic Packaging Technology Conference, Singapore, 2010.

63

Chapter 6
Application of formyl-TIPPCu(II) for temperature
and light sensing
6.1 Introduction
For the utilization of renewable energy sources, the assessment of environmental conditions is an
important factor which can be done by monitoring temperature, humidity barometric pressure, wind speed
and direction, rain fall and air pollution [1, 2]. The organic semiconductors based sensors can be used for
sensing application of these environmental parameters because organic materials are very sensitive to
temperature [3, 4], radiations [5], humidity [6, 7] and various gases [8, 9].
Temperature is the most important parameter of the environment. It has direct influence on the
physical, chemical, biological, mechanical and electronic systems. The efficient working of these systems
is possible only within a certain range of the temperatures. To optimise and control these systems under
temperature limits, the regular monitoring of temperature needs the temperature sensors. These sensors also
help to minimize the possible damages in electronic circuits due to rise or fall in temperature. The
reliability of the electronic devices can be enhanced by proper monitoring the temperature. The electrical
properties of the organic semiconductors are directly affected by the change in temperature, so these
materials can be used as active temperature sensing materials [10-12].
Porphyrin is the heterocyclic organic compound which is found in nature in the form of chlorophyll,
which is thought to be the best photo acceptor in nature. The free base porphyrin can be changed into
metalloporphyrin by inserting the metals into its core [13]. Due to its attractive properties, porphyrin has
been used for the fabrication of different organic devices such as junction diodes [14], sensors [7, 15] and
solar cells [16].
In

this

research

work,

copper

based

porphyrin

i.e.

2-formyl-5,10,15,20-tetrakis(4-

isopropylpheny)prophyrinatocopper(II) or formyl-TIPPCu(II) has been used to fabricate the organic sensor

for temperature and light sensing application.

64

6.2 Experimental
Thin film of organic semiconductor formyl-TIPPCu(II) is used as a sensing element for the
fabrication of Au/formyl-TIPPCu(II)/Au organic sensor. Microscope glass slides were used as substrates.
The substrates were cleaned ultrasonically in acetone for 25 minutes followed by thorough rinsing with
distilled water. After drying, the substrates were plasma cleaned for 5 minutes. The gold electrodes of 100
nm thickness were thermally deposited on the substrates by keeping 40 m gaps between them by using the
mask. Then the thin film of formyl-TIPPCu(II) of thickness 140 nm was thermally sublimed on the
substrates. For these thermal depositions, the Auto 306 vacuum coater with diffusion pumping system
(Edward) was used under a chamber pressure of 5.5 10-5 mbar. The thickness of formyl-TIPPCu(II) and
gold films were measured by an FTM5 crystal controlled thickness monitor. The cross-sectional view of
the fabricated Au/formyl-TIPPCu(II)/Au sensor is shown in Fig. 6.1.

formyl-TIPPCu (II)
Au

Au
Glass Substrate

Fig.6. 1Cross-sectional view of the Au/formylTIPPCu(II)/Au organic sensor.

The electrical capacitance and resistance were measured by using DVM 890L and Kiethley 196
digital multimeters. The temperature dependence measurements of the device were made using Karl Suss
PM5 probe station with a thermo chuk Alpha series system, model TP 0315A-TS-2 of Temprotic
Corporation, USA. The fabricated sensor was illuminated by a tungsten filament lamp at room temperature,
and the illumination measurements were made by CEM DT-1300 light meter.

6.3 Results and Discussion

Fig. 6.2 shows the capacitance-resistance versus temperature plots of Au/formyl-TIPPCu(II)/Au
surface type sensor. The measurements were made under the dark conditions at 40% RH. It has been
observed from these curves that capacitance increases by 4.3 times while resistance decreases by 4.4 times
65

with an increase in temperature from 27 to 1870C. The polarization and conductance of sensing film cause
the change in the magnitude of capacitance and resistance of the device [17]. With increasing temperature,
the molecular thermal movement becomes stronger, which increases the polarization and causing the
enhancement in the capacitance of the fabricated sensor. While the resistivity of the sensing material
decreases with the increase in temperature, according to the relation.
E

kT

T 0 exp

(6.1)

Where T is the resistivity at absolute temperature T, 0 is pre exponential factor, k is the Boltzmanns

0.06

0.12

0.05

0.10

0.04

0.08

0.03

0.06

0.02

0.04

0.01

0.02
20

40

60

80

100

120

140

160

180

RT/R0

CT/C0

constant and E is the activation energy of conduction.

