1318S

Fabrication and Investigation of Organic and Nano
Materials Based Sensors

By
Muhammad Tariq Saeed

Supervisor
Prof. Dr. Fazal Ahmad Khalid SI

Co-Supervisor
Prof. Dr. Khasan S. Karimov

THIS DISSERTATION IS SUBMITTED TO GIK INSTITUTE, IN PARTIAL FULFILLMENT OF THE
REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN MATERIALS ENGINEERING
Faculty of Materials Science and Engineering
GIK Institute of Engineering Sciences and Technology, Topi, Pakistan
Spring 2012
II

III

DEDICATED TO
MY BELOVED GRAND MOTHER (AYESHA MAI) AND AUNTIES
(SAFIA BIBI AND FAZALAN MAI) WHO LEFT ME FOREVER

IV

Acknowledgements
All praises and glories are for Almighty Allah the most Merciful and The Most Beneficent Who
blessed me with ability and courage to complete this dissertation. I supplicate to Almighty Allah
to shower his countless blessings on his Last Prophet Muhammad (PBUH) who is the persistent
source of knowledge and torch of guidance to all mankind; and messenger of peace for all
creatures.
I am highly indebted to my supervisor Prof. Dr. Fazal Ahmad Khalid and co-supervisor Prof. Dr.
Khasan Sanginovich Karimov for their kind supervision and sincere guidance. I can not convey
my entire feelings in words but I can pray to Almighty Allah (SWTA) to reward them for their
kindness. Really it is the great honor for me that I am student of well renowned scholars who are
among the leaders of their respective fields.
I am thankful to Higher Education Commission of Pakistan for providing me MS leading to PhD
Scholarship through its Indigenous PhD program. I am also highly indebted of Pakistani nation
and the Pakistani soil for financial support provided by HEC during this period.
I am grateful to all the faculty members Faculty of Materials Science and Engineering especially
Dr. Fida Muhammad, Dr. Zain ul Abdein, Dr. Fahd Nawaz Khan, Dr. Aqeel A. Taimoor, Mr.
Sheraz M. Khakwani and Syed Zameer Abbas. I am also thankful to my colleagues particularly
Mr. Mustasim Billah Bhatty, Muhammad Umer Farooq, Dr. Hamid Zaighum, Dr. Rana Abdul
Shakoor, Mr. Nabi Buksh, Hafiz Tareq Manzoor, Ghazanfar Saeed, Irfan Haider Abidi, Adnan
Maqbool and Asif Hussain.
I would like to appreciate the assistance of FMSE lab staff particularly Shahzad Raza, Shoaib
Rasool, Afsar Khan, Maroof, Atiq Qurashi and Safeer Ahmad. Moreover, I will never forget the
cooperation of Mr. Khalid Khan, Mr. M. Shafiq, Mr. Nizakat Khan and Jameel Shah.
I highly acknowledge my family for their love, kindness and support for my whole life. They
have always been a source of inspiration for me. By virtue of their prayers, I succeeded in my
life. I am also thankful to my uncle Malik Muhammad Hussain Chani and his family for their
moral support and encouragement.
V

Declaration

This is to certify that the results presented in this dissertation are my original work performed
entirely by myself during the course of my PhD studies at Ghulam Ishaq Khan Institute of
Engineering Sciences and Technology, Topi, Pakistan. This dissertation has not been submitted
to any other university in whole or in part. Prior approval must be accorded to use the material
contained in or derived from this dissertation.

Muhammad Tariq Saeed
Reg. No. MM0618

VI

Journal Publications
1. Carbon nanotubes-cuprous oxide composite based pressure sensors, Khasan Sanginovich
Karimov, Muhammad Tariq Saeed Chani, Fazal Ahmad Khalid, Adam Khan, Rahim
Khan, Chinese Physics B. Vol. 21, No. 1 (2012) 016102-1-5.
2. Carbon nanotubes-cuprous oxide composite based strain sensors, Khasan Sanginovich
Karimov, Muhammad Tariq Saeed Chani, Fazal Ahmad Khalid, Adam Khan Physica E,
Vol. 44, No. 4 (2012) 778-781.
3. Effect of displacement on resistance and capacitance of the polyaniline film, Khasan
Sanginovich Karimov, Muhammad Tariq Saeed, Fazal Ahmad Khalid, Syed Abdul Moiz,
Chinese Physics B, Vol. 20, No. 4 (2011) 040601-5.
4. Carbon nanotubes film based temperature sensor Khasan Sanginovich Karimov,
Muhammad Tariq Saeed Chani, Fazal Ahmad Khalid, Physica E, Vol. 43, No. 9 (2011)
1701-1703.
5. Organic Cu/Cellulose/ PEPC/Cu Humidity Sensor, Muhammad Tariq Saeed, F. Ahmad
Khalid, Kh. S. Karimov, M. Shah, OAM-RC, Vol. 4, No. 6 (2010) 88-892.
6. Carbon nanotubes based strain sensors, Khasan Sanginovich Karimov, Fazal Ahmad Khalid,
Muhammad Tariq Saeed Chani, Measurements, 10.1016/j.measurement.2012.02.003.
7. Carbon Nanotubes Based Flexible Temperature Sensor, Kh.S. Karimov, F.A. Khalid, M.
Tariq Saeed Chani, A. Mateen, M. Asif Hussain, A. Maqbool, OAM-RC Vol. 6, No. 1-2
(2012) 212-214.
8. Orange dye-polyaniline composite based impedance humidity sensors, Muhammad Tariq
Saeed Chani, Kh.S. Karimov, F. Ahmad Khalid, S. Zameer Abbas, Chinese Physics B
(Accepted).
9. Polyaniline based impedance humidity sensors, Muhammad Tariq Saeed Chani,
Kh.S.Karimov, F. Ahmad Khalid, S.A.Moiz, Solid State Sciences (under review).

VII

Conference Publications
1. A study of V
2
O
4
-PEPC composite based resistance temperature sensors Muhammad
Tariq Saeed, Kh.S. Karimov, F. Ahmad Khalid, M. Farooq, M. Saleem, , 1
st
Saudi
International Electronics, Communications and Photonics Conference (SIECPC-2011),
April 23-26, 2011, Riyadh Saudi Arabia.
2. Temperature Sensing Properties of Organic-Inorganic Ag/p-CuPc/n-GaAs/Ag Cell, Kh. S.
Karimov, F. Ahmad Khalid, Muhammad Tariq Saeed, T.A. Qasuria, Z.M. Karieva and
M. Farooq, International Symposium on Vacuum Science and Technology (ISVST),
November 2-6, 2010, Islamabad, Pakistan.

VIII

Abstract
This work presents the fabrication and investigation of organic and nano materials based sensors
for humidity, temperature and electromechanical applications. Polyaniline (PANI), orange dye
(OD)-PANI composite and of cellulose- poly-N-epoxypropylcarbazole (PEPC) have been used
for the fabrication of surface type humidity sensors. The sensors are fabricated by depositing
films of various thicknesses on glass substrates between pre-deposited metallic electrodes. The
sensing mechanism is based on the impedance and capacitance variations due to the absorption
or desorption of water vapors. The consequences of annealing, measuring frequency and
absorption-desorption behavior of the sensor have been discussed in detail. For all sensors
impedance-humidity relationship shows more uniform change as compared to capacitance-
humidity relationship in the given range humidity.
The temperature sensors have been fabricated by using multiwalled carbon nanotubes
(MWCNTs), V
2
O
4
-PEPC composite and CuPc on n-GaAs. The CNTs based sensors are
fabricated by the deposition CNT nanopowder on a paper substrate and on adhesive elastic
polymer tape. The nominal thickness of the CNT films on paper substrates is 3040 m while
that of elastic substrate is ~ 300-430 m. The DC resistance of the sensors decreases with
increase in temperature. For both types sensors, the resistance-temperature relationship shows
wide range sensitivity.
The V
2
O
4
-PEPC composite based temperature sensors are fabricated by drop-casting the blend of
composite into the gap between preliminary deposited silver electrodes on glass substrates. The
thickness of the V
2
O
4
-PEPC films is in the range of 20-40 m. It is found that with increase in
temperature the AC resistance of the samples decreases by 10-12 times. The response recovery
time is also measure.
The Ag/p-CuPc/n-GaAs/Ag cells are fabricated by the deposition of p-type copper
phthalocyanine on n-type GaAs single-crystal semiconductor substrate. The temperature sensing
and photoconductive behavior of the cells are investigated. The results reveal that with increase
in temperature from 33-75 C the resistance temperature coefficients (RTC) for the reverse and
forward bias resistances are equal to -2.0 %/C and -1.5 %/C, respectively.
IX

Electromechanical sensors based on PANI, CNTs and CNTs-Cu
2
O composites have been
fabricated and investigated. The 20-80 m thick PANI films are deposited by drop-casting on Ag
electrodes, which are preliminary deposited on glass substrates. The effect of displacement on
the resistance and capacitance of film is investigated. It is observed that with increases in
displacement the resistance decreases and the capacitance increases.
For the fabrication of CNTCu
2
O composite based pressure sensors tablets of composite are
made at a pressure of 353 MPa. The average diameter and the average thickness of the tablets are
10 mm and 4 mm, respectively, and both sides of the tablet are covered by silver paste. By
varying pressure from 0-37 kN/m
2
, the change in DC resistance of the sensor is measured.
The CNTs and CNTsCu
2
O composite based strain sensors have been fabricated by pressed
tablets and elastic polymer beam. The 1 mm thick tablets of CNTs and CNTsCu
2
O composite
are fabricated at a pressure of 200-300 MPa and 353MPa, respectively. The samples are installed
on the polymer elastic beam by glue. The electric contacts to the samples are made by silver
paste. The inter-electrodes distance (length) and diameter of the surface-type samples are in the
range of 68 mm and 10 mm, respectively. It is found that DC resistance of the strain sensors
increases under tension and decreases under compression, while the average strain sensitivities
are in the range of 50-80 and 4446 for CNTs and CNTsCu
2
O composite based sensors,
respectively.

X

Table of contents
Acknowledgements.....IV
Declaration....V
Journal Publications ...VI
Refereed Conference Publications ....VII
Abstract.....VIII
Table of Contents..........X
List of Figures.........XVII
List of Tables.......XXII
List of Abbreviations ........XXIII

Chapter-1 Introduction......1
1.1 Preamble .............................................................................................................................. 1
1.2 Aims and objectives ............................................................................................................. 2
1.3 Outline of the dissertation .................................................................................................... 2
1.3.1 Chapter-2.............................................................................................................................. 2
1.3.2 Chapter-3.............................................................................................................................. 2
1.3.3 Chapter-4.............................................................................................................................. 3
1.3.4 Chapter-5.............................................................................................................................. 3
1.3.5 Chapter-6.............................................................................................................................. 3
1.3.6 Chapter-7.............................................................................................................................. 3
References ....................................................................................................................................... 4

XI

Chapter-2 Literature Survey......6
2.1 Sensors and thei classifications ............................................................................................ 6
2.2 Sensing materials ................................................................................................................. 8
2.2.1 Organic materials ............................................................................................................... 11
2.2.2 History of organic semiconducting materials in electronic devices .................................. 12
2.2.3 Importance of organic semiconducting materials .............................................................. 12
2.2.4 Chemical nature of organic semiconducting materials ...................................................... 14
2.2.5 Charge transport properties/conduction mechanism of organic semiconductors .............. 15
2.3 Properties of various organic sensing materials................................................................. 18
2.3.1 Polyaniline (PANI) ............................................................................................................ 18
2.3.2 Carbon nanotubes (CNTs) ................................................................................................. 20
2.3.3 Copper phthalocyanine (CuPc) .......................................................................................... 21
2.4 Sensing mechanism ............................................................................................................ 22
2.4.1 Percolation theory .............................................................................................................. 23
2.4.1.1Introduction ........................................................................................................................ 23
2.4.1.2Percolative transport .......................................................................................................... 23
2.5 Applications ....................................................................................................................... 24
References ..................................................................................................................................... 26

Chapter-3 Materials and Experimental.......35
3.1 Materials ............................................................................................................................ 35
3.1.1 Polyaniline (PANI) ............................................................................................................ 35
3.1.2 Cellulose ............................................................................................................................ 35
3.1.3 Poly-N-epoxypropylcarbazole (PEPC) .............................................................................. 36
XII

3.1.4 Copper phthalocyanine (CuPc) .......................................................................................... 36
3.1.5 Orange dye (OD)................................................................................................................ 36
3.1.6 Carbon nanotubes (CNTs) ................................................................................................. 41
3.1.7 Cuprous oxide (Cu
2
O)........................................................................................................ 41
3.1.8 Vanadium oxide (V
2
O
4
) ..................................................................................................... 41
3.1.9 Gallium arsenide (GaAs) ................................................................................................... 41
3.2 Fabrication techniques ....................................................................................................... 43
3.2.1 Substrate preparation ......................................................................................................... 43
3.2.2 Metallization ...................................................................................................................... 44
3.2.3 Vacuum thermal evaporation ............................................................................................. 44
3.2.4 Drop casting ....................................................................................................................... 44
3.2.5 Adhesive tape ..................................................................................................................... 45
3.2.6 Glued film .......................................................................................................................... 45
3.2.7 Cold compaction ................................................................................................................ 45
3.3 Film characterization ......................................................................................................... 46
3.3.1 Crystal thickness monitor .................................................................................................. 46
3.3.2 Optical microscope (OM) .................................................................................................. 46
3.3.3 Scanning electron microscope (SEM) ............................................................................... 47
3.4 Experimental setups ........................................................................................................... 49
3.4.1 Apparatus for thin film deposition ..................................................................................... 49
3.4.2 Apparatus for testing of humidity sensors ......................................................................... 51
3.4.3 Apparatus for testing of temperature sensors ..................................................................... 51
3.4.4 Apparatus for testing of displacement sensors................................................................... 52
3.4.5 Apparatus for testing of pressure sensors .......................................................................... 52
XIII

3.4.6 Apparatus for testing of strain sensors ............................................................................... 52
References ..................................................................................................................................... 57

Chapter-4 Humidity Sensors...........60
4.1 Polyaniline based humidity sensors ................................................................................... 60
4.1.1 Introduction ........................................................................................................................ 60
4.1.2 Experimental ...................................................................................................................... 61
4.1.2.1Fabrication of sensors ........................................................................................................ 61
4.1.2.2Measurements .................................................................................................................... 62
4.1.3 Results and discussion ....................................................................................................... 63
4.1.4 Conclusions ........................................................................................................................ 69
4.2 Fabrication and investigation of orange-dye-polyaniline composite film based humidity
sensors ........................................................................................................................................... 73
4.2.1 Introduction ........................................................................................................................ 73
4.2.2 Experimental ...................................................................................................................... 74
4.2.2.2Measurements .................................................................................................................... 74
4.2.4 Conclusions ........................................................................................................................ 82
4.3 Organic Cu/Cellulose/ PEPC/Cu humidity sensors ........................................................... 84
4.3.1 Introduction ........................................................................................................................ 84
4.3.2 Experimental ...................................................................................................................... 85
4.3.2.2Measurements .................................................................................................................... 85
XIV

4.3.4 Conclusions ........................................................................................................................ 90
References ..................................................................................................................................... 92

Chapter-5 Temperature Sensors..........97
5.1 Carbon nanotubes film based temperature sensors ............................................................ 97
5.1.1 Introduction ........................................................................................................................ 97
5.1.2 Experimental ...................................................................................................................... 98
5.1.2.2Measurements .................................................................................................................... 99
5.1.4 Conclusions ...................................................................................................................... 103
5.2 Carbon nanotubes based flexible temperature sensors .................................................... 104
5.2.1 Introduction ...................................................................................................................... 104
5.2.2 Experimental .................................................................................................................... 104
5.2.2.1Fabrication of sensors ...................................................................................................... 104
5.2.2.2Measurements .................................................................................................................. 105
5.2.3 Results and discussion ..................................................................................................... 105
5.2.4 Conclusions ...................................................................................................................... 107
5.3 A study of V
2
O
4
-PEPC composite based resistance temperature sensors ....................... 110
5.3.1 Introduction ...................................................................................................................... 110
5.3.2 Experimental .................................................................................................................... 110
5.3.2.2Measurements .................................................................................................................. 111
XV

5.3.4 Conclusions ...................................................................................................................... 117
5.4 Temperature sensing properties of organic-inorganic Ag/p-CuPc/n-GaAs/Ag cell ........ 121
5.4.1 Introduction ...................................................................................................................... 121
5.4.2 Experimental .................................................................................................................... 123
5.4.2.1Fabrication of cells ........................................................................................................... 123
5.4.2.2Measurements .................................................................................................................. 124
5.4.4 Conclusions ...................................................................................................................... 126
References ................................................................................................................................... 130

Chapter-6 Electromechanical Sensors.......135
6.1 Effect of displacement on resistance and capacitance of polyaniline film ...................... 135
6.1.1 Introduction ...................................................................................................................... 135
6.1.2 Experimental .................................................................................................................... 136
6.1.2.2Measurements .................................................................................................................. 137
6.1.4 Conclusions ...................................................................................................................... 141
6.2 Carbon nanotubes-cuprous oxide composite based pressure sensors .............................. 144
6.2.1 Introduction ...................................................................................................................... 144
6.2.2 Experimental .................................................................................................................... 145
6.2.2.2Measurements .................................................................................................................. 146
XVI

6.2.4 Conclusions ...................................................................................................................... 149
6.3 Carbon nanotubes based strain sensors ............................................................................ 151
6.3.1 Introduction ...................................................................................................................... 151
6.3.2 Experimental .................................................................................................................... 152
6.3.2.2Measurements .................................................................................................................. 152
6.3.4 Conclusions ...................................................................................................................... 155
6.4 Strain sensors based on carbon nanotubes-cuprous oxide composite .............................. 157
6.4.1 Introduction ...................................................................................................................... 157
6.4.2 Experimental .................................................................................................................... 158
6.4.2.2Measurements .................................................................................................................. 158
6.4.3 Results and discussions .................................................................................................... 158
6.4.4 Conclusions ...................................................................................................................... 160
References ................................................................................................................................... 163

Chapter-7 summary and Future Work.......169
7.1 Summary .......................................................................................................................... 169
7.2 Future Work ..................................................................................................................... 172
Appendix...173

XVII

List of Figures
Figure 2.1 Classification of chemical sensors [10] ......................................................................... 9
Figure 2.2 Classification of physical sensors [10] ........................................................................ 10
Figure 2.3 Conjugated molecules a: copper phthalocyanine, b: polythiophene, c: fullerene, d:
polyacetylene and e: polyaniline ................................................................................................... 16
Figure 3.1 Molecular structure of Polyaniline (PANI) (n=m=0.5) [8] ......................................... 37
Figure 3.2 Molecular structure of Cellulose ................................................................................. 37
Figure 3.3 Molecular structure of Poly-N-epoxypropylcarbazole (PEPC) (where n=4-6) ........... 38
Figure 3.4 Molecular structure of Copper Phthalocyanine (CuPc)............................................... 38
Figure 3.5 General azo-dye structure ............................................................................................ 39
Figure 3.6 Molecular structure of Orange Dye 25 (OD) [7] ......................................................... 39
Figure 3.7 Schematic diagram of thermal evaporator ................................................................... 50
Figure 3.8 Apparatus for testing humidity sensors ....................................................................... 53
Figure 3.9 Schematic of testing setup for the characterization of temperature sensors ................ 54
Figure 3.10 Schematic diagram of the experimental setup for characterization of displacement
sensors [28] ................................................................................................................................... 55
Figure 3.11 Schematic of apparatus for the investigation of pressure sensors [29] ..................... 56
Figure 3.12 Simplified schematic diagram of the elastic beam of constant resistance to bending
without load; (a) side view, (b) top view, and under load (c) side view [26]. .............................. 56
Figure 4.1 Schematic diagram of the Au/PANI/Ag humidity sensor. .......................................... 65
Figure 4.2 Surface morphology of PANI film at low (a) and high (b) magnification. ................. 65
Figure 4.3 Capacitance and impedance-relative humidity (RH) relationships for the Au/PANI/Ag
sensor at 120 Hz. ........................................................................................................................... 66
Figure 4.4 Impedance-relative humidity (RH) relationships for the Au/PANI/Ag sensor at 120
Hz and 1 kHz. ............................................................................................................................... 67
XVIII

Figure 4.5 Impedance-relative humidity (RH) relationships for the Au/PANI/Ag sensor at 120
Hz during increasing and decreasing of humidity. ....................................................................... 67
Figure 4.6 Normalized experimental and simulated impedance-relative humidity (RH)
relationships for the Au/PANI/Ag sensor at 120 Hz. ................................................................... 71
Figure 4.7 Circuit diagram of Op-amp logarithmic amplifier. ..................................................... 71
Figure 4.8 The response (
res
) and recovery (
rec
) times of the Au/PANI/Ag sensor. ................... 72
Figure 4.9 Schematic diagram of the Ag/OD-PANI/Ag Humidity Sensor. ................................. 77
Figure 4.10 Optical Micrograph of the OD-PANI films surface. ................................................ 78
Figure 4.11 SEM image of the OD-PANI films surface. ............................................................ 78
Figure 4.12 Capacitance and impedance-humidity relationships for the Ag/OD-PANI/Ag Sensor
at 120 Hz. ...................................................................................................................................... 79
Figure 4.13 Impedance-humidity relationship for the thick film (170 m) Ag/OD-PANI/Ag
sensor at 120 Hz during increasing and decreasing of humidity; Inset shows the Impedance-
humidity relationship for the thin film (50 m) Ag/OD-PANI/Ag sensor. .................................. 79
Figure 4.14 Impedance-humidity relationships for the Ag/OD-PANI/Ag sensor at 120 Hz and 1
kHz. ............................................................................................................................................... 80
Figure 4.15 Normalized experimental and simulated impedance-humidity relationships for the
Ag/OD-PANI/Ag sensor at 120 Hz. ............................................................................................. 83
res
) and recovery (
rec
) times of the Ag/OD-PANI/Ag sensor. .......... 83
Figure 4.17 Cross-sectional view of the Cu/ Cellulose /PEPC /Cu sensor. .................................. 88
Figure 4.18 Relationship among capacitance, resistance, impedance and relative humidity ....... 88
Figure 4.19 Comparison of experimental and simulated capacitance with respect to relative
humidity ........................................................................................................................................ 91
Figure 4.20 Comparison of experimental and simulated resistance with respect to relative
humidity ........................................................................................................................................ 91
Figure 5.1 Schematic diagram of the CNTs film based resistance temperature sensor. ............. 100
XIX