200

Temperature [ C]

Fig.6. 2Capacitance/resistance temperature relationships for the Au/formyl-TIPPCu(II)/Au organic

sensor.
It can be observed from Fig. 6.3 that the capacitive and resistive measurements have the hysteresis
of 3.2 and 5.1%, which may be caused by polarization of the material.

66

0.12

0.05

0.10

0.04

0.08

0.03

0.06

0.02

0.04

0.01

0.02
20

40

60

80

RT/R0

CT/C0

0.06

100 120 140 160 180 200

0

Temperature [ C]

Fig.6. 3Hysteresis in the capacitive and resistive measurements of Au/formyl-TIPPCu(II)/Au organic

sensor.

Fig. 6.4 shows the relationship between relative capacitance and illumination for Au/formylTIPPCu(II)/Au surface type photocapacitive sensor. Where Cd and Cph are capacitances under dark
conditions and illumination respectively. This plot shows that the photocapacitance of fabricated sensor
increases about 13.2 times with the increase in illumination from 0 to 25000 lx. The concentration of
charge carriers, i.e. electrons, holes, ions and dipoles increases with increasing illumination, which causes
the increase in polarizability in the film which results in the increase in the capacitance of the sensor [18,
19]. The total polarizability () can be written as

dip i e t

(6.2)

Where dip, i, e and t are polarizability under illumination due to dipoles, ions, electrons and the transfer
of charge carriers, respectively.
The change in capacitance of the device may be due to electronic and ionic polarizability. The
electronic polarizability arises due to the relative displacement of orbital electrons, while the ionic
polarizability is due to charge-transfer complexes in the formyl-TIPPCu(II). The capacitance is actually
depending on the relative permittivity (r) of the material who depends on the polarizability according to
Clausius-Mossotti equation [18].

r 1 N

r 2 3 0

(6.3)
67

Where N is the concentration of charge carriers, r is the relative permittivity and 0 is the permittivity of
free space.

14
12

CPh/Cd

10
8
6
4
2
0
0

5000

10000

15000

20000

25000

Illumination (lux)

Fig.6. 4 Capacitance- illumination relationship for the Au/formyl-TIPPCu(II)/Au organic sensor.

6.4 Conclusions
The organic semiconductor formyl-TIPPCu(II) has been successfully used for the fabrication of
surface type Au/formyl-TIPPCu(II)/Au organic sensor. The changes in capacitance and resistance of the
sensor with temperature and light have been observed. The capacitance has increased by 4.3 times while
resistance of the fabricated sensor decreased by 4.4 times by rising temperature from 27 to 1870C. An
acceptable hysteresis for capacitive and resistive measurements was found. The rise of 13.2 times in
capacitance due to illumination was also observed. The association of photocapacitive response of the
organic sensor was assumed with polarization due to the transfer of photo generated electrons and holes.

68

6.5 References
[1]

A. Joyce, J. Adamson, B. Huntley, T. Parr, R. Baxter, "Standardization of temperature observed by

automatic weather stations," Environmental Monitoring and Assessment, vol. 68, pp. 127-136,
2001.

[2]

W. Qihao, Y. Shihong, "Urban air pollution patterns, land use and thermal landscape: an
examination of the linkage using GIS," Environmental Monitoring and Assessment, vol. 117, pp.
463-489, 2006.

[3]

S. A. Moiz, M. M. Ahmed, Khasan

S. Karimov, "Effects of Temperature and Humidity on

Electrical Properties of Organic Semiconductor Orange Dye Films Deposited from Solution,"
Japanese Journal of Applied Physics, vol. 44, pp. 1199-1203, 2005.
[4]

M. M. Ahmed, Kh.S. Karimov, S.A. Moiz, "Photoelectric behavior of n-GaAs/orange dye, vinylethynyl-trimethyl-piperidole/conductive glass sensor," Thin Solid Films, vol. 516, pp. 7822-7827,
2008.

[5]

P. Bhattacharya, Semiconductor Optoelectronic Devices. New Jersey: Prentice Hall International,

1994.

[6]

F. Gutman, L. E. Lyons, Organic semiconductors, Part A. Malabar, Florida, U.S.A: Krieger Robert
E. Publishing Company, 1981.

[7]

M. Saleem, M. H. Sayyad, Khasan S Karimov, Muhammad Yaseen Mukhtar Ali, "Synthesis and
application

of

Ni(II)

5,10,15,20-tetrakis(4-isopropylphenyl)porphyrin

in

surface-type

multifunctional sensor," Phys. Scr, vol. 82, pp. 015703 (6pp), 2010.
[8]

H. Bai, Gaoquan Shi, "Gas Sensors Based on Conducting Polymers," Sensors, vol. 7, pp. 267-307,
2007.

[9]

I. Muzikante, Vicente Parra, Rorijs Dobulans, Egils Fonavs, Janis Latvels, Marcel Bouvet, "A
Novel Gas Sensor Transducer Based on Phthalocyanine Heterojunction Devices," Sensors, vol. 7,
pp. 2984-2996, 2007.

[10]

Y. Kurazumi, T. Tsuchikawa, J. Ishii, K. Fukagawa, Y. Yamato and N. Matsubara, "Radiative

and

convective heat transfer coefficients of the human body in natural convection," Building

and Environment, vol. 43, pp. 2142-2153, 2008.

[11]

B. B. J. Basu and N. Vasantharajan, "Temperature dependence of the luminescence lifetime of

a europium complex immobilized in different polymer matrices," Journal of Luminescence,

69

vol. 128, pp. 1701-1708, 2008.

[12]

D. N. Khan, M. H. Sayyad, F. Wahab, M. Tahir, M. Yaseen, M. A. Munawar and

M. Ali, "Temperature dependant electrical properties of formyl-TIPPCu(II)/p-Si
heterojunction diode," Modern Physics Letters B, vol. 28(2014),
p. DOI:10.1142/S0217984914501000, .

[13]

X. Zhou, "Synthesis and Characterization of Novel Discotic Liquid Crystal Porphyrins for Organic
Photovoltaics," vol. PhD. Kent, Ohio, USA: Kent State University, 2009.

[14]

T. J. Savenije, Ellen Moons, Gerrit K. Boschloo, and Albert Goossens, Tjeerd J. Schaafsma,
"Photogeneration and transport of charge carriers in a porphyrin p/n heterojunction," Physical
Review B, vol. 55, pp. 9585-9592, 1997.

[15]

M. Saleem, M. H. Sayyad, K. S. Karimov, M. Yaseen, Mukhtar Ali, "Cu(II) 5,10,15,20-tetrakis (4isopropylphenyl) porphyrin based surface type resistive - capacitive multifunctional sensor,"
Sensors and Actuators B, vol. 137, pp. 442-446, 2009.

[16]

T. Oku, Akihiro Takeda, Akihiko Nagata, Tatsuya Noma, Atsushi Suzuki, Kenji Kikuchi,
"Fabrication and Characterization of Fullerene-Based Bulk Heterojunction Solar Cells with
Porphyrin, CuInS2, Diamond and Exciton-Diffusion Blocking Layer," Energies, vol. 3, pp. 671685, 2010.

[17]

J. Wang, Wang X-H, Wang X-D, "Study on dielectric properties of humidity sensing nanometer
materials," Sensors Actuators B, vol. 108, pp. 445-449, 2005.

[18]

F. Gutman, L.E. Lyon, Organic Semiconductors: Krieger Robert E. Publishing Company, Malabar,
Florida, USA, 1981.

[19]

M. Iwamoto, Manaka. T, "Organic lms and control of currentvoltage characteristics by the

surface polarization," presented at Proc Int. Symp. on Super-Functionality Organic Devices (IPAP
Conf. Series vol 6), 2005.