Figure 5.2 Resistance-temperature relationships of the one of CNTs film based sensors at
heating-cooling processes. .......................................................................................................... 100
Figure 5.3 Experimental and simulated relative resistance-temperature relationships of the CNTs
sensors (R
o
and R are initial resistance and resistance at elevated temperatures respectively). . 102
Figure 5.4 Al/CNT/Al resistance temperature sensor ................................................................. 106
Figure 5.5 Resistance-temperature relationship of the one of Al/CNT/Al sensors .................... 106
Figure 5.6 Experimental (solid line) and simulated (dashed line) relative resistance-temperature
relationships of the Al/CNT/Al sensors (R
o
and R are initial resistance and resistance at elevated
temperatures respectively) .......................................................................................................... 109
Figure 5.7 Schematic diagram of V
2
O
4
-PEPC composite based resistance temperature sensor 112
Figure 5.8 SEM image of V
2
O
4
-PEPC composite film .............................................................. 112
Figure 5.9(a and b) Resistance-temperature relationships for two of the V
2
O
4
-PEPC sensors
during heating process ................................................................................................................ 113
Figure 5.10(a and b). Derivatives of the resistance (dR/dT)-temperature relationships for the two
of the V
2
O
4
-PEPC sensors during heating process. .................................................................... 114
Figure 5.11 Resistance-temperature relationships at heating-cooling processes for the one of the
V
2
O
4
-PEPC sensors at 100 Hz. Experimental and simulated relative resistance-temperature
relationships of the V
2
O
4
-PEPC based temperature sensor ........................................................ 118
Figure 5.12 The log relative resistance-temperature relationship (a) and relative resistance-log
temperature relationship (b) for the V
2
O
4
-PEPC sensor ............................................................. 119
Figure 5.13 Relative resistance-time relationship for the V
2
O
4
-PEPC composite temperature
sensor. ......................................................................................................................................... 120
Figure 5.14 Cross sectional view of organicinorganic heterojunction sensor fabricated by using
n-type GaAs substrate and a thin p-CuPc film: 1-GaAs, 2-CuPc, 3-Ag, 4-Ag (semi-transparent),
5 and 6- terminals; (a) Side view (b) Top view. ......................................................................... 125
Figure 5.15 SEM image of the deposited CuPc film .................................................................. 125
XX

Figure 5.16 Dependence of reverse (R
R
) and forward (R
F
) bias resistances of the Ag/p-CuPc/n-
GaAs/Ag cell on temperature. ..................................................................................................... 128
Figure 5.17 Dependence of the simulated and experimental relative reverse (R
R
/R
oR
) bias
resistances of the Ag/p-CuPc/n-GaAs/Ag cell on temperature................................................... 128
Figure 5.18 Dependence of the simulated and experimental forward (R
F
/R
oF
) bias resistances of
the Ag/p-CuPc/n-GaAs/Ag cell on temperature ......................................................................... 129
Figure 6.1 SEM image of porous polyaniline film. .................................................................... 140
Figure 6.2 Relative resistance-displacement and capacitance-displacement relationships for the
Ag/PANI/Al sensor: polyaniline films thickness is 80 m (solid line ) and 20 m (dashed line).
..................................................................................................................................................... 140
Figure 6.3 Comparison of experimental and simulated relative resistance-displacement
relationships for the Ag/PANI/Al displacement sensor. ............................................................. 143
Figure 6.4 Comparison of experimental and simulated relative capacitance-displacement
relationships for the Ag/PANI/Al sensor. ................................................................................... 143
Figure 6.5 Photographs of sample from various angles. ............................................................. 148
Figure 6.6 Resistance-pressure relationship for the CNT-Cu
2
O pressure sensor. ...................... 148
Figure 6.7 Experimental (solid lines for the sensors shown in Figure 6.6) and simulated (dashed
line) relative resistance-pressure relationships for the CNT-Cu
2
O pressure sensor (R
o
and R are
resistances at atmospheric pressure and under uniaxial pressure, respectively). ........................ 150
Figure 6.8 Schematic diagram of the pressure sensors arrangement in the Wheatstone bridge (V
o

= output voltage). ........................................................................................................................ 150
Figure 6.9 CNT based resistive strain sensor installed on the elastic beam. .............................. 154
Figure 6.10 Resistance-strain relationships under tension for the sample 1 and 2 fabricated at a
pressure of 300 and 200 MPa, respectively. ............................................................................... 154
Figure 6.11 CNT-Cu
2
O composite resistive strain sensor installed on the elastic beam. ........... 161
Figure 6.12 Resistance-strain relationships under tension and compression for the sample
fabricated at 353 MPa. ................................................................................................................ 161
XXI

Figure 6.13 Comparison of Experimental and Simulated results ............................................... 162

XXII

List of Tables
Table 2-1 History of organic semiconductor materials and devices ............................................. 13
Table 3-1. Physical properties of organic materials ...................................................................... 40
Table 3-2. Physical properties of inorganic materials .................................................................. 42
Table 3-3 FTM5 Crystal thickness monitors technical data [24] ................................................ 48
Table 4-1 Relative standard deviation (R.S.D) of the measured data ........................................... 66
Table 4-2 Humidity sensing properties of Sensor ......................................................................... 72
Table 4-3 Humidity sensing properties of Sensor ......................................................................... 80

XXIII

List of Abbreviations
AC Alternating current
AlPc Aluminium phthalocyanine
BP Bucky-paper
CNTs Carbon nanotubes
CPs Conductive polymers
CTC Charge transfer complexes
CuPc Copper phthalocyanine
DC Direct current
DNA Deoxyribonucleic acid
DWCNTs Double-walled carbon nanotubes
EA Electron affinity
EB Emeraldine base
E
g
Energy gap
EM Emeraldine
ES Emeraldine salt
FM Frequency modulated
GaAs Gallium arsenide
GTS Generator-type sensors
HOMO Highest occupied molecular orbital
IE Ionization energy
LBL Layer by layer
LCDs Liquid crystal displays
XXIV

LM Leuco-emeraldine
LUMO Lowest unoccupied molecular orbital
LVDT Linear variable differential transformer
MPcs Metal-phthalocyanine
MTS Modulated-type sensors
MWCNTs Multi-walled carbon nanotubes
NA Nigr-aniline
NIR Near infrared
OD Orange dye
OFETs Organic field effect transistors
OLEDs Organic light emitting diodes
OM Optical microscopy
OMCs Organic molecular crystals
Op-amp Operational amplifier
OS Organic semiconductor
OSCs Organic solar cells
OTFT Organic thin film transistor
PANI Polyaniline
Pc Phthalocyanine
PEPC Poly-N-epoxypropylcarbazole
PMMA Poly (methyl methacrylate)
PNA Pernigr-aniline
RH Relative humidity
RTDs Resistance temperature detectors
XXV

SEM Scanning electron microscopy
SGS Small-gap semiconducting
SPANI Anilinesulfonic acid
SWCNTs Single-walled carbon nano tubes
TCNQ Tetracyanoquinodimethane
UV Ultraviolet
VCO Voltage-controlled oscillator
VO Vanadium oxide

1

Chapter-1
Introduction
1 1
1.1 Preamble
From last few decades extensive research is being done on the organic semiconducting materials
for their application in electronic devices [1-4]. As the conventionally used inorganic thin film
transistors have high cost because of high processing temperature and complicated fabrication
technology. Moreover inorganic semiconductors are not suitable for flexible and large area
electronics. Comparative to inorganic semiconductors, organic semiconductors have advantages
of low cost, simple technology, excellent flexibility and large area deposition [1, 5-8]. For the
fabrication of cheaper, flexible and large area electronic devices, organic thin films are deposited
by drop-casting, spin coating, spraying, printing, and physical vapor deposition technique [9-13].
Although the thin films of organic semiconductors have very low carrier mobility as compared to
their inorganic counter parts [14, 15], but in low cast applications they are competitive to
inorganic devices. Although recently few types of organic sensors has been commercialized [16]
but the organic light emitting diode is the first commercial device based on organic
semiconductor [17, 18], while the organic field effect transistors and solar cells are expected to
be commercialized in near future. Some statistics predict that in year 2020 the organic
electronics will have $ 96 billion business which will be further flourish upto $ 250 billion in
year 2025 [19]. The sensitivity of several organic semiconductors towards various types of gases,
chemicals, bio species, radiations, humidity, temperature and pressure is the highly attractive
field of current research. Keeping in view the above mentioned advantages and the potential of
organic semiconductor based devices in the future market, the fabrication of various types of
sensors based on organic and nano materials by using simple technology is very promising. This
dissertation aspires at the fabrication and investigation of sensors for humidity, light,
temperature, pressure and strain sensing applications.

2

1.2 Aims and objectives
The main objective of this dissertation is fabrication and investigation of organic and nano
materials based sensors by using low cost materials and simplest technology to introduce low
cost devices for various industrial, environmental and medical applications. By considering the
demand of industry for sensors with adequate sensitivity, low cost and simplicity of structure, the
objectives of the current research work were the
I. Use of commercially available organic and nano materials to explore their new
applications or enhance their capabilities in already existing applications.
II. Fabrication of organic-inorganic composites films and organic-on-inorganic layered
structure to improve stability and performance of sensors
III. Use of simple film fabrication techniques like drop casting, gluing, adhesive tape and
cold compaction to make the technology easy.
IV. Simple processing of materials for time efficient and cheaper fabrication.
V. Electrical characterization of sensors to find their suitability for specific applications.
1.3 Outline of the dissertation
This dissertation consists of four major sections, which include literature survey (chapter-2),
materials and experimental (chapter-3), results and discussion (chapter-4 to chapter-6) and
summary and future work (chapter-7). The chapter wise detail of the dissertation is the following
1.3.1 Chapter-2
This chapter gives the overview of sensor, sensing materials, organic semiconductors and their
history and conduction mechanism. This chapter is comprised of five sections. The section 2.1 is
about sensors and their classification, while section 2.2 provides a little description of sensing
materials, particularly, the nature of organic semiconductors with their history. The discussion
about conduction mechanism is given in section 2.3. Brief description about some of the
materials is given in section 2.4. Last section is about the application of sensors.
1.3.2 Chapter-3
Detailed information about the materials used for the fabrication of sensors is given in this
chapter. More over the fabrication techniques and the experimental setups used for fabrication
3

and characterization of various types of sensors have been discussed in detail. There are four
sections, which present the materials, fabrication techniques, characterization and the setup for
the testing of sensors in a sequence.
1.3.3 Chapter-4
The results and discussion about various types of humidity sensors along with their introduction
and experimental procedure have been presented in this chapter. This chapter is subdivided into
three sections and these sections are comprised on the basis of sensors materials. These
materials are polyaniline, orange dye-polyaniline composite and cellulose-PEPC composite.
1.3.4 Chapter-5
This chapter is comprised of four sections that present four different types of temperature
sensors. These are the resistance-temperature sensors, which include multiwall carbon nanotubes
(CNTs) film, CNTs flexible, CNTs-Cu
2
O composite, V
2
O
4
-PEPC composite and organic on
inorganic (CuPc on GaAs) sensors. The experimental results have been discussed in detail.
Moreover detailed introduction with complete fabrication processes of each type of sensor is
given in this chapter.
1.3.5 Chapter-6
The design, fabrication and investigation of three types of electromechanical sensors have been
presented in four sections of this chapter. First section presents the investigation of effect of
displacement on polyaniline film, while the second section is about Carbon nanotubes-cuprous
oxide composite based pressure sensors. The third and fourth sections describe the CNTs and
CNTs-cuprous oxide composite based strain sensors, respectively.
1.3.6 Chapter-7
In this chapter the results have been summarized and the future work has been presented.

4

References
1. N.A.M. Barakat, A. Hamza, S.S. Al-Deyab, A. Qurashi and H.Y. Kim: 'Titanium-based
polymeric electrospun nanofiber mats as a novel organic semiconductor', Materials
Science and Engineering: B, 2012, 177, 34-42.
2. Y. Gao: 'Surface analytical studies of interfaces in organic semiconductor devices',
Materials Science and Engineering: R: Reports, 2010, 68(3), 39-87.
3. S. Palaniappan and A. John: 'Polyaniline materials by emulsion polymerization pathway',
Prog. Polym. Sci., 2008, 33(7), 732-758.
4. M.X. Zhang, S. Chai and G.J. Zhao: 'BODIPY derivatives as n-type organic
semiconductors: Isomer effect on carrier mobility', Org. Electron., 2012, 13, 215-221.
5. C.J. Brabec: 'Organic photovoltaics: technology and market', Sol. Energy Mater. Sol.
Cells, 2004, 83(2), 273-292.
6. K. Itaka, M. Yamashiro, J. Yamaguchi, S. Yaginuma, M. Haemori and H. Koinuma:
'Combinatorial approach to the fabrication of organic thin films', Appl. Surf. Sci., 2006,
252(7), 2562-2567.
7. A. Manor and E.A. Katz: 'Open-circuit voltage of organic photovoltaics: Implications of
the generalized Einstein relation for disordered semiconductors', Sol. Energy Mater. Sol.
Cells, 2012, 97, 132-138.
8. Y. Wang, J. Ren, X. Yuan, Z. Dou and G. Hu: 'Effects of electric field and magnetic
induction on spin injection into organic semiconductors', Physica B: Condensed Matter,
2011, 406(4), 926-929.
9. N.A. Azarova, J.W. Owen, C.A. McLellan, M.A. Grimminger, E.K. Chapman, J.E.
Anthony and O.D. Jurchescu: 'Fabrication of organic thin-film transistors by spray-
deposition for low-cost, large-area electronics', Org. Electron., 2010, 11(12), 1960-1965.
10. A.A.M. Farag and I.S. Yahia: 'Structural, absorption and optical dispersion characteristics
of rhodamine B thin films prepared by drop casting technique', Optics Communications,
2010, 283(21), 4310-4317.
11. F.C. Krebs: 'Fabrication and processing of polymer solar cells: A review of printing and
coating techniques', Sol. Energy Mater. Sol. Cells, 2009, 93(4), 394-412.
5

12. V. Nadazdy, R. Durny, J. Puigdollers, C. Voz, S. Cheylan and M. Weis: 'Defect states in
pentacene thin films prepared by thermal evaporation and LangmuirBlodgett technique',
J. Non-Cryst. Solids, 2008, 354(19-25), 2888-2891.
13. S.A. Wilson, R.P.J. Jourdain, Q. Zhang, R.A. Dorey, C.R. Bowen, M. Willander, Q.U.
Wahab, S.M. Al-hilli, O. Nur and E. Quandt: 'New materials for micro-scale sensors and
actuators: An engineering review', Materials Science and Engineering: R: Reports, 2007,
56(1), 1-129.
14. B. Lucas, A. El Amrani, A. Moliton, A. Skaiky, A. El Hajj and M. Aldissi: 'Charge
transport properties in pentacene films: Evaluation of carrier mobility by different
techniques', Solid-State Electronics, 2012, 69, 99-103.
15. Z. Wang, M. Helander, M. Greiner, J. Qiu and Z. Lu: 'Carrier mobility of organic
semiconductors based on current-voltage characteristics', J. Appl. Phys., 2010, 107(3),
034506-034506-034504.
16. R. Zhang: 'Conductive TPU/CNT composites for strain sensing', PhD thesis, Queen
Mary, University of London, London, 2009.
17. W. Brutting: 'Physics of organic semiconductors'; 2005, KGaA, Weinheim, Wiley-VCH
Verlag GmbH & Co.
18. I. Yahia, M. Abd El-sadek and F. Yakuphanoglu: 'Methyl orange (CI Acid Orange 52) as
a new Organic Semiconductor: Conduction mechanism and Dielectrical relaxation', Dyes
and Pigments, 2012, 93(1434-1440).
19. IDTechEx.com. '

6

Chapter-2
Literature Survey
2 1
Sensors are based on active sensing materials, which include inorganic and organic materials.
The organic materials have some advantages over the inorganic counterparts such as low density,
easy processing, flexibility and low cost [1-5]. The carbon is the element on which organic
materials are based. Examples of organic materials are the polymers, low molecular weight
organic materials, fullerene, carbon nanotubes etc. In the beginning, organic materials were
considered as insulators. In the last few decades of the 20
th
century [6, 7], the discovery of
conductivity in organic materials attracted the scientists and researchers to explore their potential
to replace traditional inorganic electronic materials. History, evolution in conducting properties,
mechanisms involving in conduction and suitability of materials for various applications are the
interesting points which have been discussed in this chapter.
This chapter gives an overview of sensors and their classification, sensing materials, organic
semiconductors and their history and conduction mechanism. This chapter is also comprised of
four sections. The section 2.1 is about sensors and their classification, while section 2.2 provides
a little description of sensing materials, particularly, the nature of organic semiconductors with
their history. The discussion about conduction mechanism is given in section 2.3. In the last
section (section 2.4) few of the materials are described briefly with their applications.
2.1 Sensors and their classifications
Sensors are the devices that usually convert real-world data into electrical signals. Sensor can
provide the information on the physical, chemical and biological environment [8]. Use of sensors
in each and every field of life is common and ever increasing. In the modern era, sensors are
considered one of the prime requirements for better and easy life because sensors playing vital
role in the field of health and medicine, food and agriculture, business and industry, environment
and security, defense and aerospace and also communication. Research is in continuation for the
development of efficient and low cost sensors for wide variety measurands. To obtain the
comprehensive overview for the facilitation of comparison, classification of sensors is important
[9]. In literature various classifications are devised, which include the simplest as well as
7

complex schemes. These schemes have their own advantages and disadvantages. But because of
diversity in the growth of sensing technology, standard classification could not come into
existence so far [10].
White [9] in 1987 presented a classification system, which is derived from literature of Hitachi
research laboratory. He claims that this system is flexible with intermediate complexity and it is
apposite for personnel involve in computer based storage and retrieval system. This classification
categorizes the sensors on the basis of mesurands, technological aspects of sensors, detection
means used in sensors, sensors conversion phenomena, sensors materials and field of
applications. In year 2000 G. Harsanyi [11] classified the sensors on the basis of quantity to be
measured, basic sensor structure and sensing effect. On the basis of device structure which can
be used to measure the sensing properties of materials can be categorized as
i. Impedance type sensors
ii. Sensing semiconducting devices
iii. Sensors based on acoustic wave propagation
iv. Electrochemical cells as sensors
v. Image sensing
vi. Charged particle dependent sensing
Another classification is devised on the base of source of excitation, which divided the sensors
into Generator-type sensors (GTS) and Modulated-type sensors (MTS). The sensors which
operate without external excitation are called Generator-type sensors, while that need excitations
are called modulated sensors. Examples of GTS and MTS are thermocouple and thermistors
respectively.
Hulanicki et al. [12] categorized the sensors on the basis of operating principles of transducers.
These transducers contain number of sensors. Major types of devices are presented below
a. Optical devices
b. Electrochemical devices
c. Electrical devices
d. Mass sensitive devices
e. Magnetic devices
f. Thermometric devices
8

g. Devices used to determine chemical composition
Wang et al. [10] classify the biomedical sensors in to physical, chemical and biological sensors
on the basis of working principle. Figure 2.1 and Figure 2.2 show the classifications of chemical
and physical sensors respectively. Moreover on the basis of measuring quantity, biomedical
sensors are classified as flow sensors, temperature sensors, displacement sensors, speed sensors,
pressure sensors etc. Each type of these sensors can be further classified on the basis of materials
or the working principles of sensors. The hearing sensors, vision sensors, capacity sensors and
olfaction sensors are the sensors which are classified according to human sensing organs. These
sensors are used to replace the human organs for the similar activities.
2.2 Sensing materials
The materials which have semiconducting or conducting behavior can be used for sensor
fabrication. These materials include silicon, ferrous and non-ferrous metals and alloys, ceramics,
glasses, organic and nanomaterials [13]. There are few factors on the basis of which materials
are categorized as the most suitable, suitable and not suitable which include the ease in
fabrication, processing technology, availability of materials etc [14, 15]. According to their
nature materials are classified into inorganic, organic and composite materials. Generally
inorganic sensing materials are high density and difficult to process. The organic materials due to
low density, simple processing technology, high surface area and flexibility have potential to
replace conventional inorganic materials [15-18]. To improve the electrical and mechanical
properties of electronic devices, organic-organic or organic-inorganic composites and organic-
inorganic layered structures are also developed [13].