[20]

M. A. Omar, Elementary Solid State Physics: Principles and Applications: Pearson Education,
Singapore, 2002.

70

Chapter 7
Study of Anthracenediimide Derivatives for nchannel Organic thin film transistors
7.1 Introduction
The high order mechanical flexibility of organic semiconductors enables their use
for flexible, foldable and rollable electronic devices which seems difficult with
conventional inorganic materials [1]. One of special feature of organic materials is the
tailorability in their structure and other properties for their use for different novel
application like smart windows, e-paper and flexible electronic and optoelectronic
devices. The organic molecules have week van der Waal interactions, so they can be
processed at low temperature which provide the opportunities to develop electronic
devices with less cost as compared to traditional inorganic devices.
Over the last few years, organic thin film transistors have received considerable
attention due to their potential applications in low cost and flexible integrated circuits
such as wearable textile, active matrix displays, RFID tags and organic complementary
circuits [2, 3].

OTFTs also play important role for the exploration of important

parameters of the organic materials like charge mobility, on/off current and threshold
voltage. The organic materials which are used for the fabrication of OTFTs, either be p or
n or ambipolar properties. The p-channel OTFTs have exhibited high mobility and
stability but the importance of n-type OTFTs could not be ignored due to their use in
greater power efficient complementary circuits.
The logic gates with low power dissipation and improved noise margin are the
basic requirements of the next generation all organic integrating complementary circuits
which can be achieved by assembling hole and electron transporting (p and n channels)
organic thin film transistors [4, 5].

71

There are certain factors which have crucial role on the performance of the
OTFTs such as nature of organic material (chemical structure and intermolecular
interaction), electrodes and gate dielectric, device configuration, the morphology of
active layer, energy alignments between organic material and electrodes and between the
gate and organic semiconductors [6].
Organic thin film transistor is surface sensitive device, its performance depends
on the nature of interfacial layers between organic and the dielectric layers [7, 8]. The
electron trapping by moisture or hydroxy group at the interface of semiconductor and
dielectric is the main hurdle for getting good performance of n-channel OTFTs. The
electron mobility in these OTFTs can be enhanced by either modification in chemical
structure of organic semiconductors or by dielectric surface modification. The density of
trap sites can be reduced by either developing self assembly monolayer (SAM) or by
depositing a buffer layer of polymer on the dielectric surface.
Small molecules based OTFTs show high performance due to their purity and
crystalline nature. A variety of small molecules like rubrene, pentacene, phtalolocyanine
etc. have been used for the fabrication of OTFTs [9, 10]. The air stable n-channel OTFTs
of ADCI8 have been reported with 2.0 10-5 cm2/Vs [11], so in this research work, the nchannel OTFTs of ADCI8 and newly synthesised ADCI7 have been fabricated to get the
high value of mobility.

7.2 Device Fabrication & Characterization

Organic

thin

film

anthracenetetracarboxydiimide

transistors
(ADCI7)

(OTFTs)
and

of

N,N-di-n-heptyl-2,3:6,7N,N-di-n-octyl

2,3:6,7

anthracenetetracarboxydiimide (ADCI8) were fabricated in a bottom gate/top contacts

configuration (with symmetric Au drain and source electrodes) and thin films were grown
at room temperature on heavily n-doped silicon wafer (0.01 Ohm cm) covered with
thermally grown SiO2 layer (thickness ~ 200 nm, Ci=110-8F/cm2). Prior to deposition of
thin films, the substrates were cleaned to eliminate contaminates from the surface. All
samples were sonicated

in acetone and 2-propanol for 5-10 minutes to remove

physisorbed impurities and any other tiny dust specs. After that, the samples were
72

cleaned in freshly prepared piranha solution for 15 minutes.

Then substrates were

thoroughly rinsed by sonication in deionized water and dried in a steam of nitrogen gas.
Thin film of ADCI7 and ADCI8 were grown by vacuum deposition (10-6 to 10-7 mbar,
deposition rate 0.2-0.4 /sec) on SiO2/Si covered with a thin layer of PMMA and HMDS
treated. Thin films of PMMA in Toluene solution were deposited on SiO2 by spin coating
technique and then annealed for one hour at temperature of 1500C. Au drain and source
electrodes were uniformly deposited (at 10-6 mbar, deposition rate 0.1-0.3 /sec) to
prevent possible damages to organic film. The schematic diagram of bottom gate/top
contact OTFT of ADCI7 is shown in Fig. 7.1. The characterization of the fabricated
OFETs was performed in vacuum and ambient atmosphere in Keithley 4200-SCS.

Drain
Au

Source
Au
ADCI7

SiO2
n-Si
Fig. 7. 1 Schematic diagram of bottom gate/top contact n-channel OTFT of ADCI7

7.3 Thin-lm X-ray diffraction

X-ray diffraction measurements of thin films of ADCI7 and ADCI8 revealed that
patterns of both films showed sharp peaks and estimated d spacing is 2.19 and 2.37 nm
respectively (Fig.7.2).

73

30000

X-ray intensity (a.u)

C8=2.37nm

20000

ADCI8

C7=2.19nm
10000

ADCI7
0
0

20

40

2(deg)

Fig. 7. 2 X-ray diffraction measurements of thin films of ADCI7 and ADCI8

7.4 Thin film morphology

The surface morphology of early growth stage of vacuum sublimed films of ADI7
and ADI8 was studies by Atomic force microscopy (AFM) in the scanAsyst mode. Fig.
7.3 and 7.4 show the AFM micrographs and the histogram of the height profile of thin
films of ADI7 and ADI8 deposited on PMMA treated SiO2/Si at the deposition rate of 0.1
/s while the substrates were kept at room temperature. The typical three dimensional
island (Volmer-Weber) growth was observed from AFM analysis of early growth films.
The formation of 3D islands illustrates the stronger molecule-molecule interactions than
molecule-surface interactions.

74

1.0

Counts (a.u)

0.8

0.6

0.4

0.2

0.0
0

Height (nm)

Fig. 7. 3 AFM micrographs and the histogram of the height profile of thin films of
ADI7

1.2

Counts (a.u)

1.0

0.8

0.6

0.4

0.2

0.0
2

10

Height (nm)

Fig. 7. 4 AFM micrographs and the histogram of the height profile of thin films of
ADCI8

The early stages growth of ADI7 film consists of sub-monolayers with average
height of 2-3 nm and average size of 0.004 m2. By increasing the thickness of the film,
the grains seem to continue growing in one dimension with no substantial lateral growth
and cover the entire surface with number of grain boundaries.
Topographical AFM image of ADI8 also show one dimensional grain growing trend with
number of grain boundaries is shown in Fig. 7.4. The average height sub-monolayers is
2.40 nm and average size of .0036 m2.

75

7.5 Thin-lm transistor device characterization

OTFTs of ADI7 and ADI8 were fabricated by depositing thin films (50 nm) of
these organic materials on the PMMA/HMDS treated SiO2/Si substrates. PMMA/HMDS
were used on SiO2 to minimize the effect of electrons trapping by silanol groups. To
explore the type of majority charge carriers, characterization of the devices were
evaluated under negative and positive gate bias in vacuum.
The performance of the OTFTs was measured in vacuum at room temperature.
Fig. 7.5 and 7.7 show the output characteristics of ADCI8 and ADCI7 based n-channel
OTFTs which basically represents the source to drain current (IDS) vs voltage (VDS)
characteristics at different values of gate bias (VGS). The increase in the channel current
IDS with the rise in voltage VDS at positive gate voltage VGS shows the formation of nchannel OTFTs. At low drain voltage, these characteristics show the ohmic behavior but
at higher drain voltage, the pinching off the IDS - VDS characteristics is observed with the
existence of the current saturation which confirms that these n-channel OTFTs also
follow the standard FET theory [12]. The IDS - VDS curves can be used to find the charge
mobility for (VDSVDS-Vth) by using relation

(7.1)

Where W/L is the ratio of width and length of the channel, Ci is its capacitance,
Vth is the threshold voltage and is charge mobility.
The values of charge mobility for the PMMA surface modifies OTFTs of ADCI8
and ADCI7 were found 0.1110-2 and 0.4110-2 cm2V-1S-1, while for HMDS, 0.2510-3
and 0.1510-3 cm2V-1S-1,

respectively.

These values are much greater than the

previously reported mobility of ADCI8 [11].

Fig. 7.6 and 7.8 depict the transfer (IDS VGS) characteristics of ADCI8 and
ADCI7 OTFTs. These curves show that the on/off ratio of these OTFTs is of the order of
104. The threshold voltage for each transistor has also been measured by transfer
characteristics. Table 7.1 shows the values of mobility, on/off ratio and threshold voltage
of OTFTs of ADCI8 and ADCI7.
76

The OTFTs treated with PMMA show high mobility as compare to HMDS treated
dielectric because the PMMA has the good hydrophobicity which prevents the moistures
in penetrating to dielectric layer. The PMMA helps in the molecular ordering of ADCI7
and ADCI8 on the SiO2 dielectric layer and minimize the grain boundaries which results
the reduction in electron trapping and increasing the mobility of the OTFTs [13].