9

Figure 2.1 Classification of chemical sensors [10]

Ion selective electrodes
Ion selective field effect transistors
Light addressable potentiometric sensors
Microelectrode array
Electrochemical gas sensors
Semiconductor gas sensors
Solid electrolyte gas sensors
Surface acoustic wave sensors
Capacitive humidity sensors
Resistive humidity sensors
Thermal conductivity humidity sensors
Chemical Sensors
Humidity Sensors
Gas Sensors
Ion Sensors
10

Figure 2.2 Classification of physical sensors [10]

Photo resistor
Photodiode and transistor
Photovoltaic sensors
Fiber optic sensors
Photoelectric
Sensors
Space-variant capacitance sensors
Area-variant capacitance sensors
Medium-variant capacitance sensors
Capacitive pressure sensors
Electret microphone
2-D capacitive sensors
Capacitive
Sensors
Physical Sensors
Resistance strain sensors
Piezoresistive sensors
Self induced sensors
Differential transformer sensor
Sensors based on piezoelectric effect
Sensors based on piezoelectric resonator

Magnetoelectric induction sensor
Hall magnetic sensor
Hall viscor sensors
Hall respiration flow sensor
Magnetoelectric
Sensors
Piezoelectric
Sensors

Resistance
Sensors
Inductive Sensors

11

2.2.1 Organic materials
The carbon compounds are the base for organic materials, while the conjugation is the basic
feature of organic semiconductors. The chain of carbon atoms consisting of alternating single
and double bond is called conjugation, which in the range of semiconductors results in opening
of band gap and splitting of the energy level, and charge delocalization in these levels. The Sp
2

hybridization based bonding distinguishes the organic semiconductors from inorganic one. The
ring like structure of benzene is the archetype of the organic molecule. Difference among various
organic semiconducting molecules is based on the number of benzene rings, the polymerization,
the carbon atoms substitution by sulfur or nitrogen or the hydrogen substitution by side groups
[13, 19, 20].
On the basis of charge transport mechanism organic materials are classified as p-type (hole-
transport) and n-type (electron- movement). The majority of organic semiconductors have p-type
characteristic, while n-type organic materials also exist which have few environmental stability
problem [21]. The organic semiconducting materials are also categorized on the basis of
molecular weight as low molecular weight materials (oligomers) and polymers for which basic
unit is the monomer. The carbon atoms of the main chains of the molecules which forms the
backbone of molecule are strongly bonded by -bond which do not takes part in electronic
conduction. In the molecules of both types of organic materials the p
z
orbitals of sp
2
hybridized
carbon atoms form weakly bonded conjugated -electron system. These -electrons undergo -
* transitions which is considered lowest electronic transition with energy band gap of 1.5-3.0
eV [19, 22]. Normally polymers are comprised of carbon atoms in combination with one or more
of the elements like nitrogen, oxygen, hydrogen, silicon, sulfur, chlorine and fluorine. For the
fabrication of electronic devices, the thin films of oligomers and polymers are deposited which
are amorphous in nature. The organic molecules can be crystallized by van-der Waals interaction
to form organic molecular crystals. A variety of methods is used for the growth of single organic
molecular crystals (OMCs), which include vapor phase growth or growth by solution,
Czochralski and Bridgman-type methods and sublimation. Although OMCs show better
performance but the thin films are most practical for the fabrication of electronic devices [13, 19,
20].
12

2.2.2 History of organic semiconducting materials in electronic devices
As the invention of transistor in 1950s brought a revolution in electronic industry, the inorganic
semiconducting materials started to replace the already being used metallic materials. In the
beginning of new century it has become possible that inorganic semiconductors may replaced by
organic semiconductors. As a first commercial product organic light emitting diode (OLED)
display is available in market [19]. The discovery of semiconducting behavior in organic
materials and their commercialization have a long history, which is spread over a century. From
the beginning it was general concept that organic materials are insulators. This concept proved
wrong when in the start of last century photoconductivity was observed in the anthracene, and it
was the first known photoconductive organic material [23-25]. The research on organic
molecular crystal during 1960s resulted in exploration of basic phenomena of optical excitation
and charge carrier transport [26, 27]. In 1970s the discovery of conducting polymer was the
outcome of a laboratory accident which was granted a Nobel Prize in chemistry in the year 2000
[28-30]. This was the revolution which opened a new horizon for synthesis of conjugated
polymers and tailoring of their properties by controlled doping [31]. Brief history of organic
semiconductor materials and devices is shown in Table 2-1.
With the revolution in electronic materials, the electronic devices also revolutionized. In the
second half of 20
th
century inorganic materials based solid state electronics has replaced the
vacuum tube based electronics. Currently the wide spread microelectronic devices for our daily
life use are the gift of development of solid state electronics. After the discovery of
semiconducting and conducting organic materials the expectation for realization of low cost,
light weight, large area, printed integrated circuits, plastics solar cells and flexible light sources
and displays brought revolutionary developments in these materials [19].
2.2.3 Importance of organic semiconducting materials
Although the inorganic semiconductors have capability to perform as a sensor but the organic
semiconductors because of their salient feature related to electrical and physical parameters have
a potential for better performance as a sensing materials. Regarding electrical parameter, the
change in electrical properties of organic materials in response to external agents like humidity,
temperature, pressure, displacement, light, electromagnetic radiations, gases and chemicals etc
make the organic materials competitor of inorganic materials. The ease in tailoring of electronic
13

Table 2-1 History of organic semiconductor materials and devices
Sr.
No
Year Development Researcher Ref.
1
Before
1941
Organic materials are insulator, the metal-like appearance of few of them
intrigued chemists

2 1941-46 Initial interest in OS; -electron transfer in biological system Gyorgi
[32,
33]
3 1948 Observation of weak electric conductance in bulk phthalocyanine Eley [34]
4 1950
Assumption; -electron contribute in electrical Conduction
Introduction; term of organic semiconductor
Akamatu et al. [35]
5 1955 Electroluminescence response reported in organic molecular solids Bernanose [36]
6 1970
Development of organic semiconductor thin film by vacuum evaporation
and Longmuir-Blodgett methods.
William et al. [37]
7 1970 Field effect phenomena reported in organic semiconductor Brabe [38]
8 1976 Discovery of metallic conductivity in polyacetylene Heeger [6]
9 1983 Development of first polyacetylene based OFET
10 1983 Photovoltaic effect observed in organic semiconductors Chamberlain [39]
11 1987 Development of first polythiophene based thin film transistor (OTFT) Koezuka et al. [40]
12 1987 Fabrication of first OLED Tang [41]
13 1987-97 Research focused on improvement of charge carrier mobility ------- [42]
14 2000 Successful synthesis and development of conductive polymers ------- [43]
15 2000-09 Commercialization of some organic materials based sensors ------- [44]

14

properties of organic materials along with physical properties such as light weight, greater
flexibility, high absorption coefficient and larger surface area make organic materials superior
than their inorganic counterparts [13]. The higher biocompatibility of organic materials makes
them ideal for use in bioelectronics which includes bio-detectors or signal processing in bio-
molecular electronics, while the DNA and its constituents can be used as active materials in thin
film transistors [45-49]. In addition to above mentioned features simplicity of fabrication
techniques and lower cost attract the researchers to explore the potential of organic materials for
efficient and reliable electronic devices.
2.2.4 Chemical nature of organic semiconducting materials
As the carbon atom is the basic element of organic materials; these atoms are interconnected
with alternating single and double bonds to form a conjugated molecule, which is an organic
semiconductor [20, 50, 51]. Few examples of conjugated molecules are shown in Figure 2.3.
These semiconducting molecules are formed by the binding of positively charged nuclei and
negatively charged electrons in the atomic shells of constituent atoms. In the molecular chain
each carbon atom contains four electrons out of which three electrons exist in the Sp
2
hybridized
orbitals, while fourth one exists in p
z
orbital. The electrons in Sp
2
orbitals involve in the
formation of covalent bonds between the adjacent carbon atoms on any side in molecular chain
through molecular orbitals. These electrons also bond the carbon atom with hydrogen atoms or
side groups. While the electron in p
z
orbital forms a covalent bond with adjacent carbon atom in
a chain on only one side through bond. This type of bonding results in the formation of chains
with alternative single () and double ( & ) bonds. The only two electrons from each atom
take part in bonding; two electrons out of four bonding electrons remain in and two in
molecular orbitals. The remaining two electrons on each carbon atom in non bonding orbitals are
available for bonding of remaining chains or ligands [51].
It is the basic feature of organic molecules that due to the interaction between p
z
atomic orbitals
the splitting between and * molecular orbitals takes place. Additional smaller splitting of the
levels also takes place because of these interactions further away from the chain. The and *
molecular orbitals are also known as highest occupied molecular orbit (HOMO) and lowest
unoccupied molecular orbital (LUMO) respectively. Between HOMO and LUMO there is an
energy gap and these states are also recognized as ionization energy (IE) and electron affinity
15

(EA) respectively. The and * states in polymers are broadened into the valance (filled) and
conduction (empty) states due to orbitals coupling along the chain [20, 30].
In organic materials, the splitting of HOMO and LUMO energy levels in the semiconductors
range is due to the formation of alternative single and double bonds in the chains. The materials
having molecular chains with only single bonds () or double bonds () are difficult to include in
the category of semiconductors because of wider energy band gap. So, for semiconducting
properties, the organic materials should have alternative single and double bonds (conjugation)
[51].
2.2.5 Charge transport properties/conduction mechanism of organic semiconductors
In organic molecular solids the ionic molecular states are involved in the transport of electrons or
holes. To create a hole in a neutral molecule M, it is necessary to remove electron to transform it
into radical cation M
+
. This hole (deficiency of electron) move from molecule to molecule.
Similarly electron transport is the result of negatively charged radical ions M
-
. In the case of
conjugated polymers, instead of charged states term of negative and positive polarons is used
[19]. As in organic semiconductors, the bonding orbitals and quantum mechanical wave-
function overlap are responsible for the charge transport. But due to inadequacy of -bonding
overlapping between the molecules of disordered organic semiconductors, the concept of
quantum mechanical tunneling is considered appropriate to explain the charge transport in these
materials [52]. The transport properties of organic semiconductors are categorized by the
following [20]
i. Polaronic Effect
ii. Hopping Conduction
iii. Low Mobility, Low Saturation Velocity
The formation of polaron is the result of interaction of charges with lattice deformation and
polarization [20, 51]. The extension of this deformation in organic materials is on atomic scale
and the mobility of charges reduces due to self trapping [51]. If the same deformation is shared
by two charges is called bi-polaron while the attraction between oppositely charged polaron is
similar to exciton. Polarons are responsible for conduction in single chain molecule [20]

16

Figure 2.3 Conjugated molecules a: copper phthalocyanine, b: polythiophene, c: fullerene,
d: polyacetylene and e: polyaniline
17

As the molecule to molecule movement (conduction between different molecules) of charge
carriers is the basis for charge transport, which is generally called as hoping transport. This name
is given to charge transport process because of its quantum mechanical tunneling nature and
reliance on the probability function [53]. This thermally activated process is dependant on the
energy gap between HOMO and LUMO Levels. The thermal activation can be expressed as [20]

2.1
where E
a
is an energy of the order of 1 eV.
In organic semiconductors the mechanism of charge carrier transport can lay between band and
hopping transport, which are two extremes. Normally, the band transport is observed in highly
purified molecular crystals at temperatures which are not too high. But as compared to inorganic
semiconductors the weak delocalization with small band width is found in organic
semiconductors, which result in low mobility (in the range of 1-10 cm
2
/Vs) at room temperature.
Equation 2.2 shows that temperature dependence of the band transport follows the power law
[19].

2.2
Hopping conduction is somewhat different from band conduction. It occurs in amorphous
organic solids and leads to lower mobility values (around 10
-3
cm
2
/Vs). Only the localized states
exist or play a role in hoping conduction rather than delocalized bands, which are too far or the
required temperature for the charge carrier is too high. As the charges expend their time on
localized states and conduction of charges takes place by hopes between these states. This type
of carrier conduction (mobility) may be influenced by temperature and electric field of the
system as given in Eq.2.3 [19].

2.3
At room temperature the maximum low-field mobility of the most of organic semiconductors is
about 1 cm
2
/Vs and it is less reliant on temperature. This mobility is comparable with amorphous
silicon but much small than that of crystalline silicon. The low temperature causes to increase the
mobility as for example mobility of naphthalene increases below 100K. This increase in mobility
18

is credited to the freeze-out of phonons and hoping to band transport transition. Moreover, for
the description of charge transport in organic solids trapping effect, space charge and charge
carrier injection mechanism should be considered [19, 51]
The drift velocity and charge carrier density are the parameters which define the current through
material on a microscopic level. As given in Eq.2.4, the drift velocity is articulated by mobility
and electric field [19].

2.4
At high field, the drift velocity shows saturation and its values are much smaller even at low
temperature. The charge carrier density n is also the most important parameter. In a
semiconductor having energy band gap Eg and N
o
effective density of states, the intrinsic carrier
density is given as

2.5
A hypothetical density of at room temperature can be lead by
and , which is never reachable until much densities of impurities can be achieved
in real materials. In organic semiconductors the carrier density can be improved by the following
ways:
1. Electro-chemical doping
2. Carrier injection from contacts
3. Photo generation of carriers
4. Field effect doping
2.3 Properties of various organic sensing materials
2.3.1 Polyaniline (PANI)
Polyaniline as a potential conductive polymer has developed great research interest because of its
significant properties like excellent environmental stability, reversible acid-base and redox
chemistry, optical and electrochemical properties [54-56]. Moreover its cheapness, easy
availability of raw materials and simple synthesis technique make polyaniline relatively popular
among the conductive polymers [17, 57]. PANI undergoes solution or counter ion-induced
19

process-ability and it may also be crystallized. To enhance its potential applications, the
secondary doping of PANI is carried out [56].
The general formula for the polyaniline is [(-B-NH-B-NH-)
y
, (-B-N=Q=N-)
1-y
]
x
, where B and Q
are the benzenoid and quinonoid forms of C
6
H
4
rings. Depending on the neutral intrinsic redox
states PANI is classified as [56].
1. Pernigraniline (PNA, y = 0), which is the fully oxidized state with blue/violet color.
2. Nigraniline (NA, y = 0.75), which is the 75% intrinsically oxidized with blue/violet color.
3. Leucoemeraldine (LM, y = 1), which is the fully reduced state having white/clear &
colorless appearance.
4. Eemeraldine (EM, y = 0.5), which is the 50% intrinsically oxidized. The emeraldine salt
has green while emeraldine base has blue color
Emeraldine exist in two forms which are emeraldine base (EB) and emeraldine salt (ES). Among
these the emeraldine base (EB) is the basic form of PANI which consists of four-ring tetramer
structure having two segments of amine and two of imine, and is non-conductive. The dopants
can be doped (included) into PANI or de-doped (released) from it reversibly due to their non-
redox and physical interaction. The conductive emeraldine salt (ES) is produced by the
electrostatic attraction between the anions of incorporated dopants and the nitrogen on the
backbone of polyaniline [54].
The polyaniline has capability to sense acidic, basic and some neutral vapors or liquids. The
sensing mechanism is based on change in electrical conductivity and color upon exposure to such
environments. These features make polyaniline suitable for sensors, indicators and detectors [16,
57-66]. Fuke et al. [60, 61] also studied the Co-polyaniline and Ag-polyaniline nanocomposite
based humidity sensors. They evaluated Co-polyaniline based sensors with various film
thicknesses for humidity sensing and measured the hysteresis and response & recovery times. In
the study of sensors based on Ag-polyaniline nanocomposite clad on optical fibers; the clad
length and nao-particle size were optimized for humidity sensing. A rapid response humidity
sensor based on ultra thin film layer by layer (LBL) assembly of poly (anilinesulfonic acid)
(SPANI) were fabricated by Nohria et al. [64] and compared with SPANI based sensors
fabricated by spin coating. They compared the sensitivity and response and recovery times of
humidity sensors. Pandey et al. [67] fabricated pellets of polyaniline and studied the change in
20

resistance with change in relative humidity. Parvatikar et al. [68] synthesized
polyaniline/tungsten oxide composite by in situ deposition technique and the fabricated pellets
and then characterize them for temperature and humidity sensing.
2.3.2 Carbon nanotubes (CNTs)
The discovery of carbon composed spherical molecule (fullerene) lead the Harry Kroto, Robert
Curl, and Richard Smalley for the award of Nobel Prize in Chemistry in 1996. Research on
theory and synthesis of fullerene was in its full bloom during 1980s and early 1990s [69] when
Iijima [70] discovered multiwall carbon nano tube, which he observed with the help of
transmission electron microscope. At that time this structure was considered as filamentous
carbon. The single wall carbon nanotube was also discovered in 1993 by Iijima [71]. The
discovery of CNT made it the most popular material of global scientific arena and it became one
of the most investigated materials of the 20
th
century.
Carbon nano tubes are rolled sheets of graphene in a cylindrical fashion, while the graphene is a
sheet of hexagonally arranged carbon atoms which are bonded by SP
2
hybridization, while in
CNTs there is very little mixing of and orbitals. These graphene sheets are classified as
single layer or few layer graphene. Depending upon the nature of graphene sheet CNTs are
categorized as single wall, double wall triple wall and multiwall carbon nanotubes [20].
Properties of the CNTs are dependant on chiral angle (angle at which sheets are rolled) and the
radius. Electronically, carbon nanotube (CNT) can be metallic, semiconducting, or small-gap
semiconducting (SGS) materials, it depends on the orientation of the graphene lattice with
respect to the axis of the tube [72]. The numbers of unit vectors along two direction of graphene
crystal lattice defines the electronic behavior of CNTs and these vectors are represented by
indices n and m which are commonly written as (n, m). In case of n=m the nanotube is metallic
and if n-m is the multiple of 3, the tube is small band-gap semiconducting, while in all other
cases normal semiconducting.
The excellent electrical, electronic and mechanical properties along with chemical stability make
the CNTs a popular material for engineering applications. These properties are regarded to the
extremely small size with hollow cylindrical shape and high aspect ratio of CNTs [73, 74]. Due
to their small particle size and large surface area, their ability to promote electron transfer and
bio-sensing properties, the CNTs have proven to be the best material for various kinds of sensors
21

[73]. An extensive research is being carried out to explore the potential of CNTs for
electrocatalytic and sensing applications [75] which include temperature, pressure, strain,
humidity, chemical, gas and bio sensing etc. In various sensing applications, the CNT-based
sensors have advantages of exceptionally higher sensitivity and a faster response at room
temperature over conventional solid state sensors, which are operated at high temperatures (300-
500 C) for higher chemical reactivity [76]. Various types of sensors have been fabricated and
investigated on the basis of single-walled carbon nanotubes (SWCNTs), double-walled carbon
nanotubes (DWCNTs), and multi-walled carbon nanotubes (MWCNTs) [77-86].
It has been confirmed theoretically and experimentally that CNTs are compatible with strain
sensors. In response to torsion or axial strain, the CNTs undergo band-gap changes, which are
chirality dependent [87]. The thin films based on randomly oriented CNTs and CNTs reinforced
composite have proved sensitive to mechanical loading, which demonstrate the macro scale
fabrication of strain sensors. The direct change in resistance results in response to mechanical
loading [88].
2.3.3 Copper phthalocyanine (CuPc)
Phthalocyanine (Pc) is planar aromatic macro-cyclic compound with dark green-blue color
which forms coordination complexes with more than 70 metals including Cu, Al, Ni, Co, Fe and
V etc. These compounds are constituted by alternatively arranged carbon and nitrogen atoms
which forms four isoindole units with a cloud of 18 delocalized electrons [89]. Initially, since
their discovery in 1928 Pcs were used as inks, paints, colors and dyestuff for textiles. Later on,
because of their peculiar physical properties, the phthalocyanines and their derivatives became
fascinating subject of research for materials scientists to explore their potential applications in
various fields including nano-technological devices and molecular materials [89, 90]. Currently
Pcs along with other materials are being used as active materials in LCDs, information storage
systems, photovoltaics, laser dyes, semiconductor and electro-chromic devices and sensors [89,
91, 92].
The copper phthalocyanine is a complex of copper (Cu) with phthalocyanine having blue color,
which is because of to
*
transition at wavelength of ~610 nm. It has exceptional properties
like high stability (i.e. not degraded with time), broad absorption spectra, excellent absorption
coefficient and admirable photoconductivity [93-95]. Its properties like outstanding film growth
22

and chemical and thermal stability make the CuPc the most suitable for thin film organic
semiconductor devices [96]. Moreover CuPc is considered as model system for low molecular
organic semiconductors [97]. For last three decades significant research has been carried out on
CuPc based electronic devices and results for solar cells, secondary batteries, light emitting
diodes, field effect transistors, chemical sensors and gas sensors are reported in literature [98-
104].
2.4 Sensing mechanism
Porous organic materials based thin films or thick films may be used for humidity sensing. The
film contains micro-pores where the condensation of water vapors takes place; and because of
the presence of water molecules, water absorption and/or doping by H
2
O results in change in
some physical properties. On the basis of this change sensors are classified into two basic types,
which are resistive-type and capacitive-type sensors. The change in humidity is responded by
resistive sensor and capacitive sensor by change in conductivity and dielectric constant
respectively [8, 13, 105].
As the temperature is the measure of heat energy which is directly related to the molecular
energy of a system or an object. The mechanism of temperature sensing is based on the change in
physical parameter (eg. as concentration of charges or voltage output) with respect to
temperature variation. Depending upon their structure and sensing mechanism temperature
sensors are classified as electronic, electromechanical and resistive sensors [106]. In this study
we fabricated and investigated resistive type temperature sensors, which are discussed in detail in
chapter 5.
Sensing mechanism of the electromechanical sensors is normally based on piezoresistive effect.
This change in resistance is related to change in electrical conductivity under the effect of
pressure, displacement and strain and can be explained by the percolation theory [107, 108]. In
case of pressure and displacement sensors the resistance decreases or increases with application
or removal of load, while in case of strain sensors, the resistance increases under the effect of
tensile strain, while it decreases under the effect of compression strain. Further explanation for
sensing mechanism of electromechanical sensors is given in chapter 6.
23

2.4.1 Percolation theory
2.4.1.1 Introduction
Percolation theory is considered as a transport mechanism which is applied in various fields of
science and technology having the use of composite materials [109]. The foundation for the
development of percolation theory was the n-dimensional infinite lattice. The occupation of such
(1, 2, 3 or n-dimensional) lattice by various items is the focus of percolation theory. These items
may be atoms, molecule, coarse particles, nanoparticles, trees in the forest etc. Numerous
mechanical properties can be explained by percolation theory. Moreover percolation has
applications in gelation, diffusion in disordered medium, pharmaceutical powder technology,
phase transition in solids etc [44, 110].
The percolation theory is based on a system which consists of sites in a virtual or real lattice of
infinite length. As explained by Stauffer et al. [111] the percolation theory is concerned about the
formation of clusters in a lattice and their properties. The definition of cluster depends upon the
type of percolation phenomena, and the percolation phenomena are mainly classified as site and
bond percolation. According to site percolation, a group of adjacent occupied sites in a lattice is
called cluster, while in bond percolation the collection of occupied neighbors which are
connected by bonds is called cluster. The clusters are further categorized as finite (isolated
cluster) and infinite (cluster that percolates a lattice) clusters. The probability at which some
property change in system causes to percolate a crystal is called the percolation threshold [112].
Percolation theory is suitable for the description of morphological properties of random packings
of solid particles. These properties include coordination number and morphological factor related
to electrical conductivity and tensile strength of structure. The number of contacts made by each
particle with its neighbors is called the coordination number, which is associated to the
percolation threshold and the probability of connection. This probability is related to the
particles, which provide the connected conduction pathway in the percolating clusters [109].
2.4.1.2 Percolative transport
The segregation of conducting regions in highly disordered conductive polymers (CPs) may
occur by insulating barriers or the resistive pathways make a feeble connection between them.
The charge transport mechanism in this situation may be due to one of the following; because of
24

charging effects in granular metals or because of percolation. The percolative transport can be
observed in blends in which conducting polymer is dispersed in insulating matrix. A new class of
percolating systems (having conducting objects aspect ratio greater than one) is provided by the
development of self assembled conducting network. This results in much lowering of percolation
threshold, which was observed 16 % volume fraction in conventional percolating system.
Percolation theory may also be used for the modeling of conduction that occurs in
interpenetrating network by thermally assisted hopping transition between spatially separated
sites. According to percolation theory, the average conductivity of one component may be
expressed as

2.6
Where, l is the characteristic length and it depends upon concentration of sites, Z is the resistance
of the path with the lowest average resistance [108].
2.5 Applications
The effect of universal existence of water in air is considerable not only for the comfort of living
organisms but also for the control of industrial processes. The applications of humidity sensors
have become very important for smart control of living environment, cooking and laundry at
domestic level, monitoring of humidity during wafer processing in electronic industry and motor
assembly lines and rear window defogger in automobile industry. The monitoring of air-
conditioning and soil moisture, plant protection and cereal storage all require the humidity
sensors [105].
Temperature sensors are widely used in medical technology and industry, in particular,
aerospace, nuclear, mechanical, chemical, electronics. These sensors are also used in houses,
workshops, stores and farms.
The displacement sensors are used for the displacement measurement of a physical object. This
measurement plays an important role in security systems, robotics, control of feedback,
transportation traffic control and performance evaluation [13]. Moreover these sensors are also
25

used for the measurement of deflection, deformation, distortion, thickness and vibration of an
object [106].
Pressure sensors widely used in process control, HVAC systems, for the measurement of altitude
of aircraft and its turbidity, earth moving equipment and forklifts. These sensors are also used in
medical equipment to regulate intravenous infusions, monitor blood pressure and for the
detection of changes in glaucoma, cranial pressure and hearing problem. Pressure sensors are
also frequently used in daily life [106].
Strain sensors have capability to monitor strain, pressure, force and shape [54]. These sensors
have wide use in different fields of engineering for detection of damage in an object and
infrastructure [113], control of robotic arms, monitoring of human motion, speech therapy [114],
study of bone tumors and onset of osteoporosis, and wear and tear monitoring in prosthetic limbs
or implants. Strain sensors are under extensive research for future applications, especially for
mechanical and biomechanical applications [115].

26

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implants', 2007, IEEE, 119-122.
35

Chapter-3
Materials and Experimental
3 1
Detailed information about materials, techniques of fabrication and experimental setup is
provided in this chapter. This chapter consists of four sections. The section one contains
information about materials used for the fabrication of sensors and their physical and chemical
characteristics. Second section consists of fabrication technique used for the development of
sensors, which include the substrate preparation, metallic and organic thin film deposition, and
pellet formation. Third section describes the details of devices used for fabrication and
characterization of devices. The elaborated description of experimental setups used for the
testing of various sensors is given in section four.
3.1 Materials
3.1.1 Polyaniline (PANI)
Polyaniline based humidity and displacement sensors are fabricated by using gold, silver and
aluminium metal electrodes. Humidity sensors are characterized for various electrical and
physical parameters such as impedance, capacitance, absorption-desorption behavior and
response and recovery times. The effect of annealing, film thickness and frequency are also
studied. For the displacement sensors change in AC resistance and capacitance are measured
with change in displacement [1]. The detailed discussion about the chemical and physical
properties of polyaniline and its uses is given in chapter 2. Molecular structure and physical
properties of PANI are shown in Figure 3.1 and Table 3-1 respectively.
3.1.2 Cellulose
The commercially available cellulose ((C
6
H
10
O
5
)
n
) is blended with poly-N-epoxypropylcarbazole
for the fabrication of humidity sensors. The blend is deposited on copper electrodes having gap
between them. Cellulose is a water insoluble white powder with density of 1.592 g/cm
3
and
decomposes on heating at elevated temperatures [2, 3]. The Figure 3.2 and Table 3-1 represent
the molecular structure and physical properties of cellulose respectively.
36

3.1.3 Poly-N-epoxypropylcarbazole (PEPC)
The Poly-N-epoxypropylcarbazole (PEPC) has a formula (C
16
H
13
NO)
n
. As the molecular weight
of PEPC having density of 1.3 g/cm
3
is 941.1-1411.6 a.m.u. and its melting point is 260 C. The
blend of PEPC with cellulose powder is used to make humidity sensors [4], while its composite
with vanadium oxide (V
2
O
4
) is used for the fabrication of temperature sensors [5]. The molecular
structure and physical properties of PEPC are given in Figure 3.3 and Table 3-1 respectively.
3.1.4 Copper phthalocyanine (CuPc)
Copper phthalocyanine (CuPc) is a p-type semiconductor and is used for the fabrication of
organic-inorganic Ag/p-CuPc/n-GaAs/Ag cell. Thin films of CuPc are deposited on the surface
of highly doped single crystal GaAs substrates. For the Ag/p-CuPc/n-GaAs/Ag cell the forward
and reverse bias resistances-temperature relationships are investigated in the temperature range
of 33-75 C [6]. Figure 3.4 and Table 3-1 show the molecular structure and Physical properties
of CuPc respectively.
3.1.5 Orange dye (OD)
Orange dye belongs to the family of organic materials known as azo-dyes [7]. The blend of
orange dye with polyaniline is deposited on silver electrodes for the fabrication of surface type
humidity sensors. The sensors were characterized for electrical properties like capacitance and
impedance, while the effect of annealing on the electrical properties was also studied. Physical
parameters like absorption-desorption behavior and response and recovery times are also
investigated. Figure 3.5 and Figure 3.6 show the molecular structures of general azo dye and
orange dye respectively, while the physical properties of orange dye are given in Table 3-1.

37

Figure 3.1 Molecular structure of Polyaniline (PANI) (n=m=0.5) [8]

Figure 3.2 Molecular structure of Cellulose

n
x
m
N
N
H
N
H
N
38

Figure 3.3 Molecular structure of Poly-N-epoxypropylcarbazole (PEPC) (where n=4-6)

Figure 3.4 Molecular structure of Copper Phthalocyanine (CuPc)

N
n
CH2
CH CH2
O
39

N N NO
2
N
R
R'

Figure 3.5 General azo-dye structure

If R = R = H then Orange Dye 3
If R = CH
2
CH
3
& R = CH
2
CH
2
OH then Red Dye 1
If R = CH
2
CH
3
& R = CH
2
CH
2
CN then Orange Dye 25

N N NO
2
N
CH
2
CH
3
CH
2
CH
2
CN

Figure 3.6 Molecular structure of Orange Dye 25 (OD) [7]

40

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41

3.1.6 Carbon nanotubes (CNTs)
The nanopowder of multiwalled carbon nanotubes (MWNTs) having diameter ranging from 10-
30 nm [11, 12] are used for the fabrication of temperature, strain and pressure sensors.
Temperature sensors with two different designs are fabricated; to make flexible sensors CNTs
are deposited on adhesive polymeric tape and aluminium foils are used as electrodes, while other
type of sensor is fabricated by depositing CNTs on paper with the help of glue, where the silver
paste is used as an electrode [13]. The change in DC electrical resistance with respect to
temperature is studied. For strain and pressure sensors [14, 15], pellets of CNTs and CNTs-Cu
2
O
nano composite have been made at various pressures by using hydraulic press.
3.1.7 Cuprous oxide (Cu
2
O)
Copper (1) oxide which is also called cuprous oxide is a semiconducting material with energy
band gap of 2.7 eV. The cuprous oxide has been used to fabricate strain and pressure sensors. For
the fabrication of strain and pressure sensors, the tablets of CNTs-Cu
2
O nanocomposite are
prepared on hydraulic press. The physical properties of Cu
2
O are given in Table 3-2.
3.1.8 Vanadium oxide (V
2
O
4
)
Vanadium oxide has interesting nature, it shows large reversible changes in electrical, magnetic
and optical properties at temperatures around 68-70
C [16-18] where semiconductor to metal

transition takes place. In this study the V
2
O
4
powder (average particle size=20 m) is blended
with PEPC to make the composite for the fabrication of bulk hetero junction thin films
temperature sensors. The fabricated sensors are investigated for the resistance-temperature
relationships. Table 3-2 shows the physical properties of vanadium oxide.
3.1.9 Gallium arsenide (GaAs)
For the fabrication of electronic devices both organic and inorganic materials have some
advantages and disadvantages. In the present study we make the combined use of two kinds of
semiconductor materials in order to improve the characteristics of the cell [19]. For this purpose

42

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43

we use Gallium arsenide in combination with copper phthalocyanine for the fabrication of
organic-on-inorganic Ag/p-CuPc/n-GaAs/Ag cells.
Gallium arsenide is III/V n-type semiconductor with energy band gap of 1.4 eV. A single crystal
of GaAs (n-type inorganic semiconductor) was used for the fabrication of cell. The GaAs crystal
was oriented at (100) plane. The donor impurities level (N
D
) was 2 x 10
18
cm
-3
. The physical
properties of GaAs are also given in Table 3-2.
3.2 Fabrication techniques
Fabrication technology can highly affect the cost, stability and performance of organic
semiconductor devices. The organic semiconducting materials are categorized as oligomers and
polymer depending upon the number of monomer units. These materials have strong
intramolecular bonding (covalent bonding) while weak Vander Walls forces exist between
molecular chains. For the selection of suitable fabrication method, the nature of material and
design of the device play a major role. Normally polymers are deposited by solution methods
while oligomers are deposited by evaporation techniques. For the fabrication of efficient device
and to make the fabrication process repeatable the structural control of organic film is very
important which can be obtained by optimizing the process parameters.
During current study, keeping in view the simplest, cheapest and repeatable process, following
fabrication techniques have been used and the fabrication processes are found repeatable with
percentage standard deviation of 5-10%.
Vacuum thermal evaporation
Drop casting
Adhesive tape
Glued film
The detailed information about the substrates and organic film deposition techniques used for the
fabrication of devices is given below.
3.2.1 Substrate preparation
Ordinary medical glass slides were used as a substrate. For cleaning, substrates were immersed
in beaker filled with acetone and placed in an ultrasonic bath for 15 minutes. After sonication
44

substrates were washed with hot distilled water (70-80 C) and dried. To make gap between two
electrodes the substrates were masked by using copper wire. The substrates were plasma cleaned
before metallization.
3.2.2 Metallization
After cleaning metallic electrodes having thickness 50-100 nm were deposited on the glass
substrates by using EDWARD AUTO 306 vacuum Thermal Evaporator. For metallization, high
purity (99.99 %) gold, silver, aluminium and copper metals were cleaned by dipping in acetone.
To deposit thin film electrodes, dried metals were evaporated under a vacuum of 1 x 10
-5
mbar.
During this work single layered metallic electrodes were deposited, which are adherent to the
glass substrates and can not be scratched easily.
3.2.3 Vacuum thermal evaporation
This technique is commonly used for the thin film deposition of low molecular weight organic
semiconducting materials. EDWARD-306 vacuum thermal evaporator was used for deposition.
The apparatus consists of a chamber which is connected with pumps which are used to create
vacuum up to 10
-7
mbar and a control panel. Vacuum chamber contains resistively heated boats
which are connected with terminals, a sample holder, a crystal thickness monitor and a shutter to
control the deposition. For thin film deposition material is evaporated by placing it in the boat
which is heated under vacuum. The evaporated material goes upward and its mean free path
depends upon the intensity of vacuum. The deposition rate is controlled by adjusting the current
supplied to the heating boat. By this technique very good quality thin films or layers with smooth
surface and uniform structure are deposited. During current study CuPc thin films were deposited
on GaAs single crystal substrates by using vacuum thermal evaporator.
3.2.4 Drop casting
Drop casting also called casting is the simplest and cheapest film forming technique [20, 21],
which is based on the tendencies of organic materials to self-assemble [22]. This technique has a
potential for large area deposition for technological applications [23]. By this technique materials
which can be dissolved in any kind of solvent are deposited. The blends of organic-organic and
organic-inorganic materials can be prepared by using suitable solvent to dissolve both the
components. The prepared solution is poured on to the horizontally placed substrates followed by
45

drying. In this study solutions of polyaniline, orange dye-polyaniline, Cu
2
O-PEPC, PEPC-
Cellulose, V
2
O
4
-PEPC have been drop casted to fabricate the thin films on to the preliminary
deposited metallic electrodes. Solvents used for PANI and OD-PANI solution are water with 10
wt% alcohol and only water respectively, while for all remaining materials benzol was used. The
deposited films are adherent to the substrates and their surfaces show slightly rough topography,
which may be due to factors like solubility of materials in solvent and surface tension etc. [21].
3.2.5 Adhesive tape
It is very simple technique to make flexible thin films in which adhesive tape is used as a
substrate. To make the thin film, material is sprayed on to the adhesive tape in dry powder form.
During current study dry powder of multiwalled carbon nanotubes were sprayed on to the
adhesive tape to make the thin films for flexible temperature sensors, while aluminium foils were
used as metallic electrodes. To make the device structure durable and minimize the effect of
humidity, the CNTs deposited substrates were raped by same adhesive tape. The structure was
found repeatable.
3.2.6 Glued film
It is also a very easy film forming technique in which dry powers are sprayed on to the freshly
applied layer of glue. This technique can be applied to both flexible and non-flexible substrates.
In this study we applied this technique on paper substrate for the fabrication of multiwalled
carbon nanotubes based temperature sensor. Both gluing and adhesive tape techniques are
promising for large area deposition.
3.2.7 Cold compaction
The materials from the powder form are pressed in the form of pellets. These pellets are used as
an active material in sensors. During present work, the cold compaction technique has been used
for the preparation of CNTs and Cu
2
O-CNTs composites pellets. To make the composites the
constituent materials are mixed thoroughly by using mortar and pestle. The powders are pressed
at pressures of 200, 300 and 353 MPa by hydraulic press with die and plunger as accessories and
the pressed pellets have finished surface. The exerted pressure was calculated by the following
expressions

46

3.1

and

3.2

Where
= Force
= Area of die plunger at which force is exerted
= Gauge pressure
= Area of press ram at which force is exerted
3.3 Film characterization
3.3.1 Crystal thickness monitor
For the thickness measurements of the films deposited by the vacuum thermal evaporator, the
FTM5 thickness monitor is used. It uses microbalance technique for the measurement of
thickness along with deposition rate. The FTM5 is a micro-processor based frequency counter,
which needs density and acoustic impedance data of material to be deposited and it works in
conjunction with a quartz crystal and oscillator unit. This crystal is placed in deposition field and
controls the oscillators frequency. On the basis of provided data the micro-processor converts
the frequency changes into deposition rate and thickness. Technical data of crystal thickness
monitor is presented in Table 3-3.
3.3.2 Optical microscope (OM)
Optical or light microscope is a type of microscope which uses visible light and a system of
lenses to magnify images of small samples. OLYMPUS B061 microscope was used for
observations of surface morphologies of organic films.
47

3.3.3 Scanning electron microscope (SEM)
SEM is a type of electron microscope that images the sample surface by scanning it with a high-
energy beam of electrons in a raster scan pattern. The signals are produced by the interaction of
electrons with the atoms that make up the sample and these signals contain information about the
sample's surface topography, composition and other properties such as electrical conductivity.
Philips XL30 scanning electron microscope was used for microstructural analysis.

48

Table 3-3 FTM5 Crystal thickness monitors technical data [24]
Frequency of crystal sensor 6 MHz unloaded
Density 0.1 to 99.9 g/cm
3

Acoustic impedance 1.0 to 99.9 x 10
5
gcm
-2
s
-1

Range of rate of deposition measurement 0.0 nms
-1
to 999.9 ms
-1

Resolution of deposition measurement range 0.1 nms
-1

Range of thickness measurement 0.0-999.9 m
Thickness resolution 0.1 nm

49

3.4 Experimental setups
3.4.1 Apparatus for thin film deposition
Metallic and polymeric thin films are deposited by physical vapor deposition technique in a
vacuum. This process is also called thermal evaporation process which is comprised of three
steps that include the generation of vapor by sublimation/boiling of source material,
transportation of vapor from source to target and condensation of vapor as solid film on to the
target. No chemical reaction is involved in this process [25]. Materials like metals, alloys and
low molecular weight organic materials can be deposited by this technique. The composite films
can also be deposited by co-evaporation of two or more materials. Vacuum plays an important
role in lowering the boiling or sublimation temperature and increasing the mean free path of the
vapors. Quality of films depends upon the gap between source and substrate, temperature of the
substrate, vacuum level and the rate of deposition.
During the course of experimental work EDWARD AUTO 306 vacuum coater was used for the
fabrication of metallic electrodes and organic thin films. Thicknesses of films deposited by
thermal evaporator may range from nanometers to few micrometers. This apparatus consists of
vacuum chamber, pumping system and control panel as illustrated in Figure 3.7. Samples are
placed in a vacuum chamber at the top of the boat containing the source material. Material is
evaporated by the resistive heating of boats which are made of molybdenum. The rate of
evaporation is controlled by adjusting the current passing through the boat and also by
controlling the vacuum. Pumping system is used to create vacuum in the chamber by evacuating
the gases from the chamber. Low vacuum (upto 10
-3
Torr) is attained by the rotary pump, while
the diffusion pump backed by rotary pump is used to create high vacuum (10
-7
mbar). The
temperature of the sample holder can be adjusted in a range of temperature by resistive heating
elements and water-cooling. Number of boats and shutter are used for layer by layer deposition
of materials. The deposition rate and the films thickness are measured by the quartz crystal
oscillator.

50

Figure 3.7 Schematic diagram of thermal evaporator
1. Vacuum Chamber 2. Sample Holder
3. Sample 4. Shutter
5. Flow of Vapors 6. Evaporant
7. Resistive Heating Boat 8. Vacuum Pumps
9. Quartz crystal oscillator
8
1
2
3
4
5
6 7
9
51

3.4.2 Apparatus for testing of humidity sensors
For electrical characterization of humidity sensors testing setup was indigenously designed and
fabricated. Setup is shown in Figure 3.8, it consists of following parts
1. Testing chamber
2. Sample holder
3. Gas Cylinder
4. Pressure gauges for control of gas flow
5. Water chamber
6. Inlet and outlet valves
7. Standard humidity meter
8. Electrical meter
Both testing and water chambers are made of 12 mm thick plates of PMMA and their sizes are
15.6x10
3
cm
3
and 15.5x10
3
cm
3
respectively. Testing chamber contains a small chamber in it
which have sample holder and can easily be isolated by manual system for closing and opening
of window. This system is used for measuring response and recovery time by the sudden
exposure of sensors to a certain level of humidity. Humidity level in the testing chamber is
maintained by the supply of nitrogen gas, which is controlled by pressure gauges. To increase the
humidity, gas is initially humidified by passing it through the water chamber and then injected to
the testing chamber, while the humidity is decreased by directly injecting the dry nitrogen into
the chamber. The humidity range of this apparatus is 0 % to 100 % relative humidity (RH).
Humidity is measured by standard humidity meter. For the measurement of sensors response to
change in humidity the LCR meter is attached to the sensor.
3.4.3 Apparatus for testing of temperature sensors
Apparatus for testing of temperature sensors is shown in Figure 3.9. This apparatus consists of a
glass chamber which is surrounded by a thermally isolated cylinder. For heating, an electrical
heater made of nichrome wire is fixed in the lower part of the cylinder beneath the glass
chamber. Chambers temperature can be maintained in the range of room temperature to 250 C,
while the glass chamber is closed by the insulating plate. The temperature is maintained at a
specific value to let the sensor saturate. Samples are placed on the sample holder and, a mercury
thermometer and Fluke 87 V meter are used for the measurement of temperature.
52

3.4.4 Apparatus for testing of displacement sensors
Testing setup for the displacement sensor shown in Figure 3.10. It consists of micrometer
vertically clamped with table. A spring and a round piece of elastic rubber are attached with the
face of spindle. For testing, sandwich type sensors are fixed between elastic rubber and the anvil
of micrometer. The displacement is changed by the upward and downward movement of spindle.
As the spindle moves down in vertical direction the value of the displacement increases. The
range of the displacement depends upon the heights of the spring and elastic rubber. Due to
limited use at lab scale the elastic rubber maintains its mechanical properties for a long time.
3.4.5 Apparatus for testing of pressure sensors
Figure 3.11 shows the experimental setup for the investigation of pressure sensors. The setup is
comprised of (1) support, (2) weight holder (3) weights and sensor (4). In this setup sensor is
installed on a rigid cantilever beam. One end of the beam is fixed on a vertical column which is
welded with a support. Pressure is applied on the sensor by putting the weight in weight holder.
The pressure can be changed by changing weights, in the conventional laboratory setup Flexor:
Cantilever Flexure Frame.
3.4.6 Apparatus for testing of strain sensors
The elastic beam having constant resistance to bending with and without load is fixed by clamp
on a stand with a solid base as shown in Figure 3.12. Length and thickness of specially designed
elastic beam are 150 mm and 2 mm respectively, while width at foot of the beam is 30mm. The
average modulus of elasticity of the beam is 2.71 GPa. Samples are installed on a beam by glue.
Loads are hanged on the tip of beam to strain the sample: for tensile and compression strain,
samples are fixed on the upper surface and lower surface of the beam respectively. The
longitudinal strain is determined by using the following expression [26, 27].

3.3
where L is length, b
o
is width at foot of the beam, h is thickness of the beam, E is modulus of
elasticity and P is load. For a beam of specific dimensions and modulus of elasticity strain is
changed by varying the applied load (P).
53

Figure 3.8 Apparatus for testing humidity sensors
1. Nitrogen Gas Hose
2. Pressure control gauges
3. Water chamber
4. Stand for pressure gauges
5. Humidity chamber
6. Testing Chamber

5
1
6
3
2
4
54

Figure 3.9 Schematic of testing setup for the characterization of temperature sensors

55

Figure 3.10 Schematic diagram of the experimental setup for characterization of
displacement sensors [28]
56

Figure 3.11 Schematic of apparatus for the investigation of pressure sensors [29]
1. Support 3. Weights
2. Weight Holder 4. Pressure Sensor

Figure 3.12 Simplified schematic diagram of the elastic beam of constant resistance to
bending without load; (a) side view, (b) top view, and under load (c) side view [26].

Sample Beam
L
b
o
Beam
Sample
P
Sample under
tension

Sample under
compression
Beam
2
Pressure
1
3
4
a c b
57

References
1. K.S. Karimov, M.T. Saeed, F.A. Khalid and S.A. Moiz: 'Effect of displacement on
resistance and capacitance of polyaniline film', Chinese Physics B, 2011, 20, 040601.
2. Z. Ahmad, M.H. Sayyad and K.S. Karimov: 'Bi-layer capacitive type light and humidity
sensors', Journal of Ovonic Research Vol, 2008, 4(5), 91-95.
3. S. Kimura, H. Kusano, M. Kitagawa and H. Kobayashi: 'TEM characterization of
cellulose Langmuir-Blodgett films', Appl. Surf. Sci., 1999, 142(1-4), 579-584.
4. M.T. Saeed, F.A. Khalid, K.S. Karimov and M. Shah: 'Organic Cu/cellulose/ PEPC/Cu
humidity sensor', Optoelectronics and Advanced Materials-Rapid Communications,
2010, 4(6), 888-892.
5. M.T. Saeed, K.S. Karimov, F.A. Khalid, M. Farooq and M. Saleem: 'A study of V2O4-
PEPC composite based resistance temperature sensors', 1st Saudi International
Electronics, Communications and Photonics Conference, Riyadh, Saudi Arabia, April 23-
26, 2011, IEEE, 1-5.
6. K.S. Karimov, F.A. Khalid, M.T. Saeed, T.A. Qasuria, Z.M. Karieva and M. Farooq:
'Temperature sensing properties of organic-inorganic Ag/p-CuPc/n-GaAs/Ag cell',
International Symposium on Vacuum Science and Technology Islamabad, Pakistan,
November 2-6, 2010.
7. S.A. Moiz: 'Temperature dependent electrical characterization of orange dye, poly-N-
epoxypropylcarbazole and copper phthalocynanine based organic semiconductor diodes
for sensor technology', PhD thesis, Ghulam Ishaq khan Institute of Engineering Sciences
and Technology, Topi, Pakistan, 2005.
Prog. Polym. Sci., 2008, 33(7), 732-758.
9. http://www.sigmaaldrich.com/catalog. '.
10. K. Akhmedov: 'Synthesis, properties and application of carbazolile containing polymers',
PhD thesis, Academy of Sciences, Dushanbe, Tajikistan,, 1998.
11. http://www.sunnano.com. '
12. A. Mateen: 'Synthesis and properties study of copper, cuprous oxide CNT reinforced
nanocomposite', PhD thesis, GIK Institute of Engineering Sciences and Technology,
Topi, Pakistan, 2007.
58

13. K.S. Karimov, M.T.S. Chani and F.A. Khalid: 'Carbon nanotubes film based temperature
sensors', Physica. E, low-dimentional systems and nanostructures, 2011, 43(9), 1701-
1703.
14. K.S. Karimov, M.T.S. Chani, F.A. Khalid, A. Khan and R. Khan: 'Carbon nanotube
cuprous oxide composite based pressure sensors', Chinese Physics B, 2012, 21, 016102.
15. K.S. Karimov, M.T. Saeed Chani, F. Ahmad Khalid and A. Khan: 'Strain sensors based
on carbon nanotubescuprous oxide composite', Physica E: Low-dimensional Systems
and Nanostructures, 2012, 44(4), 778-781.
16. E.E. Chain: 'Optical properties of vanadium dioxide and vanadium pentoxide thin films',
Appl. Opt., 1991, 30(19), 2782-2787.
17. G. Guzman. 'Vanadium dioxide as infrared active coating', 2000; Available from:
http://www.solgel.com/articles/August00/thermo/Guzman.htm.
18. I.P. Parkin, R. Binions, C. Piccirillo, C.S. Blackman and T.D. Manning: 'Thermochromic
coatings for intelligent architectural glazing', Journal of Nano Research, 2008, 2, 1-20.
19. K.S. Karimov, M.T. Saeed, F.A. Khalid and Z.M. Karieva: 'Photoconductive properties
of organic-inorganic Ag/p-CuPc/n-GaAs/Ag cell', Journal of Semiconductors, 2011, 32,
072001.
20. A.A.M. Farag and I.S. Yahia: 'Structural, absorption and optical dispersion characteristics
of rhodamine B thin films prepared by drop casting technique', Optics Communications,
2010, 283(21), 4310-4317.
21. F.C. Krebs: 'Fabrication and processing of polymer solar cells: A review of printing and
coating techniques', Sol. Energy Mater. Sol. Cells, 2009, 93(4), 394-412.
22. V. Nadazdy, R. Durny, J. Puigdollers, C. Voz, S. Cheylan and M. Weis: 'Defect states in
pentacene thin films prepared by thermal evaporation and LangmuirBlodgett technique',
J. Non-Cryst. Solids, 2008, 354(19-25), 2888-2891.
23. N.A. Azarova, J.W. Owen, C.A. McLellan, M.A. Grimminger, E.K. Chapman, J.E.
Anthony and O.D. Jurchescu: 'Fabrication of organic thin-film transistors by spray-
deposition for low-cost, large-area electronics', Org. Electron., 2010, 11(12), 1960-1965.
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Royal, Crawley, West Sussex, RH 102LW, UK.
59

25. J. Affinito: 'A new method for vacuum deposition of polymer films', Thin Solid Films,
2002, 420, 1-7.
26. K.S. Karimov: 'Electric properties of organic materials at deformation', PhD thesis,
Academy of Sciences, Tashkent, Uzbekistan, 1994.
27. C.S. Smith: 'Piezoresistance effect in germanium and silicon', Physical Review, 1954,
94(1), 42.
28. K.S. Karimov, M. Saleem, Z. Ahmad, M. Farooq, Z. Karieva and A. Khan: 'The resistive
and capacitive Cu2OPEPC composite-based displacement transducer', Phys. Scr., 2010,
82, 065702.
29. K.S. Karimov, M. Saleem, M. Mahroof-Tahir, T. Khan and A. Khan: 'Pressure sensitive
organic field effect transistor', Physica E: Low-dimensional Systems and Nanostructures,
2010, 43(1), 547-551.