Table 7.1

ADCI8
ADCI8
(PMMA)
ADCI8
(HMDS)
ADCI7
(PMMA)
ADCI7
(HMDS)

Deposition
temp (0C)
900C
230C (rt)

(cm2V-1S-1)

Ion/Ioff

Vth (V)

2.010-5
1.07 10-3

104
104

45 [11]
55

230C (rt)

2.49 10-4

104

43

230C (rt)

4.11 10-3

104

65

230C (rt)

1.45 10-4

104

58

0.10
120V

0.08

0.06
ISD(A)

Compound

0.04

0.02

105V

0.00

90V

20

40

60

80

100

120

140

VSD(V)

Fig. 7. 5 Output characteristics of ADCI8

77

0.7

305.9
112.5

0.6

41.4
0.5

15.2

1/2

IDS(nA)

0.4

2.1

(IDS) (A)

5.6

0.3

1/2

0.8
0.3

0.2

0.1
0.1
0.0
0.0
0

20

40

60

80

100

120

VG(V)

Fig. 7. 6 Transfer characteristics of ADCI8

0.7

120V
0.6

0.5

ISD (A)

0.4

0.3

105V
0.2

0.1

90V
0.0
0

20

40

60

80

100

120

140

VSD(V)

Fig. 7. 7 Output characteristics of ADCI7

78

831.5

1.0

112.5

0.8

0.6

1/2

(IDS) (A)

IDS(nA)

15.2

2.1
0.4

1/2

0.3
0.2
0.0
0.0
0

20

40

60

80

100

120

VG (V)

Fig. 7. 8 Transfer characteristics of ADCI7

7.6 Conclusion
The n-channel organic thin film transistors of ADCI7 and ADCI8 were fabricated
on dielectric layers of SiO2. To minimize the trapping of electron the dielectric surface
were modified by buffer layer of PMMA and self assembly monolayer of HMDS. The
high charge mobility of ADCI8 was found as compare to already reported value. The
newly synthesised organic material of same family ADCI7 has also shown high mobility.
Both OTFTs exhibited the on/off ratio of order of 104.

7.7 References

[1] H. Klauk, "Organic thin-film transistors," Chem.Soc.Rev, vol. 39, p. 26432666,

2010.
[2] H. Sirringhaus, N. Tessler and R. H. Friend, "Integrated optoelectronic devices
79

based on conjugated polymers," Science, vol. 280, p. 17411744, 1998.

[3] A. N. Flora, W. Yiliang and S. O. Beng, Organic Thin Film Transistor Integration: A
Hybrid Approach, John Wiley & Sons, 2011.
[4] B. Crone, A. Dodabalapur, Y. Y. Lin, R. W. Fillas, Z. Bao, A. LaDuca, R.
Sarpeshkar, H. E. Katz and W. Li, "Large-scale complementary integrated circuits
based on organic transistors," Nature, vol. 403, pp. 521-523, 2000.
[5] D. J. Gundlach, K. P. Pernstich, G. Wilckens, M. Grter, S. Haas and B. Batlogg,
"High mobility n-channel organic thin-film transistors and complementary
inverters," J. Appl. Phys, vol. 98, p. 064502, 2005.
[6] C. Wang, H. Dong, W. Hu, Y. Liu and D. Zhu, "Semiconducting-Conjugated
Systems in Field-Effect Transistors: A Material Odyssey of Organic Electronics,"
Chem. Rev, vol. 112, pp. 2208-2267, 2012.
[7] T. Muck, V. Wagner, U. Bass, M. Leufgen, J. Geurts and L. W. Molenkamp, "In situ
electrical characterization of DH4T field-effect transistors," Synthetic Metals, vol.
146, pp. 317-320, 2004.
[8] R. Ruiz, A. Papadimitratos, A. C. Maye and G. G. Malliaras, "Thickness dependence
of mobility in pentacene transistors," Adv. Mater, vol. 17, p. 1795, 2005.
[9] D. Braga, M. Campione, A. Borghesi and G. Horowitz, "Organic MetalSemiconductor Field-Effect Transistor (OMESFET) Fabricated on a Rubrene Single
Crystal," Advanced Materials, vol. 22, pp. 424-428, 2010.
[10] S. Lee, G. Jo, S. J. kang, G. Wang, M. Choe, W. Park, D. Y. Kim, Y. H. Kahun and
T. Lee, "Enhanced Charge Injection in Pentacene Field-Effect Transistors with
Graphene Electrodes," Adanced Materials, vol. 23, pp. 100-105, 2011.
[11] Z. Wang, C. Kim, A. Facchetti and T. J. Marks, "Anthracenedicarboximides as AirStable N-Channel Semiconductors for Thin-Film Transistors with Remarkable
Current On-Off Ratios," J. Am. Chem. Soc, vol. 129, pp. 13362-13363, 2007.
[12] K. Nomura, H. Ohta, A. Takag, T. Kamiya, M. Hirano and H. Hosono, "Roomtemperature fabrication of transparent flexible thin-film transistors using amorphous