60

Chapter-4
Humidity Sensors
This chapter includes investigation of impedance humidity sensors based on polyaniline, orange
dye-polyaniline composite and cellulose-PEPC composite. For preparation of surface type
sensors, thin film metallic electrodes having 40-50m gap between them were deposited on to
the 25mm x 25mm size microscope glass slides. Thin films of organic materials having different
film thicknesses were deposited from their solutions in to the gap between metallic electrodes.
The sensors were investigated for a wide range of humidity (upto 90% RH). The investigations
show that the sensing mechanism is based on the impedance and capacitance variations. It is also
observed that annealing enhanced the sensitivity of the sensors by two times. The consequences
of measuring frequency and absorption-desorption behavior of the humidity sensors are also
discussed in detail. The response (
res
) and recovery (
rec
) times are also presented. Moreover
experimental results are simulated and simulation is found in good agreement with experimental
data.
4 3
4.1 Polyaniline based humidity sensors
4.1.1 Introduction
Measurement and control of humidity is very important not only for human comfort but also for
manufacturing processes and industrial products [1] because of universal existence of water,
which affects the human health and physical properties of materials [2]. Humidity sensors are
widely used in semiconductor, automobile, medical, pharmaceutical, health caring, textile, paper,
agriculture and food industry [3, 4].
Commercially available humidity sensors are fabricated by conventional sensing materials like
alumina, ceramics and electrolytic metal oxides [4]. The humidity sensors based on organic
sensing materials are classified in to capacitive, resistive [4], oscillating, mechanical [5], and
thermoelemental [6] type sensors depending upon basic sensing principle. Based on its unique
advantages each type of sensor has specific applications. To make the sensor suitable for
commercialization; the wide range sensitivity, linear response, small hysteresis, short response
61

and recovery time, low cost and low power along with long term physical and chemical stability
are the required characteristics [5, 6].
The polyaniline (PANI) is one of the most interesting polymers due to its good stability, easy
preparation and its potential for fabrication of different microelectronic devices [7-10]. The
existence of oxidation states in PANI provides basis for its sensitivity to water [11]. The change
in resistance of polyaniline with change in relative humidity was studied by Pandey et al. [12]. In
this study 0.55-0.89 mm thick pellets of polyaniline with 13 mm diameter were prepared by
using 7 ton hydraulic press. The change in resistance from 5.8 G to 13.9 M is reported for
change in humidity from 15 to 90% RH, while response and recovery time was 1 minutes for 30
% change in humidity. A rapid response humidity sensor based on ultra thin film layer by layer
(LBL) assembly of poly (anilinesulfonic acid) (SPANI) were fabricated by Nohria et al. [3] and
compared with SPANI based sensors fabricated by spin coating. For LBL and spin coated
structure the reported sensitivity is 11 % and 6 % respectively for 5 % change in relative
humidity. The response time is 15 s and 27 s respectively for LBL and Spin coated sensors,
while the overall recovery time is 60 s. The present work describes the fabrication and
investigation of Au/PANI/Ag humidity sensors.
4.1.2 Experimental
4.1.2.1 Fabrication of sensors
A commercially available polyaniline (PANI) emeraldine base (EB) with molecular weight
~20,000 and formula C
24
H
20
N
4
was purchased from Sigma Aldrich and was used for preparation
of samples. The solution was prepared by mixing 1 wt% PANI powder in a mixture of 90 wt%
water and 10 wt% alcohol, and stirred at room temperature. Microscope glass slides of size
25x25x1 mm
3
were used as substrate. Glass substrates were cleaned for 10 minutes using
acetone in ultrasonic cleaner and dried. Then the substrates were also plasma cleaned for 5 min.
By using EDWARDS AUTO 306 vacuum thermal evaporator the Au and Ag thin film electrodes
were deposited on cleaned substrates by keeping a gap of 50 2 m between them. The thickness
of the Au and Ag electrodes was 100 1 nm and the gap length was kept 10 mm. Polyaniline
films having thickness of 30-70 3 m were deposited at room temperature from solution by
drop-casting between the Au and Ag electrodes, which were pre-deposited on glass substrates.
Figure 4.1 shows schematic diagram of the Au/PANI/Ag samples. Before testing the fabricated
62

devices were kept at room temperature for 72 hours to let the moisture evaporate from the films.
To remove the structural defects of organic film, the samples were annealed at 100
C for 1 hr in
air at atmospheric pressure.
4.1.2.2 Measurements
The sensors were tested in indigenously made humidity chamber, which has been developed in
our device testing laboratory. It is a closed chamber with inlet and outlet valves for gas. To
create humidity in the chamber, nitrogen gas is passed through the water and then injected in to
the chamber. The humidity is measured by Fisher Scientific Digital Hygrometer. The capacitance
(C) and dissipation (D) are measured by using ESCORT ELC-132 A LCR meter at different
frequencies, while the parasitic capacitance is deducted from the data. The resistance (R) and
impedance (Z) are calculated by the following expressions [13]:

4.1
and

4.2

where f is frequency and Y is admittance. Here the impedance of the hygrometer was considered
as an impedance of parallel connected resistance and capacitance. Testing is carried out at a
room temperature. The accuracy of humidity and capacitance measurement is 2.5% and 1.0
% respectively, while the error in the impedance is 3.5%.
To check the repeatability of the results, the sensors are tested four times and the percent relative
standard deviation of the experimental results is calculated by using the following expression
[14]

4.3

Where V is the relative standard deviation (RDS), s is the absolute standard deviation and is
the mean. From the experimental results shown in Table 4-1, the percentage standard deviation is
found as 5%.
63

4.1.3 Results and discussion
Figure 4.2 shows SEM images of polyaniline thin film. It can be seen that the polyaniline film's
surface structure is porous and non-uniform; it also contains clusters of particles and the size of
clusters are in the range of 5-15 m. Figure 4.3 shows the relationships of capacitance and
impedance with relative humidity for the Au/PANI/Ag sensor at 120 Hz. It can be seen that the
capacitance shows enormous increase in the intervals of 70-90% RH, while change in impedance
with increase in humidity is more uniform in the range of 36-90% RH. The change of the
sensors capacitance and impedance over whole humidity interval are 167 and 471 times
respectively. This change in the electrical properties of PANI due to change in relative humidity
is because of firstly, adsorption (chemisorptions and physisorption) and absorption of water
molecules and secondly, increase of charges concentration due to doping of PANI and formation
of charge transfer complexes (CTC) [11]. The emeraldine base PANI structure is comprised of
oxidized and reduced (non-oxidized) forms of structures. These both forms can be protonated
due to the un-bonded electron pair on the nitrogen atom as [15]
NH + H
+
NH
2
+

And
N= + H
+
NH
+
=
The protons are obtained by the dissociation of some absorbed water molecule[16]. The buildup
model explains that when water content in PANI reaches 0.1% (mole ratio) the hopping is the
dominant conduction process [15, 17]. In this process electron is transferred from the protonated
reduced form (NH
2
+
) to the protonated oxidized form (NH
+
=). In the conduction process
water plays a vital role and reaction by which proton is transferred to the water is the following
[3, 15]
NH
2
+
+ H
2
O NH
+
= + H
3
O
+
+ e
-

The electron hopping assisted by proton exchange makes PANI sensitive to water vapors. Hence
it may be considered that electronic and ionic conduction take place during humidity sensing
process [15].
100 m
64

Figure 4.4 shows impedance-relative humidity relationship for frequencies of 120 Hz and 1 kHz
respectively. From Figure 4.4 it can be seen that the calculated values of the samples impedance
decrease uniformly with increase of humidity. The values of the impedance also decrease with
the increase of frequency on any relative humidity level. Dependence of the impedance on the
frequency can be explained by the dependence of dielectric permittivity [18], mobility of ions
(firstly) and electrons (secondly) and transit time of charges transfer on the frequency [19].
Figure 4.5 shows impedance-humidity relationship during increasing and decreasing of humidity
where the values are taken at room temperature at a frequency of 120 Hz. It can be seen that the
curves are coincided within the experimental error of 2 %. It means that no hysteresis or
humidity memory effect was found which were observed in PANI and PANI doped with 5-
formyl-2-furansulfonic acid [20, 21] earlier. Table 4-2 shows the humidity sensing properties of
the PANI.
For simulation of the experimental results of impedance-humidity relationship shown in Figure
4.3, the following exponential function [22] is used:

4.4
which for the present experiment can be represented in the following form:

4.5
where A is constant with value 1, H is the change in humidity (H=H H
o
), H
m
is maximum
humidity (H
m
=90 %), K is humidity factor, Z and Z
o
are impedances at different humidity and
humidity of 36 % respectively. From experimental data shown in Figure 4.3 the humidity factor
K is determined (K= 0.114/%) for the H=90%.
Figure 4.6 shows normalized (Z/Z
o
) experimental (from Figure 4.3) and simulated (by Eq. 4.5)
impedance-humidity relationship. It can be seen that the deviation of the simulated curve from
experimental is in the reasonable range.

65

Figure 4.1 Schematic diagram of the Au/PANI/Ag humidity sensor.

Figure 4.2 Surface morphology of PANI film at low (a) and high (b) magnification.

a b
66

Table 4-1 Relative standard deviation (R.S.D) of the measured data
Sr
#
R1 R2 R3 R4 Mean S.D R.S.D (%)
1
22
669.010 665.169 671.574 664.901 667.664 3.212 0.481
3 657.654 650.388 669.648 648.154 656.461 9.682 1.475
4 391.155 412.584 417.825 394.770 404.083 13.102 3.242
5 279.899 272.605 283.962 277.190 278.414 4.769 1.713
6 123.079 120.214 127.951 119.039 122.571 3.968 3.237
7 63.111 68.787 71.107 60.138 65.786 5.046 7.670
8 26.375 29.073 31.980 24.461 27.972 3.274 11.703
9 13.995 14.398 15.511 13.682 14.397 0.799 5.548
10 7.451 7.917 8.180 7.670 7.805 0.315 4.032
11 3.579 3.951 4.363 3.721 3.903 0.343 8.780
12 2.353 2.110 2.453 2.104 2.255 0.176 7.794
13 1.382 1.461 1.486 1.342 1.418 0.067 4.742
Avg. 5.035

30 40 50 60 70 80 90
10
0
10
1
10
2
10
0
10
1
10
2
10
3
Capacitance

Relative Humidity (%RH)
C
a
p
a
c
i
t
a
n
c
e

(
p
F
)
Impedance
I
m
p
e
d
a
n
c
e

(
M
O
)

Figure 4.3 Capacitance and impedance-relative humidity (RH) relationships for the
Au/PANI/Ag sensor at 120 Hz.

67

30 40 50 60 70 80 90
10
0
10
1
10
2
10
3
120 Hz
1 KHz
I
m
p
e
d
a
n
c
e

(
M
O
)
Relative Humidity (% RH)

Figure 4.4 Impedance-relative humidity (RH) relationships for the Au/PANI/Ag sensor at
120 Hz and 1 kHz.
30 40 50 60 70 80 90
10
0
10
1
10
2
10
3
I
m
p
e
d
a
n
c
e

(
M
O
)

Figure 4.5 Impedance-relative humidity (RH) relationships for the Au/PANI/Ag sensor at
120 Hz during increasing and decreasing of humidity.
68

Figure 4.6 shows that experimental impedance-humidity curve actually follows to exponential
function. As this curve is not exact linear for utilization of the samples as a humidity sensor, the
linearization circuit should be used. Practically the linearization can be made by logarithmic
amplifier (Figure 4.7) [23]. The log diode, for example 1N914 diode, in this circuit is operating
in forward-bias region. As diode is temperature-dependent element, so the diode and amplifier
should be kept in a temperature-controlled chamber [23].
Table 4-2 shows the comparison of humidity sensing properties of sensor in as fabricated and
annealed conditions. It can be observed that annealing has improved the sensitivity of the
samples by two times. The change in properties, particularly impedance humidity sensitivity as a
result of annealing can be attributed to the structural changes which take place due to annealing
[24]. Annealing increases the porosity, which results in increase in initial impedance and hence
improved sensitivity.
The obtained experimental results reveal that impedance-humidity relationship shows more
consistent changes over wide range of the humidity (36-90%) as compared to the capacitance-
humidity relationship that is important for the design of humidity sensor on the base of
investigated materials. The impedance depends on both resistance and capacitance changes (Eq.
4.2) this is a reason that the impedance-humidity relationship is uniform as compared to the
relationships of the resistance and capacitance. At the same time the impedance decreases with
increase in humidity, in principle, in the same manner as the resistance of the sensor. It is
obvious that the effect of the resistance to impedance is dominating with respect to the effect of
the capacitance. The decrease in impedance for frequency of 120Hz and 1 KHz when humidity
changes from 36% to 90% is 471 and 137 times respectively.
Figure 4.8 shows the response (
res
) and recovery (
rec
) times of the Au/PANI/Ag samples. The
response and recovery time is the time required by the sensor to measure the 90% of the total
impedance change [6]. It can be seen that
res
and
rec
are equal to 8 and 27 second respectively.
These curves are obtained by suddenly changing relative humidity from 36 to 90% and 90 to
36%.
It is well-known that the value of the capacitance depends on the polarizability of the material,
which has several basic sources i.e dipolar
dip
, ionic
i
and electronic
e
polarizability [18]. In
this case the dipolar (
dip
) polarizability due to the presence of dipoles (H
2
O) absorbed by the
69

polyaniline seems to play a very important role. Electronic polarizability is universal and arises
due to relative displacement of the orbital electrons. Polyaniline may comprise charge-transfer
complexes with water molecules; it can be assumed that ionic polarization takes place as well in
this organic material. The polarizability due to the transfer (
t
) of charge carriers such as
electrons and holes that are present at normal conditions in the organic material was investigated
by [25-27].
The increase in capacitance with increase in humidity can be explained by the following way.
The dielectric permittivity of the polyaniline increases due to absorption of water molecules,
having higher dielectric permittivity value, by diffusion through the surface of the PANI. The
decrease in resistance and increase in capacitance firstly may be due to the presence of
displacement current caused by water molecule, and secondly may be due to possible doping of
the polyaniline by the water molecules and increase of the polarizability and concentration of
charges related to presence of the extra charge carriers. These mechanisms have been described
in detail with respect to some solids [27].
The results show that with the increase in frequency, the sensitivity of the samples decreases. It
may be due to comparability of the relaxation time of the related processes with period of applied
measuring AC voltage [18].
The results also showed that the resistance and capacitance measurements for investigation of the
humidity response of the samples are complimentary and can be replaced by impedance
measurement only. The high sensitivity of the polyaniline to humidity is first of all due to high
diffusivity of the water molecules in the polyaniline. Secondly, it is due to molecular interactions
between water molecules and polyaniline which resulted in the formation of charge-transfer
complexes and accordingly increased the concentration of the charge carriers as electrons and
holes.
4.1.4 Conclusions
The humidity sensing properties of the polyaniline films deposited by drop casting were
investigated. The capacitance and impedance of the samples were evaluated under the effect of
humidity in the range of 36%-90% RH. It was observed that the capacitance of the sensor
increases and impedance decreases with increase of the relative humidity. It was found that
impedance-humidity relationship shows more uniform changes in the interval of 36%-90% RH
70

with respect to capacitance-humidity relationship that show less consistent changes in this
interval. It was observed that resistance contribution in the impedance was dominated with
respect to the capacitance. From the measurements, it was also found that annealing increases
sensors sensitivity to humidity for two times. Only impedance-humidity measurements are
sufficient for design of the polyaniline based humidity meter. It was found that the impedance-
humidity relationships actually follow an exponential function. It can be explained by op-amp
electronic circuit to linearize the impedance-humidity relationships. Humidity dependent
impedance of this sensor makes it attractive for use in impedance humidity meter. The
impedance humidity meter may be used in the instruments for environmental monitoring and
assessment of humidity.

71

30 40 50 60 70 80 90
0.01
0.1
1
Experimental
Simulated
N
o
r
m
a
l
i
z
e
d

i
m
p
e
d
a
n
c
e
Relative Humidity (%RH)

Figure 4.6 Normalized experimental and simulated impedance-relative humidity (RH)
relationships for the Au/PANI/Ag sensor at 120 Hz.

Figure 4.7 Circuit diagram of Op-amp logarithmic amplifier.

V
o

R
7

R
2

Log diode
R
1

V
in

-V
+V
+V
o

-V
D
R
3

R
4

R
5

R
6

72

Table 4-2 Humidity sensing properties of Sensor
Thickness
(m)
Frequency
(Hz)
C(90%)/C(36%) Z(36%)/Z(90%)
As-Fabricated Annealed As-Fabricated Annealed
70
120
167 324 471 727
1000
42 59 137 161

0 50 100 150 200 250 300 350
0
150
300
450
600
750
90 % RH
I
m
p
e
d
a
n
c
e

(
M
O
)
Time (sec)
36 % RH

res
) and recovery (
rec
) times of the Au/PANI/Ag sensor.

73

4.2 Fabrication and investigation of orange-dye-polyaniline composite film
based humidity sensors
4.2.1 Introduction
From last few decades, lot of research work has been done and applied in industry on polymer
based humidity sensors [4]. As a result of extensive investigations; polymers like polypyrrole,
polythiophene and polyaniline have gained significant attention as a humidity sensing material
[4, 16, 28]. The humidity sensing mechanism of most of the polymers is the same. Formation of
hydrogen bonds takes place as a result of interaction between the water molecules and the
nitrogen centers of the polymer backbone, which results in increase of number of charge carriers
[16]. These charge carriers decrease the resistance and increase the conductivity of the material.
[10, 16, 28].
Due to its wide range of applications [4] and salient features like simple preparation and doping,
easy polymerization, excellent chemical stability, relatively high levels of conductivity and low-
cost, the PANI has become the most attractive polymer for researchers [4, 10, 29]. The PANI and
its derivatives are famous humidity sensing materials but their response is low due to weak
hygroscopicity. One of the methods to improve the humidity sensing properties of the PANI is its
blending with the hygroscopic polymeric materials [10, 20].
For the measurement of humidity and temperature the composite of polyaniline/tungsten oxide
was synthesized through in situ deposition technique by Parvatikar et al. [30]. In this study, the
pellets (3 mm thick and 10 mm diameter) of composites (having 10-50 wt% tungsten oxide)
were characterized for humidity and temperature sensing. The change in resistivity for various
compositions of PANI-tungsten oxide composite was measured from 1.7 to 0.45 K-cm for
change in humidity from 10 to 95 %.
In this work we fabricated and investigated Ag/OD-PANI /Ag humidity sensors based on blend
of orange dye (OD) and PANI. The orange dye (OD) is p-type semiconductor and its properties
like high purity, well defined chemical structure, harmless nature, normal condition stability and
good light absorption in visible spectrum make it a possible entrant for use in electronic devices
[31]. It is also highly sensitive to humidity [32].
74

4.2.2 Experimental
Laboratory synthesized orange dye (C
17
H
17
N
5
O
2
) [33] and commercially available emeraldine
base (EB) polyaniline (PANI) (C
24
H
20
N
4
) were used for the fabrication of humidity sensors. The
density of orange dye is 0.9 g cm
3
and its molecular weight is 323, while the molecular weight
of PANI is ~ 20,000.
The solution was prepared by mixing 3 wt % OD and 1 wt% of PANI powder in 1ml of water
and stirring at room temperature. Before deposition of metallic electrodes, the glass substrates
were cleaned for 10 minutes in an ultrasonic cleaner by dipping in acetone and then dried. Dry
substrates were plasma cleaned for 5 min in a thermal evaporator. The 50 1 nm thick silver
electrodes were deposited on cleaned substrates by vacuum evaporation and there was a 45 2
m gap between two electrodes. The gap length was kept 10 mm. The OD-PANI composite
films having thicknesses of 50-170 3 m were deposited by drop-casting the OD-PANI solution
on to the silver electrodes. Figure 4.9 shows schematic diagram of the Ag/OD-PANI/Ag
samples. The fabricated devices were dried at room temperature for two weeks. After drying,
films show very good adhesion with glass substrate. The samples were annealed at 100 C for
one hour in an oven in air at atmospheric pressure. For microstructural analysis of the films;
optical and scanning electron microscopes were used.
The sensors were tested in indigenously made humidity chamber, which has been fabricated in
our device testing laboratory. It consists of a closed chamber with inlet and outlet valves for gas.
To create humidity in the chamber, nitrogen gas is passed through the water and then injected in
to the chamber. The Fisher Scientific Digital Hygrometer is used to measure humidity, while the
ESCORT ELC-132A LCR meter is used to measure capacitance (C) and dissipation (D) at
different frequencies. The resistance (R) and impedance (Z) are calculated by the Eq. 4.1 and Eq.
4.2, respectively [13] with an error of 3.5%, which was estimated by using procedure described
by Dally et. al. [34]. Moreover, in this case the impedance of the hygrometer is considered as an
impedance of parallel connected resistance and capacitance. Testing is carried out at room
temperature for four times to ensure the repeatability of the results and the relative standard
deviation was found within 5%.
75

Figure 4.10 (Optical micrograph) and Figure 4.11 (SEM image) show the surface morphology of
polyaniline thin film in as fabricated condition. It is evident from the micrographs that the OD-
PANI composite forms two phase structure, which consists of granular matrix and the network of
microtubes. This structure is different from the pure polyamine films structure, which was
fabricated by us by using same solvent and deposition method. These results reveal that orange
dye causes better dispersion of polyaniline powder and also the nucleation and growth of
microtubes. These microtubes improve the electrical properties of the composite [35].
Figure 4.12 shows the relationships of capacitance and impedance with humidity (during
absorption) for the Ag/OD-PANI/Ag sensor at 120 Hz. The film (OD-PANI composite)
thickness was 170 m. It can be seen that the impedance shows consistent change with change in
humidity, while change in capacitance is not uniform. The plot of impedance-humidity
relationship on a semi-logarithmic scale is more linear as compared to capacitance-humidity
relationship in the humidity range of 30-90% RH. The changes in the capacitance and impedance
of sensors over whole humidity interval are 1.5 x 10
4
and 5.2 x 10
4
times respectively.
These results depict that with increase in humidity the resistance of material reduces. It is also
believed that the absorbed water molecules dissociated into proton (H
+
) and hydroxyl ions (OH
-
).
The migration of positive charges in PANI increases its conductivity which is called the proton
effect [16]. The oxidized and reduced (non-oxidized) forms of emeraldine base PANI (Figure
3.1) can be protonated due to the un-bonded electron pair on the nitrogen atom [30] such as -NH-
-NH
+
2
and -N= -NH
+
= etc. These protonated sites are named as charged sites and H-bond
accepting/ donating sites, and Zeng et al. [16] explained how these sites contribute in conduction
mechanism of PANI. It is also considered that the H
+
ions produced as a result of dissociation of
water molecule react with orange dye and generate holes as shown below [36].
2 H
+
+ 1/2O
2
+ 2(C
17
H
17
N
5
O
2
) H
2
O + 2(C
17
H
17
N
5
O
2
)
+
(C
17
H
17
N
5
O
2
)
+
(C
17
H
17
N
5
O
2
) + h
+
The generation of these holes also contributes to increase the conductivity of the composite. The
impedance-humidity relationship during increase and decrease of humidity is shown in Figure
4.13, where the values are taken at room temperature at a frequency of 120 Hz. The sensors with
76

relatively thick film (170 m) show hysteresis, while the curves of thin film (50m) sensor
(shown in the inset of Figure 4.13) are coincided within the experimental error of 2 %. It
means that with increase in thickness of film the hysteresis increases and reason for this may be
the differences in the rate of absorption and desorption of water vapors. Another reason for
hysteresis is the porosity of the film which facilitates the absorption process due to large surface
area and capillary effect, but it makes the desorption process slightly difficult [1, 37]. It also
reveals that it may not be the humidity memory effect which was described earlier in doped
PANI and PANI with 5-formyl-2-furansulfonic acid [20, 21]. These materials show irreversible
changes of their sheet resistance and capacitance under the effect of humidity. As a result of
irreversible dedoping process under the effect of humidity the phase separation and
crystallization of hydrated form of its protonating agent take place.
The effect of annealing on the humidity sensing properties of the OD-PANI composite is shown
in Table 4-3. The annealing resulted in the improvement of capacitance-humidity and
impedance-humidity sensitivities up to 1.7 and 2.5 times respectively. This change in sensitivity
can be attributed to the increase in porosity of the film, which takes place due to annealing [24].
The impedance-humidity relationship for frequencies of 120 Hz and 1 kHz are shown in Figure
4.14. From Figure 4.14 it is evident that with increase in frequency at a specific humidity level
the sensors impedance decreases. The increase in humidity also results in consistent decrease in
impedance. The results also reveal that the sensitivity of the sensors decreases with increase in
frequency. It can be explained by the dependence of dielectric permittivity [18], mobility of ions
(firstly) and electrons (secondly) and transit time of charges transfer on the frequency [19].
The more consistent changes can be observed in impedance-humidity relationship in the range of
30-90% RH as compared to the capacitance-humidity relationship and it is imperative for the
design of humidity sensor on the base of investigated materials. The reason behind this is the
same as given in section 4.1.3 for PANI based humidity sensors. The decrease in impedance for
frequency of 120Hz and 1 KHz when humidity changes from 30% to 90% RH is 5.2 x 10
4
and
8.8 x10
3
times respectively.

77

Figure 4.9 Schematic diagram of the Ag/OD-PANI/Ag Humidity Sensor.

Ag
PANI+OD
Glass substrate
Ag
45 m
78

Figure 4.10 Optical Micrograph of the OD-PANI films surface.

Figure 4.11 SEM image of the OD-PANI films surface.

50 m
PANI Microtubes
PANI Microtubes
79

10
-2
10
-1
10
0
10
1
10
2
30 40 50 60 70 80 90
10
-3
10
-2
10
-1
10
0
10
1
10
2
Capacitance

C
a
p
a
c
i
t
a
n
c
e

(
n
F
)
Impedance
I
m
p
e
d
a
n
c
e

(
M
O
)

Figure 4.12 Capacitance and impedance-humidity relationships for the Ag/OD-PANI/Ag
Sensor at 120 Hz.
30 40 50 60 70 80 90
10
-3
10
-2
10
-1
10
0
10
1
10
2
30 40 50 60 70 80 90
10
-2
10
-1
10
0
10
1
10
2
I m
p
e
d
a
n
c
e

(
M
O
)
I
m
p
e
d
a
n
c
e

(
M
O
)

Figure 4.13 Impedance-humidity relationship for the thick film (170 m) Ag/OD-PANI/Ag
sensor at 120 Hz during increasing and decreasing of humidity; Inset shows the
Impedance-humidity relationship for the thin film (50 m) Ag/OD-PANI/Ag sensor.

80

Table 4-3 Humidity sensing properties of Sensor
Thickness
(m)
Frequency
(Hz)
C
90%
/ C
30%
Z
30%
/Z
90%

As-Fabricated Annealed As-Fabricated Annealed
170
120 1.5x10
4
2.6x10
4
5.2x10
4
1.3x10
5

1000 1.7x10
3
2.7x10
3
8.8x10
3
1.98x10
4

30 40 50 60 70 80 90
10
-3
10
-2
10
-1
10
0
10
1
10
2
1000 Hz
120 Hz
I
m
p
e
d
a
n
c
e

(
M
O
)

Figure 4.14 Impedance-humidity relationships for the Ag/OD-PANI/Ag sensor at 120 Hz
and 1 kHz.

81

For simulation of the experimental results of impedance-humidity relationship which are shown
in Figure 4.12, the following exponential function [22] given in Eq. 4.4 is used in the modified
form, which is the following

4.6
where A is constant with value 1, H is the change in humidity (H=H H
o
), H
m
is the
maximum humidity, K is humidity factor, Z and Z
o
are impedances at different humidity and
humidity of 30% RH respectively. From experimental data shown in Figure 4.12 the humidity
factor K is determined (K = 0.181/%) for the 90% RH. The comparison of normalized
experimental (from Figure 4.12) and simulated (by Eq. 4.6) impedance-humidity relationship is
shown in Figure 4.15. It is evident that the deviation of the simulated curve from experimental is
in the reasonable range.
The experimental impedance-humidity curve actually follows the exponential function and this
curve is not exactly linear for utilization of the samples as a humidity sensor. For linearization
the electronic circuits like logarithmic amplifier are used [23].
The response and recovery time is defined as time required by the sensor to measure the 90% of
the total impedance change [6]. The curves for response (
res
) and recovery (
rec
) times of the
Ag/OD-PANI/Ag sensor are obtained by suddenly changing humidity from 30 to 90% RH and
90 to 30% RH as shown in Figure 4.16. It is evident from the curves that
res
and
rec
are 34 and
450 second respectively.
The results reveal that for the investigation of humidity response of sensors the measurements of
resistance and capacitance are complimentary, which can be replaced by impedance
measurement. High diffusivity of water molecules in to the OD-PANI composite and the
interactions between water molecules and OD-PANI composite are two main reasons for high
sensitivity of the OD-PANI composite films to humidity. The interactions between water
molecules and OD-PANI composite resulted in the formation of charge-transfer complexes and
accordingly increase in the concentration of the charge carriers as electrons and holes.
82

4.2.4 Conclusions
The humidity sensors were fabricated by the deposition of OD-PANI composite films from the
blend of orange dye and PANI in distilled water by drop casting. The capacitance and impedance
of the sensors were evaluated under the effect of humidity at room temperature in the range of
30%-90% RH. It was observed that with increase in humidity the impedance of the sensor
decreases and capacitance increases. In the interval of 30-90% RH, the impedance-humidity
relationship shows more uniform changes with respect to capacitance-humidity relationship. It
was observed that the resistance plays a dominating role as compared to the capacitance in the
impedance. It was also found that annealing increases sensors sensitivity to humidity upto 2.5
times. Due to difference in the diffusion rates during humidification and dehumidification the
hysteresis was observed in sensors with large thickness. For the design of OD-PANI composite
based humidity meter only impedance-humidity measurements are sufficient. It was found that
the impedance-humidity relationships actually follow an exponential function. It can be
linearized by using op-amp electronic circuit. Humidity dependent impedance of this sensor
makes it attractive for use in impedance humidity meter. The impedance humidity meter may be
used in the instruments for environmental monitoring and assessment of humidity.

83

30 40 50 60 70 80 90
10
-5
10
-4
10
-3
10
-2
10
-1
10
0
Experimental
Simulated
N
o
r
m
a
l
i
z
e
d

I
m
p
e
d
a
n
c
e

(
Z
/
Z
o
)

Figure 4.15 Normalized experimental and simulated impedance-humidity relationships for
the Ag/OD-PANI/Ag sensor at 120 Hz.
0 500 1000 1500 2000 2500 3000 3500 4000
0
20
40
60
80
100
120

I
m
p
e
d
a
n
c
e

(
M
O
)
Time (Sec)
30% RH
90% RH

res
) and recovery (
rec
) times of the Ag/OD-PANI/Ag sensor.

84

4.3 Organic Cu/Cellulose/ PEPC/Cu humidity sensors
4.3.1 Introduction
Sensing devices play an important role in our modern age. The measurement of humidity is
frequent because of the universal existence of water, which affects physical properties of
materials [2] and health of human beings. On base of sensing principles, humidity sensors have
various types. The capacitive type humidity sensors are fabricated by hydrophobic polymers
while the resistive sensors are fabricated by polymer electrolytes [38]. Sensors are investigated in
two designs; one is surface type configuration and other, which is mostly used, sandwich
configuration. It has been found that sandwich type devices carry some demerits like complex
technology, expensive processes and short circuiting, while surface type devices provide the best
alternative due to their simplicity in design and technology, and lower cost [39]. Organic
semiconducting materials have great potential due to their electric, optical and dielectric
properties, but they need modification [40].
For humidity sensing polymers are used in their original form, polymers blend, doped polymers,
copolymers or polymer composites with organic and inorganic semiconducting materials [28, 41-
43]. The working principles of humidity sensing polymers are different. Ionic polymers are
based on variation of electrical conductivity or resistance with adsorption of water molecule [41].
The adsorption or desorption of water molecule causes a change in the dielectric constant of the
polymer thin film lying between two electrodes. This change in dielectric constant in capacitive
type humidity sensors can be explained by this equation [44].

4.7
where C is the capacitance, is total permittivity, A is area of electrode and d is the gap between
two electrodes. In resistive type humidity sensors upon adsorption of water molecules produce
conductive ions due to ionization of polymer electrolyte [38] or changes due to doping.
Generally with the increase in humidity and by dissociation of mobile carriers the conductivity of
a polymer electrolyte increases [45].
Concurrently high sensitivity and resistivity to water molecule are the required properties for
humidity sensing materials [38]. Some organic polymers are highly sensitive at low humidity but
85

due to their dissolution in water they can not be used at higher humidity [40, 46]. For humidity
sensors, suitable materials are water insoluble organic compounds like polyimide and cellulose
acetate butyrate [46] and cross linked poly methyl methacrylate [47]. Cellulose and PEPC are
water insoluble materials [48], previously Metal/cellulose/Metal hygrometers [49] and Poly-N-
epoxypropylcarbazole complexes photocapacitive detectors[50] were fabricated in a previous
study.
The formation of charge transfer complexes of PEPC with low molecular organic materials make
it electrically conductive and highly photosensitive [51]. PEPC and its derivatives due to their
photosensitivity and adhesiveness [50] have potential to use in organic semiconductor devices
like sensors, solar cells, recording media in electrography and photoelectric convertors [52]. In
the present work it has been endeavored to develop a humidity sensor, which may show good
sensitivity over a range of humidity level. Therefore, humidity sensors based on the thin film of
poly-N-epoxypropylcarbazole (PEPC) and cellulose composite have been fabricated.
4.3.2 Experimental
For the fabrication of humidity sensor, PEPC was synthesized in laboratory [50] and a
commercially available cellulose ((C
6
H
10
O
5
)
n
) having density of 1.592 g/cm
3
,

was used. The
cellulose was used in as received form. A suspension of 2 wt% cellulose was prepared in a
solution of 4 wt% PEPC in benzol. Glass substrates were cleaned in BANDELIN SONOREX
RH100H Sonicator for 13 minutes by using methanol. After drying the glass substrates, the
metallic electrodes were deposited by using ADWARD S150B sputter coater. The thickness of
the electrodes was 100 1 nm, and between two electrodes there was a gap of 40 2 m, while
the gap length was 15 mm. The 100 5 m thick films of PEPC and cellulose composite were
deposited by drop casting method. The fabricated devices were dried at room temperature for 20
hours. The schematic diagram of the Cu/Cellulose/PEPC/Cu humidity sensor is shown in Figure
4.17.
The change in capacitance and dissipation with respect to relative humidity was measured by
using the same procedure as given in section 4.2.2.2. Testing was done at room temperature and
86

the experiments were conducted three times to ensure the repeatability of the results, which were
found repeatable with the relative standard deviation of 4%.
Figure 4.18 shows the capacitance, resistance and impedance relationship with relative humidity
for the Cu/ Cellulose/PEPC/Cu humidity sensor at a frequency of 1 KHz. The capacitance versus
humidity relationship shows that the capacitance initially increases in a gradual mode from 67-80
% RH but an abrupt change occurs in the humidity range of 80-89 %. Although the capacitance
increases upto 21 times but its response covers a short range of humidity. It is also evident from
the Figure 4.18 that by change in humidity from 45 to 89 % RH, the resistance decreases by
1.74x10
3
times. The reasons behind this increase of capacitance and decrease of resistance with
increase in humidity may be the following [27, 49-52]:
i. Absorption of water molecule in semiconductor thin film, which increases the dielectric
constant and decreases the resistance due to displacement current.
ii. Doping of the organic material by H
2
O molecule.
iii. Formation of charge transfer complexes.
The resistance (R) of the samples was determined from the values of capacitance and dissipation
(D) by using Eq. 4.1 [13]. Although the resistance response covers a wide range of humidity as
compared to capacitance response but the response range is still short. Impedance-humidity
relationship in Figure 4.18 shows that impedance response covers a wide range of humidity
from 45 % to 89 % RH. This is the total impedance of capacitance and resistance connected in
parallel.
The impedance-humidity relationship of the sensor shows that with increase of humidity the
impedance of the sensor decreases. The more uniform change in impedance as compared to
capacitance and resistance changes is due to the alterations in capacitance and resistance. The
simultaneous decrease in impedance and resistance with increase in humidity reflects that the
resistance strongly affects the impedance as compared to capacitance.
There are a number of factors which affect the capacitance of the sensor. They are relative
dielectric constant of the thin film material, area of electrodes, and gap between electrodes. The
capacitance relies upon materials polarizability; sources of which are electronic (
e
), dipolar
87

(
dip
) and ionic (
) [18]. Another form of polarizability due to transfer of charge carriers

(electrons and holes) at normal conditions is also reported [25-27]. In general due to relative
displacement of orbital electrons, electronic polarizability occurs, which possibly at higher
frequencies (>1000 Hz) affect the capacitance measurements. It is assumed on the basis of sensor
response that the absorption of water molecules in cellulose-PEPC composite thin film increases
dipolar polarizability of sensor.
The simulation of capacitance to relative humidity relationship is done by using the following
exponential function

4.8
For the capacitance-humidity relationship, above function is modified to

4.9
where C is capacitance under the effect of humidity, C
0
capacitance at normal conditions, H is
instantaneous humidity and k is humidity capacitance factor. From the experimental data given in
Figure 4.18 the values of A, B and k are determined as 0.9998, 1.6x10
-9
and 0.263, respectively.
Figure 4.19 shows the comparison of experimental and simulated capacitance-humidity
relationships. The experimental and simulated results coincide within the accuracy of 10%.
Simulation of the resistance-humidity relationship is done by following equation [24]

4.10
where A is the area, L is the gap between two electrodes, is the conductivity, q is charge, p is
concentration of charges and is mobility of charge carriers.
The above equation is based on following assumptions:
i. Water molecules act as dopant.
ii. Electronic conductivity and displacement current take place.

88

Figure 4.17 Cross-sectional view of the Cu/ Cellulose /PEPC /Cu sensor.

0
50
100
150
200
250
40 50 60 70 80 90
0
100
200
300
400
500

p
F
Resistance
Impedance x 20
Capacitance
M
O

Figure 4.18 Relationship among capacitance, resistance, impedance and relative humidity

89

At initial humidity the relative resistance with respect to R
o
(initial resistance) can be expressed
as:

4.11
where p
o
and p are the concentrations and
o
and are the motilities of charges at initial and
higher humidity levels respectively. As the equation for determination of concentration of
dopants [24] for example water molecules at the surface (C
s
) and in the bulk (C) of the composite
is:

4.12
In above equation x is distance from the surface, t is time and D is the diffusion coefficient. If in
the absorption process D is approximately taken constant, then C(x, t) is linear proportional to C
s
.
Hence it may be considered that

4.13
where A and B are constants with values 3.3x10
-2
and 1.1x10
-4
respectively. By putting the value
of p in Eq. 4.11, we get,

4.14
Hence

4.15
Comparison of experimental resistance-humidity relationship and its simulation is shown in
Figure 4.20. It is evident from the figure that the simulated values of resistance fall close to the
experimental values.
90

The results of the simulation of resistance are exactly same as the experimental results but there
is slight deviation from experimental results in the humidity range of 75% to 83 %. The
simulated results of capacitance are reasonably close to experimental results as indicated in
Figure 4.19, which may be further improved.
4.3.4 Conclusions
A surface type humidity sensor based on cellulose and PEPC composite thin film was fabricated
and investigated. The effect of relative humidity on capacitance, resistance and impedance of
sensor was studied in the humidity range of 45% to 89% RH. Results revealed that with increase
in humidity, capacitance increases and resistance and impedance decreases. Although
capacitance and resistance-humidity relationships showed significant changes in the range of 67-
89% RH and 45-83% RH respectively but the impedance-humidity relationship demonstrated
more uniform change in the range of 45-89% RH. Due to its wide sensing range and uniformity
in behavior, impedance humidity relationship is suitable for designing a cheaper, simpler and
efficient meter for the measurement of humidity for the purpose of environmental monitoring.
91

40 50 60 70 80 90
0
5
10
15
20
25
Experimental
Simulated
R
e
l
a
t
i
v
e

C
a
p
a
c
i
t
a
n
c
e

Figure 4.19 Comparison of experimental and simulated capacitance with respect to relative
humidity
40 50 60 70 80 90
0.0
0.2
0.4
0.6
0.8
1.0
Experimental
Simulated
R
e
l
a
t
i
v
e

R
e
s
i
s
t
a
n
c
e

Figure 4.20 Comparison of experimental and simulated resistance with respect to relative
humidity

92

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97

Chapter-5
Temperature Sensors
5 4
In this chapter various types of resistance-temperature sensors have been discussed, which
include multiwall carbon nanotubes (CNTs) film, CNTs flexible, CNTs-Cu
2
O composite, V
2
O
4
-
PEPC composite and organic on inorganic (CuPc on GaAs) sensors. This chapter consists of four
sections depending upon the design of sensors. In section one, the carbon nanotubes film based
sensors fabricated by sequential deposition of the thin layers of glue and CNT nanopowder on
the paper substrate have been discussed in detail. These are the surface type sensors in which
contacts are made of silver paste. Second section of this chapter is about CNTs based flexible
temperature sensors, which are fabricated by depositing CNTs on an adhesive tape, and
aluminium foils are used as electrodes. The change in DC resistance of the sensors was measured
in response to change in temperature for both the above mentioned sensors. The surface type
sensors fabricated by depositing V
2
O
4
-PEPC composite films onto the thin metallic electrodes
are described in detail in section three. Section four presents the temperature sensing properties
of organic-inorganic Ag/p-CuPc/n-GaAs/Ag cell. These sandwich type structures were fabricated
by depositing CuPc thin film on one side of GaAs single crystal substrate and one of the sliver
electrodes on back side of GaAs substrate, while other semitransparent silver electrode is
deposited on the CuPc layer.
5.1 Carbon nanotubes film based temperature sensors
5.1.1 Introduction
Many aerospace, nuclear, mechanical, chemical, medical, food and agriculture industries
extensively use temperature sensors. Although the existence of CNTs and cementite nanowires
in the ancient engineering products were reported few years ago [1], since their discovery in
1991 CNTs have been intensively investigated [2]. Due to their unique electronic and mechanical
properties, CNTs have proved to be very interesting for researchers. Depending on the
orientation of graphene lattice with respect to the axis of the tube, CNTs are electronically
classified as metallic, semiconducting or small-gap semiconducting (SGS) [3]. Various types of
sensors have been fabricated and investigated on the basis of single-walled nanotubes (SWNTs)
98

[4-7], double-walled carbon nanotubes (DWNTs) [8] and multiwalled carbon nanotubes
(MWNTs) [9].
The temperature dependent electrical transport in highly disordered multiwalled carbon
nanotubes of large outer diameter (60 nm) was investigated by Friedman et al. [10]. These
nanotubes were fabricated by means of the chemical vapor deposition process. Kumar et al. [11]
also investigated the temperature and chemical sensitivities of carbon nanofilms made on
diamond surface by high temperature surface modification followed by plasma treatment. The
conductance of these amorphous nanofilms was found to be sensitive to temperature and
exposure to vapors of different organic compounds.
Zaitsev et al. [12] developed a temperature sensor based on an array of carbon nanowires, and it
was fabricated by a 30 keV Ga focused ion beam on diamond substrate. The sensor shows
increase in current with increase in temperature in the range 40140 C. Saraiya et al. [13]
fabricated a low-temperature (10300 K) resistance sensor based on CNTs, which were grown
on nickel film by the ion beam deposition technique. The results revealed that CNTs behave as
semiconductors. In this study the carbon nanotubes film based temperature sensors have been
designed, fabricated and investigated.
5.1.2 Experimental
To fabricate the sensor, the thin films of a glue and commercially produced (Sun Nanotech Co
Ltd., China) CNTs powder were deposited in sequence on a paper substrate. The diameter of
multiwalled nanotubes (MWNTs) varied between 10-30 nm. To make the CNTs films more
adhesive and durable, the substrates with deposited films were pressed under a pressure of 10
KNm
-2
. Thicknesses of the paper substrate and CNTs film were 100 m and 30-40 3 m
respectively. The inter-electrodes distance (length between electrodes) and width of the surface-
type samples films were 5 mm and 4 mm respectively. Terminals of the sensors were connected
to the CNTs films by silver paste. Figure 5.1 shows schematic diagram of the CNTs film based
temperature sensor.
99

DC resistance of the samples was measured by using ESCORT ELC-132A meter. Laboratory
setup for the measurement of influence of temperature to the resistance of the samples was used
for the experiments. The sample was placed in the chamber that was heated by resistive electric
heater that was made of nichrome. The temperature was measured by multimeter FLUKE 87 and
controlled manually by changing the current passing through the resistive electric heater. The
experimental error for the measurement of the temperature was equal to 1
o
C and the accuracy
of electric resistance measurement was equal to 2% (it was estimated as described by Dally et.
al. [14]). To check the repeatability, the sensors were tested three times and the relative standard
deviation of the results was 5 percent.
Figure 5.2 shows resistance-temperature relationship for one of the CNTs sensors. The DC
resistances of the sensors decreased on average by 1.2 times respectively as the temperature was
increased from 20
C to 75
C. It can be seen in Figure 5.2 that there is hysteresis in heating-

cooling process. The effects of temperature on the sensors resistances were approximately the
same for thicker CNT films (40 m) and thinner films (30 m). The average resistance
temperature coefficient (S) of the sample can be calculated by following equation:

5.1
where R
o
, R and T are initial value of the sensors resistance, and changes in the resistance
and temperature respectively. From data presented in Figure 5.2 it can be found that at 20
C the
value of S is -0.24%
C
-1
. The temperature sensitivity was found higher than that of hydrogenated
multiwalled carbon nanotubes (S= -0.16%
o
C
-1
) [11],

carbon nanofilms deposited on diamond
crystals (S = -0.14%
o
C
-1
) [10] and of carbon-polymer flexible temperature sensor (S= -0.13%K
-
1
) [12].