80

oxide semiconductors," Nature, vol. 432, pp. 488-492, 2004.

[13] J. Y. Kim, J. M. Kim, T. S. Yoon, H. H. Lee, D. Jeon and Y. S. Kim, "Pentacene
Thin Film Transistors with Various Polymer Gate Insulators," Journal of Electrical
Engineering & Technology, vol. 4, pp. 118-122, 2009.

81

Summary
In this research, the organic semiconducting materials formyl-TIPPCu(II), ADCI7
and ADCI8 have been investigated to explore their electronic and optoelectronic
properties for their applications for developing different organic devices.
The junction diodes and organic sensors of formyl-TIPPCu(II) have been
fabricated by thermal evaporation technique. The electronic parameters of junction diode
of formyl-TIPPCu(II) with p-type silicon were found strongly temperature dependent.
The ideality factor decreases while the barrier height decreases with the rise of
temperature from 299-339K. The parasitic series resistance of the diode which is
basically limiting the current in the device decreases with the increase in temperature.
The formyl-TIPPCu(II) has also been used as active sensing material to detect the
humidity, temperature and light. The surface type Ag/formyl-TIPPCu(II)/Ag humidity
sensors have been fabricated for the detection of relative humidity by measuring the
capacitance and resistance of the sensors from 45% to 95%RH. The remarkable change in
capacitance and resistance has been observed at different humidity levels. An acceptable
7% hysteresis has also observed in these sensors at the frequency of 1kHz of ac signal.
The ability of formyl-TIPPCu(II) for sensing light and temperature has been
studied by fabricating the surface type Au/formyl-TIPPCu(II)/Au sensor. With the rise of
temperature from 27oC to 180oC, the increase in relative capacitance of 4.3 times has
been observed. While the same sensor exhibited 13.2 time rise in relative capacitance by
increasing the illumination from dark to 25000 lx which prove that formyl-TIPPCu(II)
can be used as active sensing material.
Newly synthesised n-type organic semiconductors ADCI7 and ADCI8 have been
used to fabricate n-channel organic thin film transistors. The appreciable increase in the
mobility of ADCI8 has been observed as compared to already reported its value, while
ADCI7 as the compound of same show high mobility and on/off ratio. To get the high
performance of OTFTs, the surface of dielectric has been modified by buffer layer and by
self assembly monolayer of PMMA and HMDS respectively.

82

Future Work
The low cost, light weight and flexible organic complementary circuits is the need of next
generation electronics. The n-channel OTFTs have still limitations which can be minimized by introducing
the air stable n-type organic semiconductors having the electron transporting capability. The atmospheric
humidity also affects the mobility of n-type organic materials which can be reduced by synthesising the
materials which resist these environmental effects or introducing a proper packaging to avoid the
wandering atmospheric water droplets. By improving the fabrication techniques, the performance of the nchannel OTFTs can also be enhanced.
As the organic single crystal devices show higher performance than the amorphous or
polycrystalline materials, so a comprehensive study is required to develop the single crystal of the organic
materials and to fabricate their devices on nanoscale.
For developing highly efficient organic devices, the need is to know the chemistry of the organic
materials to explore their electronic and optoelectronic properties.

Dil Nawaz Khan

83