It means that the role of the substrate and CNTs films processing technology are very
important in the performance of the sensors.
The sensors resistance (R) is determined as [15]:

5.2
100

Figure 5.1 Schematic diagram of the CNTs film based resistance temperature sensor.

20 30 40 50 60 70 80
96
100
104
108
112 Heating
Cooling
R
e
s
i
s
t
a
n
c
e

(
O
)
Temperature (C)

Figure 5.2 Resistance-temperature relationships of the one of CNTs film based sensors at
heating-cooling processes.
Ag Paste
Paper Substrate
CNTs film
Glue
Terminal
Terminal
101

where d is the length or inter-electrode distance and A is the cross-section of the CNT layer, and
is the resistivity (
1
o
= , where is conductivity) of the CNT layer. As CNTs are nanopowder,
the observed resistance-temperature relationship shows increase in conductivity of the CNTs
film due to increase in the concentration of charge carriers, which is exactly like semiconductors
under the effect of temperature [16]. For simulation we can use an exponential function given in
Eq. (5.3) [17].

5.3
For heating this relationship can be represented as:

5.4
While for cooling the relationship is the following:

5.5
where A is constant (A=1), R is the samples resistance at elevated temperatures (T), T
m
is
maximum temperature, K is the resistance temperature factor. The value of K were determined
from the experimental data shown in Figure 5.2, which are 2.8x10
-3
C
-1
and 2.6 x10
-3
C
-1

respectively for heating and cooling curves. Figure 5.3 shows the experimental and simulated (by
using Eqs. 5.4 & Eq. 5.5) results, that coincides with an accuracy of 0.5 percent.
The mechanism of conductivity in CNT samples can be considered as transitions between
spatially separated sites, or particles that can be attributed to the percolation theory [18, 19].
According to percolation theory the effective conductivity () of the CNT samples can be
calculated as

5.6
102

20 30 40 50 60 70 80
0.84
0.87
0.90
0.93
0.96
0.99
1.02
Experimental
Simulated
Experimental
Simulated
R
e
l
a
t
i
v
e

R
e
s
i
s
t
a
n
c
e

(
R
/
R
o
)
Temperature (C)

Figure 5.3 Experimental and simulated relative resistance-temperature relationships of the
CNTs sensors (R
o
and R are initial resistance and resistance at elevated temperatures
respectively).

103

where L is a characteristic length, which depends on the concentration of sites, Z is the resistance
of the path with the lowest average resistance. With an increase in temperature, the CNT layer is
heated that may cause the reduction of Z due to generation of charge carriers. On the other hand,
as the CNT particles are glued on the substrate, the particles may be squeezed due to the thermal
expansion and the contact areas between particles or effective cross-section of the sample (Eq.
5.2) may also increased that in turn decrease the resistance of the sample. As a result, the
conductivity of the CNT samples increases and the resistance decreases with increase in
temperature accordingly, as is observed experimentally (Figure 5.2). The CNT system can be
assumed as a bulk hetero system that results in high sensitivity of the CNT layers to the effect of
temperature, where by an increase in the inter-particles contact areas as well as the intrinsic
conductivity of the nanoparticles may also takes place resulting in increase in conductivity and
decrease in resistance.
The structures of the investigated sensors are the same as presented by Yong et al. [20], because
the flexible substrates are used for deposition of the CNT layers in both the cases. But in [20] the
flexible substrate was fixed on a silicon wafer by gluing, while in our case the CNT layer was
glued on paper substrate. As the experimental resistance-temperature (Figure 5.2) relationships
for the CNTs sensors are quasi-exponential, it can be easily linearized by nonlinear op-amps
[21].
5.1.4 Conclusions
The surface-type CNTs film temperature sensors were designed fabricated and investigated.
Resistance of the sensors decrease as the temperature increased, i.e. resistance-temperature
relationship has semiconductive behavior. The average temperature sensitivity of the samples
was -0.24% C
-1
. The resistance-temperature relationship of the sensor was simulated. For
explanation of conduction mechanism, the percolation theory has been used. The CNT system is
assumed as a bulk hetero system that results in high sensitivity of the CNTs layers to
temperature, where the increase in the inter-particles contact areas and intrinsic conductivity of
the nanoparticles takes place resulting in increase in conductivity and decrease in resistance. The
temperature sensors based on CNTs glued on paper substrates show good performance.
104

5.2 Carbon nanotubes based flexible temperature sensors
5.2.1 Introduction
Temperature sensors are widely used in industry. So called flexible electronic sensors [22-26], in
particular, flexible temperature sensors, which improve greatly the functionality of integrated
bio-parameter monitoring systems are of increasing interest to the researchers, especially for
body temperature controlling systems. The miniaturized flexible temperature sensors based on
polymer compositions filled with multiwalled carbon nanotubes were described by Sibinski et al.
[27]. This sensor didnt show tensometric effect that was very common for other carbon-polymer
sensors. The temperature sensitivity of the sensor was around of 0.13%/K. Based on an array of
carbon nanowires temperature sensor that was written by a 30 KeV Ga
+
focused ion beam on
diamond substrate has been developed [12]. In the temperature range from 40 to 140
C the
sensor shows an exponential increase in current with temperature at a rate of 0.1dB/
C. Low-
temperature resistance sensor based on CNTs grown on nickel film using ion beam deposition
technique for measurement at 10 K-300 K was developed [13]. It was found that CNTs behave
as semiconductors.
The temperature and chemical sensitivity of carbon nanofilms made on diamond surface by high
temperature surface modification followed by plasma treatment were investigated [11]. The
structure of nanofilms was found amorphous. The films electrical conductance was sensitive to
temperature and exposure to vapors of different organic compounds. In another study highly
disordered multiwalled carbon nanotubes of large outer diameter (60 nm) were fabricated by
means of a chemical vapor deposition process and their temperature dependent electrical
transport was investigated [10]. In this study, the carbon nanotubes based flexible temperature
sensors have been designed, fabricated and investigated.
5.2.2 Experimental
Commercially produced (Sun Nanotech Co Ltd., China) CNTs powder was deposited on the
adhesive elastic polymer tape of thickness of 35 m, with built-in Al foil electrodes, and then it
was covered by the same kind of tape. As shown in Figure 5.4 the tape played a role of elastic
casing. The diameter of multiwalled nanotubes (MWNTs) was in the range of 10-30 nm. The
105

nominal thickness of the CNTs layers was ~ 300-430 m. The inter-electrodes distance (length
between electrodes) and widths of the surface-type samples layers were in the range of 4-6 mm
and 3-4 mm respectively.
DC resistance of the samples was measured by using ESCORT ELC-132 A meter. Laboratory
setup for the measurement of the influence of temperature to the resistance of the samples was
used for the experiments. The experimental error in the measurement of the temperature was
1
C, while the accuracy of resistance measurement was equal to 2%. The repetition of sample
tested four times showed 6% deviation in the results.
Figure 5.5 shows resistance-temperature relationship for one of the Al/CNT/Al sensors. The DC
resistance of the sensors decreased on average by 1.4 times respectively with the increase in
temperature from 20
C to 70
C. The effects of temperature to the sensors resistances were

approximately the same for the thicker CNT films (~430 m) and thinner films (~300 m).
The resistance temperature coefficient (S) of the sample is calculated by Eq. 5.1. From data
presented in Figure 5.5 it can be found that at 20
C the value of S is -1.26%
C
-1
. The
temperature sensitivity of the investigated Al/CNT/Al sensor was found larger than that of
hydrogenated multiwalled carbon nanotubes (S = - 0.16%
C
-1
) [10], carbon nanofilms deposited
on diamond crystals (S = -0.14%
C
-1
) [11] and carbon-polymer flexible temperature sensor (S= -
0.13% K
-1
) [27]. The sensors resistance (R) is determined as given in Eq. 5.2 [15]. As CNT is a
nanopowder, for the observed resistance-temperature relationship the increase in the conductivity
of the CNT film under the effect of temperature may be due to the increase in concentration of
charge carriers, same like in semiconductors [16]. Using an exponential function given in Eq.
5.3, the relationship can be represented as given in Eq.5.7 [17]. From the experimental data
shown in Figure 5.5, the calculated average value of K is 0.689 10
-2

C
-1
, while A is constant with
value 1. Experimental and simulated (by using Eq. 5.7) results are plotted in Figure 5.6 and these
results are matched with an accuracy of 2 percent.

106

Figure 5.4 Al/CNT/Al resistance temperature sensor

20 30 40 50 60 70
8
9
10
11
R
e
s
i
s
t
a
n
c
e

(
K
O
)
Temperature (C)

Figure 5.5 Resistance-temperature relationship of the one of Al/CNT/Al sensors

Elastic casing CNTs
Terminal Terminal
107

5.7

The mechanism of conductivity in CNT samples can be considered as transitions between
spatially separated sites, or particles that can be attributed to the Percolation Theory [18, 19].
According to percolation theory, the effective conductivity () of the CNT samples can be
calculated as given in Eq. 5.6.
With an increase of temperature, the CNT layer will be heated that will cause the reduction of Z
due to generation of charge carriers. On the other hand, as the CNT nano-particles are
encapsulated due to the thermal expansion the particles will be squeezed and the contact areas
between particles or effective cross-section of the sample (Eq. 5.6) will be increased as well that
will decrease the resistance of the sample. As a result, the conductivity of the CNT samples
increases and the resistance decreases with increase of temperature accordingly, as is observed
experimentally (Figure 5.5). The CNT system can be assumed as a bulk hetero system that
results to high sensitivity of the CNT layers to the effect of temperature. With the rise in
temperature the increase in inter-particles contact areas and intrinsic conductivity of the
nanoparticles takes place that results in an increase in conductivity and decrease in resistance of
the samples.
Formally, the structure of the investigated sensors is the same as presented in [20], as in both
cases the flexible substrates are used for deposition of the CNT layer. But in [20] the flexible
substrate was fixed on silicon wafer by gluing. Moreover in our case the CNT layer is actually
encapsulated in plastic casing to prevent effect of humidity on the resistance as CNT based
layers are very sensitive to the influence of humidity [4-9], i.e. in this case the influence of the
humidity to electric properties of the sensors is neglected.
As the experimental resistance-temperature (Figure 5.5) relationship for the Al/CNT/Al sensor is
quasi-exponential, it may be easy to linearized by nonlinear op-amps [21].
5.2.4 Conclusions
The surface-type Al/CNT/Al flexible temperature sensors were designed, fabricated and
investigated. The resistance-temperature relationship has semiconductive behavior. The average
108

temperature sensitivity of the samples is -1.26%
C
-1
. For the explanation of a conduction
mechanism, the percolation theory is used. The CNT system is assumed as a bulk hetero system.
In this system the increase in the inter-particle contact areas and intrinsic conductivity of the
nanoparticles takes place as well, which results in decrease in resistance and increase in
conductivity of the samples with increase of the temperature. The temperature sensors show
good performance, and as the CNT layer is encapsulated in flexible elastic casing the effect of
humidity on the electric properties of the sensors is neglected.

109

20 30 40 50 60 70
0.70
0.75
0.80
0.85
0.90
0.95
1.00
Experimental
Simulated
R
e
l
a
t
i
v
e

R
e
s
i
s
t
a
n
c
e

(
R
/
R
o
)
Temperature (C)

Figure 5.6 Experimental (solid line) and simulated (dashed line) relative resistance-
temperature relationships of the Al/CNT/Al sensors (R
o
and R are initial resistance and
resistance at elevated temperatures respectively)

110

5.3 A study of V
2
O
4
-PEPC composite based resistance temperature sensors
5.3.1 Introduction
Vanadium oxide (VO
2
) shows large reversible change in electric, magnetic and optical properties
at temperatures around 68-70
C [28-30] where semiconductor to metal transition takes place.

The optical properties of vanadium dioxide change quickly at transition temperature: the optical
transmission decreases and reflectivity increases. Its transition temperature may be decreased by
the addition of transition metals such as niobium, molybdenum or tungsten. These characteristics
make vanadium dioxide an attractive material for smart windows for solar energy control, optical
and electrical switches. The hysteresis of transition in thin films of VO
2
is affected by their
microstructure and crystallinity.
It was found that VO
2
films demonstrate holographic storage and bit recording properties when
used under a near-infrared laser [31, 32]. Switching time of about 30 nsec and writing energy of
the order of a few mJ/cm
2
are reported [33]. The vanadium dioxide is an interesting candidate for
modern applications of active thin films in electric or optical [34] switches as well.
As photosensitive organic semiconductor the complexes of poly-N-epoxypropylcarbazole
(PEPC) have good adhesive properties and are used for the fabrication of photoelectric sensors
and photocapacitors [35]. PEPC based highly sensitive resistance strain gauges have also been
fabricated and investigated as well [36].
Fabrication of the temperature sensors and investigations of their properties on the basis of
vanadium oxide and PEPC composites would be useful from practical point of view and for
deepening of the knowledge about the physical properties of the composites. It would be
reasonable to investigate the resistance-temperature relationships. In this study, surface-type
resistance temperature sensors based on V
2
O
4
-PEPC composite have been designed, fabricated
and investigated.
5.3.2 Experimental
The commercially available V
2
O
4
micropowder was purchased from ALDRICH and was used
without further purification. Average size of V
2
O
4
micro particles was 20 microns. The blend of
laboratory [36] synthesized PEPC and V
2
O
4
was prepared by mixing 10 wt.% vanadium oxide
111

(V
2
O
4
) micro-powder and 2 wt.% poly-N-epoxypropylcarbazole (PEPC) in 1 ml of benzol. To
fabricate thin (20-40 m thick) films of V
2
O
4
-PEPC microcomposite, the blend was drop-casted
on silver electrodes which were pre-deposited on glass substrates and there was a 30-40 2 m
gap between the electrodes. The area of each silver electrode was 15x10 mm
2
while its thickness
was 100 1 nm. Figure 5.7 shows schematic diagram of the V
2
O
4
-PEPC composite films based
temperature sensor.
The change in AC resistance of the sensor with change in temperature in the range of 33-90 C
was measured at 100 Hz, 1 kHz and 10 kHz by using Agilent U1732A LCR meter. After
repeating the measurement thrice the relative standard deviation in results was found with in
5%.
Figure 5.8 shows SEM micrograph of the V
2
O
4
-PEPC film obtained by JEOL JSM-6460. It can
be seen that the structure of the film contains clusters of the particles. Figure 5.9 (a and b) shows
resistance-temperature relationships for two of the V
2
O
4
-PEPC sensors during heating process.
When temperature increases from 33
C to 90
C, the AC resistance of the samples decreases by

10-12 times. It can be seen that resistancetemperature relationships are similar for two samples:
the resistance slightly decreases with increase of the frequency from 100 Hz to 10 kHz, and the
change in the slope of curve takes place in the temperature range of 58-64
C, that can be
associated with well-known phase transformation [28-30] in V
2
O
4
. Figure 5.10 (a and b) shows
derivative of the resistance (dR/dT)-temperature relationships for the two samples, that clearly
show the location of the phase transformation in the temperature domain. Figure 5.11 shows
resistance-temperature relationships of heating-cooling processes for one of the samples at a
frequency of 100 Hz. In Figure 5.11, the hysteresis can be seen in the case of V
2
O
4
-PEPC
composite as well, that was observed in transmission and resistance-temperature relationships for
the pure V
2
O
4
films [28-30]. At the same time the phase transition temperatures of V
2
O
4
-PEPC
composite during heating and cooling processes are lower than that of pure V
2
O
4
: the T
h
and T
c

are 60
C and 52
C in the case of V
2
O
4
-PEPC composite while in the case of V
2
O
4
T
h
and T
c
are
approximately 80
C and 60
C respectively [29].
112

Figure 5.7 Schematic diagram of V
2
O
4
-PEPC composite based resistance temperature
sensor

Figure 5.8 SEM image of V
2
O
4
-PEPC composite film

V
2
O
4
-PEPC
Ag Ag
Glass Substrate
113

Figure 5.9(a and b) Resistance-temperature relationships for two of the V
2
O
4
-PEPC sensors
during heating process

30 40 50 60 70 80 90
0
100
200
300
400
500
600
100 Hz
1 KHz
10 KHz
R
e
s
i
s
t
a
n
c
e

(
K
O
)
Temperature (C)
a
30 40 50 60 70 80 90
0
20
40
60
80
Heating-100 Hz
Heating-1 KHz
Heating-10 KHz
R
e
s
i
s
t
a
n
c
e

(
K
O
)
Temperature (C)
b
114

Figure 5.10(a and b). Derivatives of the resistance (dR/dT)-temperature relationships for
the two of the V
2
O
4
-PEPC sensors during heating process.

30 40 50 60 70 80 90
0
-5
-10
-15
-20
-25
-30
d
R
/
d
T
Temperature (C)
a
30 40 50 60 70 80 90
0.0
-0.5
-1.0
-1.5
-2.0
-2.5
d
R
/
d
T
Temperature (T)
b
115

The effects of temperature on the sensors resistances were slightly different, depending on the
samples thickness; for thicker (40 m) and thinner (20 m) V
2
O
4
-PEPC films the resistance
temperature coefficient (S) of the samples were calculated by Eq. 5.1 [14, 37]. For thicker and
thinner films, the calculated values of S at 33
C are -2.3 and -3.5 %/
C, respectively. The values

of the resistance temperature coefficient (S) are in the range of industrially produced
semiconductor temperature sensors [14, 37].
The sensors resistance (R) can be represented by the Eq. 5.2 [38]. As V
2
O
4
-PEPC is a micro-
composite, for the observed resistance-temperature relationship the increase in the conductivity
of the V
2
O
4
-PEPC film is due to increase in concentration of charge carriers; a similar effect
occurs in semiconductors [16] under the effect of temperature.
By using an exponential function given in Eq. 5.3, the resistance temperature relationship can be
represented as given in Eq. 5.8 [17]:

5.8
where A is constant with value 1, R is the samples resistance at elevated temperatures (T), K is
resistance temperature factor. Equation 5.8 is used for the simulation of heating curve, while
cooling curve is simulated by Eq.5.7.
From the experimental data shown in Figure 5.11, the average values of K were determined as
3.3x10
-2

C
-1
and 3.5 x10
-2

C
-1
for heating and cooling curves respectively. The experimental and
simulated results are plotted in Figure 5.11, they coincide with an accuracy of 8.5 percent.
The decrease in the sensors resistance with an increase in temperature can be explained in an
alternative way. The composite consists of two components, V
2
O
4
and PEPC. The conductivity
of the PEPC is lower (4x10
-9
cm
-1
-1
) [36] with respect to the conductivity of V
2
O
4
(6x10
-4
cm
-
1
-1
) [39], and actually, conductivity of the composite (3x10
-11
cm
-1
-1
) is controlled by PEPC.
Taking into account that the conductivity of the composite is lower than the conductivity of the
PEPC and V
2
O
4
, it can be assumed that in the interface of the V
2
O
4
-PEPC particles junctions,
there are depletion regions. Therefore, V
2
O
4
-PEPC system can be considered as a bulk
heterojunction system. This may be one of the reasons that the composite shows high sensitivity
to the effect of heating, as observed from the resistance-temperature relationships (Figure 5.9).
116

In polycrystalline organic semiconductor thin films as in disordered system, mostly hopping
mechanism of conduction has been observed [39-41], due to phonon assisted hopping of carriers
from one localized state to another. As a rule the mobility increases with temperature, but it
depends on the actual contribution from scattering phenomenon. It was found that the mobility
may increases, decreases or be independent of temperature in different organic semiconductors
[40, 41]. Usually a value of mobility around 1 cm
2
V
-1
s
-1
is considered as a boundary between
band transport and hopping [39-41] mechanisms. Ioffe and Regel [42] have shown that at
mobility lower than 1 cm
2
V
-1
s
-1
the mean free path of carriers calculated from band transport
approach is less than the inter atomic distances in semiconductors that would be incorrect from
physics point of view.
Tunneling effect actually is the most universal phenomenon, but it may contribute mostly at very
low temperatures where band and hopping mechanism have less contribution. It is believed that
in the tunneling mechanism mobility shows temperature independent behavior and values of
mobility are very low (<<1 cm
2
V
-1
s
-1
).
The mechanism of conductivity in PEPC can be considered as thermally assisted hopping
transitions between spatially separated sites, molecules or particles that can be attributed to the
Percolation Theory [18, 19]. The average conductivity () of the one component (in this case
PEPC), according to percolation theory, can be calculated by the expression given in Eq 5.6.
With an increase of temperature, the V
2
O
4
particles in the composite film will be slightly
squeezed due to their thermal expansion, firstly, and, secondly, conductivity of the PEPC will
increases due to temperature activated hopping mechanism of conductivity. As a result with
increase in conductivity the resistance of the sample decreases accordingly as observed
experimentally (Figure 5.9).
In V
2
O
4
-PEPC system it may be considered that the conductivity of PEPC is much less than that
of V
2
O
4
. Therefore at low concentration of the V
2
O
4
particles, when there is no direct electric
contact of the particles with each other, the conductivity of PEPC can control the conductivity of
the composite. At larger or critical concentration of V
2
O
4
in the V
2
O
4
-PEPC composite the V
2
O
4
particles can form conductive channels that can increase the composites conductivity
enormously.
117

Figure 5.12 (a and b) shows log relative resistance-temperature and relative resistance-log
temperature relationship for the V
2
O
4
-PEPC sensor. It is seen that the graph is quasi-linear. It
means the original graphs can be linearized by the nonlinear op-amps [21], that is important for
practical application of the sensors.
Figure 5.13 shows relative resistance-time relationship for the V
2
O
4
-PEPC composite
temperature sensor. It can be seen that response and recovery times for the sensor are equal to
2.5 and 3 minutes respectively.
5.3.4 Conclusions
The surface-type V
2
O
4
-PEPC composite based temperature sensors were designed, fabricated
and investigated. The resistance-temperature relationships were simulated. For the explanation of
the conduction mechanism, the percolation theory is used. The V
2
O
4
-PEPC system is assumed as
a bulk hetero junction system that results in high sensitivity of the composite. The resistance
temperature coefficients of the samples were in the range of (-2.3 -3.5 %
C
-1
) at 33
C.

118

30 40 50 60 70 80 90
0.2
0.4
0.6
0.8
1.0 Experimental-Heating
Simulated-Heating
Experimental-Cooling
Simulated-Cooling
R
e
l
a
t
i
v
e

R
e
s
i
s
t
a
n
c
e

(
R
/
R
o
)
Temperature (C)

Figure 5.11 Resistance-temperature relationships at heating-cooling processes for the one
of the V
2
O
4
-PEPC sensors at 100 Hz. Experimental and simulated relative resistance-
temperature relationships of the V
2
O
4
-PEPC based temperature sensor

119

Figure 5.12 The log relative resistance-temperature relationship (a) and relative resistance-
log temperature relationship (b) for the V
2
O
4
-PEPC sensor

30 40 50 60 70 80 90
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
0.0
L
o
g

(
R
/
R
o
)
Temperature (C)
a
1.5 1.6 1.7 1.8 1.9 2.0
0.0
0.2
0.4
0.6
0.8
1.0
R
/
R
o
Log (T)
b
120

0 5 10 15 20 25 30
0.2
0.4
0.6
0.8
1.0
90C
R
e
l
a
t
i
v
e

R
e
s
i
s
t
a
n
c
e
Time (Min)
30C

Figure 5.13 Relative resistance-time relationship for the V
2
O
4
-PEPC composite
temperature sensor.

121

5.4 Temperature sensing properties of organic-inorganic Ag/p-CuPc/n-
GaAs/Ag cell
5.4.1 Introduction
Although the devices fabricated by organic materials are low power consuming but there is a
need to improve the efficiency and stability of these devices. For this purpose different
techniques are used, out of which organicinorganic structure is most popular. Walter Rieb et al.
[43] investigated organic-inorganic multilayer structure in which they devised a route for high
efficiency light emitting diode by arranging alternate organic and inorganic thin films between
two metallic electrodes. The hybrid organic-inorganic solar cells were fabricated by Nguyen
Cong et al. [44] and they investigated the photovoltaic junctions of PMeT(Y)/CdS(X) thin films
which were deposited on ITO glass. The element (X) and anion (Y) are dopant for inorganic and
organic thin films respectively. Deng et al. [45] investigated the organic-inorganic interface of
the organic electroluminescence devices, and results reveal that by insertion of inorganic layer,
energy offset of devices can be changed and ozone treatment decreases the interface
contamination which in turn enhances the emission intensity and stability of the devices. Gullu et
al. [46] also fabricated and investigated the electronic properties of sandwich type Schottky
device made of Al/CR (Congo Red)/p-Si. This metal/organic interlayer/inorganic semiconductor
device was the modification of metal/semiconductor (Al/p-Si) diode. On the basis of forward
bias I-V characteristics of modified device they reported an ideality factor (n) 1.68 eV and
barrier height (
b
) 0.77 eV, which is notably higher than the barrier height of Al/p-Si diode. The
organic thin layer of CR affects the silicons space charge region due to which barrier height
increases.
Based on the concept of organic-on-inorganic structures the Ag/p-CuPc/n-GaAs/Ag cells were
fabricated. The GaAs and CuPc are the well known inorganic and organic photosensitive
semiconducting materials respectively. Being widely used inorganic semiconducting material for
electronic devices the GaAs has energy band gap of 1.4 eV [47, 48], while that of CuPc is 1.6 eV
at room temperature. At 27 C the conductivity of CuPc is 5 x 10
-13
O
-1
cm
-1
[40, 41].

As a
photosensitive material the p-type CuPc under low intensity radiation has high photo-
electromagnetic sensitivity along with higher absorption coefficient in wide spectrum range [47,
48]. The fabricated organic-on-inorganic sensors were characterized in photovoltaic mode of
122

operation at room temperature and source of illumination was the tungsten filament lamp.
Results showed that the Ag/p-CuPc/n-GaAs/Ag cell has sensitivity in large spectral range from
UV to visible and NIR spectrum (wavelengths 200-1000 nm) [47]. These sensors were
characterized for different electrical and photo electrical properties in low as well as high
temperature environment. The study of photoelectric and voltage-current characteristics of Ag/p-
CuPc/n-GaAs/Ag sensors in the temperature range of 82 to 350 K showed that open-circuit
voltage, short-circuit current, rectification ratio, threshold voltage and junction shunt and series
resistances are temperature dependent parameters [49]. The frequency response and temperature
dependent I-V characteristics of organic-inorganic heterojunction diodes in the temperature
interval of 23-74 C, and the information about the organic inorganic junction study of electric
and photoelectric properties of cells in integral mode of operation has been stated in [50]. By
investigating the differential responsivity it was observed that the sensors output voltage and
current depends on the position of light beam probe in differential mode of operation [51]. The
energy-band diagram of the p-CuPc/n-GaAs heterojunction was developed on the basis of
experimental data on absorbance and voltage-current properties [49].
For measurement of the temperature in very wide range metallic resistance temperature
detectors (RTDs) and semiconductor thermistors are used [14]. These devices can measure only
temperature. As Ag/p-CuPc/n-GaAs/Ag cells are sensitive to light. It was reasonable to
investigate temperature sensitivity of the cells that would be practically important for fabrication
of multi-functional sensors for measurement of the illumination and temperature as well.
Normally temperature is measured on spot by using temperature sensors. But for some specific
cases telemetry systems (which may be long-range or short-range) are needed for temperature
measurement. In these systems sensor with transmitter are placed at a distance from receiver and
transfer of information takes place through wireless communication [14]. In response to
temperature, the sensor generates a voltage, which is used to modulate the frequency of voltage-
controlled oscillator. The receiver demodulates frequency modulated (FM) signals and process
them accordingly [14]. The modulation of oscillators frequency directly by the sensor can make
the process of frequency modulation simple. The fabricated organic on inorganic type CuPc-
GaAs cells may be used as multifunctional sensors for the measurement of temperature and
illumination.
123

5.4.2 Experimental
5.4.2.1 Fabrication of cells
The experimental procedure has been discussed in detail previously [49]. For the deposition of
organic (p- CuPc) and metal (Ag) thin films on inorganic (n-GaAs) substrate by thermal
sublimation in vacuum, a thermal evaporator was used. To form the ohmic contact [47]
semitransparent film of Ag was deposited on the surface of GaAs substrate on one side while on
the other side CuPc was deposited. Before deposition of CuPc on to the GaAs, the CuPc powder
was sublimed in vacuum to get purification while the GaAs substrate was etched with a solution
of 1 part H
2
O
2,
1 part

NH
4
OH and 3 parts H
2
O for 30 seconds. After etching substrates were
cleaned by washing with hot distilled water (70-80 C) followed by drying with spirits vapors.
To deposit the 20-40 nm thickness thin film, substrate was held at ~40 C and CuPc was
sublimed at 400- 450 C. The deposition process was done in a vacuum chamber having vacuum
of ~10
-4
Pa. Prior to Ag deposition on to it the CuPc thin film was exposed to atmospheric
oxygen to dope it for 30 minutes. A thin semitransparent layer of Ag with 6-10 percent
transmittance of incident light was deposited on to the CuPc again by vacuum evaporation.
The crystal orientation of GaAs is 100 and its donor impurity (N
D
) level is 2 x 10
18
cm
-3
. The
CuPc exists in seven crystalline polymorphic states which are , , , R, , etc [52]. The
commonly encountered states are and CuPc. The to state transformation is more frequent
and it can takes place thermally or by solution technique. The is the metastable state of CuPc at
a temperature of 165 C. Its molecular weight is 576 a.m.u, while at pressure of 10
-4
Pa, its
sublimation temperature varies from 400 C to 580 C [48, 53].
The fabrication detail of cell can be seen in Figure 5.14 in cross-sectional and top view. The
CuPc film diameter which is the active diameter of the cell is about 3 cm. To stabilize the
parameters, aging of the Ag/p-CuPc/n-GaAs/Ag cell was carried out at 100 C for 80-120 hrs
under illumination of filament lamp (with light intensity 50 mW/cm
2
). Complete aging process
consisted of 10-15 heating (up to 100 C) and cooling (to 25 C) cycles which were completed in
80-120 hrs. The aging might result in short circuiting of cells due to applied conditions, which
are close to service conditions.
124

A Digital Hi-Tester 3256 multimeter was used to measure the resistance. The output voltage of
multimeter was 2.54 V. The forward and reverse bias resistances-temperature relationships for
the Ag/p-CuPc/n-GaAs/Ag cell were investigated in the temperature interval of 306-348 K.
Investigations of samples for resistancetemperature relationships were carried out in
indigenously made chamber in our laboratory. Tests were carried out thrice to confirm
repeatability and the variation in the results was 4 percent.
The surface structure and morphology of the CuPc film was investigated. Figure 5.15 shows the
SEM image of the CuPc film. Figure 5.16 shows temperature dependences of forward (R
F
) and
reverse (R
R
) bias resistances of the fabricated cell. It can be seen that R
F
and R
R
decreases with
increase of temperature. The temperature coefficient of resistance or sensitivity (S) has been
calculated for R
F
and R
R
[14, 54] by using Eq. 5.1 and in this equation R and R
o
are resistances at
temperature and 33 C, respectively. The obtained S value of the cell is comparable with the S
values of thermistors [14]. For R
R
and R
F
the values of sensitivity are -0.020/C and -0.015/C
respectively.
The resistance-temperature relationship (Figure 5.16) can be simulated by the following
expressions [14] that are used for the thermistors:

5.9
where is the specific resistance of the material, A
1
, A
2
, A
n
are material constants, is the
absolute temperature, or by
where R is the resistance of temperature sensor at temperature , R
o
is the resistance of
temperature sensor at reference temperature
o
, is a material constant that ranges from 3000 to
5000 K, and
o
are absolute temperatures in K. The material constant () is determined by the
following expression [14]:

5.10
125

Figure 5.14 Cross sectional view of organicinorganic heterojunction sensor fabricated by
using n-type GaAs substrate and a thin p-CuPc film: 1-GaAs, 2-CuPc, 3-Ag, 4-Ag (semi-
transparent), 5 and 6- terminals; (a) Side view (b) Top view.

Figure 5.15 SEM image of the deposited CuPc film

1
2
4
5
6
1

3

4

5

6

2

(a) (b)
126

5.11
By using Eq. 5.11 and Eq. 5.12 which is the modified form of Eq. 5.10; the resistance-
temperature relationship of the cell can be simulated.

5.12
where A is the multiplication factor, for R
R
its value is 1.18 while for R
F
up to temperature of 60
C its value is 1.4 but when temperature exceeds than 60 C its value becomes 1.9. It is evident
from Figure 5.17 that during resistance measurement in forward bias mode when temperature
exceeds 60 C its sensitivity changes abruptly. Figure 5.17 and Figure 5.18 show the
experimental and simulated results of R
R
and R
F
respectively. It can be seen that the average
deviation of the simulated graph from experimental is in the range of 5 %.
For the fabrication of multifunctional sensors it is important to investigate the temperature
sensitivity of the cell. On the basis of the same heterojunction; the Ag/p-CuPc/n-GaAs/Ag cell
behaves as temperature and light sensor. It is photosensitive in photovoltaic and photoconduction
modes of operations [49, 50]. In multifunctional probe unit the light sensor should have
transparent lid while the temperature sensitive device should have opaque lid. The dual
sensitivity error is the well known problem of the devices which sense two parameters [14]. In
light temperature multifunctional sensors the effect of temperature can be minimized by the use
of Wheatstone bridge. It is the widely used method of engineering measurements [14] in which
two cells, one with transparent lid and other with opaque lid are connected with two arms of
bridge. For the light and temperature sensitive cells the Wheatstone bridge compensates the
effect of temperature on light sensitivity while during temperature measurement the Wheatstone
bridge makes possible the connectivity of only cell with opaque lid.
5.4.4 Conclusions
The Ag/p-CuPc/n-GaAs/Ag cell was fabricated. It was found that the resistance temperature
coefficients (S) for the reverse and forward bias resistances are equal to -2.0% /C and -1.5% /C
respectively. Resistancetemperature relationships simulation showed reasonable agreement
with experimental results. The cell is photosensitive and can be used as multifunctional sensors.
127

The potential applications of the cell may include temperature and light meters, teaching aid
(solid state electronics) and telemetry systems (use in data transmission) [14, 54, 55].

128

30 40 50 60 70 80
0
100
200
300
400
R
R
R
F
R
e
s
i
s
t
a
n
c
e

(
K
O
)
Temperature (C)

Figure 5.16 Dependence of reverse (R
R
) and forward (R
F
) bias resistances of the Ag/p-
CuPc/n-GaAs/Ag cell on temperature.
30 40 50 60 70 80
0.2
0.4
0.6
0.8
1.0
R
R
/R
R0
-Experimental
R
R
/R
R0
-Simulated
R
R
/
R
R
0
Temperature (C)

Figure 5.17 Dependence of the simulated and experimental relative reverse (R
R
/R
oR
) bias
resistances of the Ag/p-CuPc/n-GaAs/Ag cell on temperature
129

30 40 50 60 70 80
0.0
0.2
0.4
0.6
0.8
1.0
R
F
/R
F0
-Experimental
R
F
/R
F0
-Simulated
R
F
/
R
F
0
Temperature (C)

Figure 5.18 Dependence of the simulated and experimental forward (R
F
/R
oF
) bias
resistances of the Ag/p-CuPc/n-GaAs/Ag cell on temperature

130

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Verlag GmbH & Co.

135

Chapter-6
Displacement and Pressure Sensors
6 6
In this chapter three types of sensors have been discussed. This chapter consists of four parts.
Part one presents the investigation of the effect of displacement on polyaniline film, part two is
about carbon nanotubes-cuprous oxide composite based pressure sensors, third and fourth
sections describe the CNTs and CNTs-cuprous oxide composite based strain sensors,
respectively. For the investigation of effect of displacement, 20-80 m thick films of PANI are
deposited on silver electrodes which were pre-deposited on glass substrates. The films are
deposited from a solution of 1 wt.% of PANI micro-powder mixed with 90 wt.% of water and 10
wt.% alcohol at room temperature. The effect of displacement on resistance and capacitance of
films are studied and simulated results have been presented here. Pressure sensors are fabricated
by pressing the mixture of CNTs and Cu
2
O in the form of tablets and silver paste is deposited on
the two sides of the tablets to make a low resistance contact. The changes in DC resistance of the
sensors are measured under the effect of pressure. Simulated results of pressure sensors along
with detailed discussion are given in part two of this chapter. The CNTs and CNTs-cuprous
oxide composite based sensors are fabricated by making pellets of respective materials followed
by deposition of electrode and fixation of these pellets on to a flexible beam. Both sensors are
tested under strain in tensile and compressive modes and the simulated results have been
presented in this chapter.
6.1 Effect of displacement on resistance and capacitance of polyaniline film
6.1.1 Introduction
There are different types of displacement sensors that have been commonly used with the
following sensing modes: capacitive, eddy-current, linear variable differential transformer
(LVDT), multiple resistor, optical instruments, photoelectric sensor and resistance
potentiometers [1, 2]. These sensors usually cover a long range of displacement from microns up
to centimeters, as well. Some of the sensors are non-contacting as capacitive, eddy-current and
photoelectric while some others are contacting type as LVDT, multiple resistor, resistance
potentiometers [1].
136

Cantilever-type displacement sensors using diffused silicon strain gauges based on two kinds of
alloys have been developed by Mitsuo et al. [3]. A new device has been designed, and a
prototype has been built and tested, that can simultaneously measure the displacements and/or
the components of a force in three orthogonal directions. This 3D sensor consists of four/eight
strain gauges attached to the four arms of a single cross-shaped force-measuring cantilever
spring [4]. The resistance-displacement characteristic of a magnetoresistor moving in a
magnetic field was examined by Ferris et al. [5].
It is known that polyaniline (PANI) is one of the most interesting conducting polymer due to its
good conductivity, stability, easy preparation and potential applications for fabrication of
different organic semiconductor devices [6-8]. The fabrication of the displacement sensor and
investigations of the squeezing effect to the PANI would be useful from practical point of view
and for the deepening of knowledge about the physical properties of the polymer. It would be
reasonable to investigate the resistance-displacement and capacitance-displacement relationships.
6.1.2 Experimental
The emeraldine base (EB) polyaniline (PANI) commercially available by Sigma Aldrich with
formula C
24
H
20
N
4
and a molecular weight ~ 20,000 was used. The 1 wt % of PANI powder was
mixed in a solution of 90 wt. % water and 10 wt. % of alcohol and stirred at room temperature.
Glass substrates were cleaned for 10 minutes using distilled water in ultrasonic cleaner and dried.
Then the substrates were also plasma cleaned for 5 min. The Ag thin film electrodes were
deposited by vacuum evaporation on cleaned substrates. The thickness and the size of the Ag
electrodes was 100 nm, 10x10 mm
2
respectively. The PANIs films with thickness ranging from
20-80 3 m were deposited from solution by drop-casting on Ag electrodes at room
temperature.
Figure 6.1 shows SEM image of PANI film which was obtained by Philips XL-30 Scanning
electron microscope. It can be seen that the structure of the film is not uniform and contains
clusters of the PANI particles. The sizes of the clusters are in the range of 5-15 m.
The fabricated sensors were kept at room temperature for one night to evaporate the moisture
from the films. To make sandwich-type Ag/PANI/Al resistance and capacitance displacement
137

sensor (Figure 3.10) thin aluminum foil of thickness 40 m and size 5 x 5 mm
2
was used as a
second electrode. The sensor consists of the following elements: glass substrate (1), silver film
(2), PANI film (3), aluminum foil (4), terminals (5 and 6), elastic rubber (7) with 2 mm height
and 6 mm diameter, spring (8) having 3 mm height and 5 mm diameter, and micrometer (9). The
value of the displacement was measured by micrometer. As micrometer moves down in vertical
direction the value of the displacement increases. The range of the displacement depends upon
the heights of the spring and elastic rubber (Figure 3.10) and elastic properties of their materials.
The Capacitance (C) and the resistance (or dissipation (D)) were measured at a frequency of 120
Hz by using of ESCORT ELC-132A handheld LCR meter. Depending on the value, the
resistance (R) was measured directly or calculated by the measurement of dissipation by the
following expression [9]:

6.1
where f is frequency. The accuracy of the resistance measurement was 3%, while that of
capacitance is 1.0 %. The sensors were tested three times and results were found repeatable with
relative standard deviation of 5%.
Figure 6.2 shows relative resistance- displacement and capacitance- displacement relationships
of the Ag/PANI/Al sensor. It can be seen that with the increase of the displacement from 0-0.5
mm the sensors resistance decreases by 2 times and capacitance increases by 1.4 and 1.8 times
for polyaniline films of 20 m and 80 m respectively.
The sensors resistance (R) can be represented by the following expression [10]:

6.2
where d is the length or inter-electrode distance and A is the cross-section of the sample (in this
case the area of the aluminum electrode), is resistivity ( = 1/, where is conductivity ). The
resistance-displacement relationship shown in Figure 6.2 may be due to decrease in thickness (d)
of the film under the effect of squeezing by the micrometer or/and increase of the conductivity
138

() of the film due to decrease in distance between the polyaniline molecules (Eq. 6.2). It can be
assumed that the last process is dominating.
For the simulation of the experimental results (Figure 6.2), the following exponential function
[11] can be used:

6.3
For the present case, Eq. 6.2 can be represented in the following expression:

6.4
where A is constant having value 1, D is displacement, K
1
is resistance displacement factor. From
the experimental data shown in Figure 6.2 the displacement factor K
1
was determined (K
1
=
1.386 mm
-1
) for the displacement of 0.5 mm.
Figure 6.3 shows experimental (from Figure 6.2) and simulated (by Eq. 6.3) graphs. It can be
seen that the simulated curve matches well with the experimental data with an accuracy of 2.6
percent.
The decrease in sensors resistance with increase in displacement can be explained as follows.
The mechanism of conductivity in PANI can be considered as thermally assisted hopping
transitions between spatially separated sites, molecules that can be attributed to the percolation
theory [12, 13]. According to percolation theory the average conductivity () of the material can
be found by the expression:

6.5
where L is a characteristic length, depending on the concentration of the sites, Z is the resistance
of the path with the lowest average resistance. With the increase in displacement the PANI film
will be squeezed between silver film and aluminum foil (Figure 3.10). This squeezed film may
cause, firstly, the decrease of L and, secondly lowering of Z. As a result, conductivity of the
sample increases and the resistance decreases accordingly, as observed experimentally (Figure
6.2).
139

The room temperature AC capacitance of the Ag/PANI/Al sensors was in the range of 0.02-0.3
nF at zero displacement. The sensors capacitance (C) can be represented by the following
expression [10]:

6.6
where A is the area of capacitor, is the relative permittivity,
o
c is the permittivity of free space
and d is the distance between plates of the capacitor. The capacitance-displacement relationship
shown in Figure 6.2 may be due to (i) decrease in the thickness (d) of the PANI film under the
pressure of micrometer and/or (ii) increase in the relative permittivity of the polyaniline film,
which is due to (a) the decrease in distances between the molecules (Eq. 6.5), and (b) change in
its polarizability. We consider that the contribution of the last process dominates the change of
capacitance of the sensor.
For the simulation of the experimental capacitance-displacement relationships for the
Ag/PANI/Al sensor (Figure 6.2), the following phenomenological expression [14] can be used:

6.7
where and
s
are the permittivity coefficients of the polyaniline film at normal and under
squeezed state, respectively, and C
o
and C are the corresponding capacitances. The factor n is
related to the morphology of the material. Eq. 6.7 can be represented as

6.8
where

6.9
K
2
is capacitance displacement factor.
Figure 6.4 shows experimental (from Figure 6.2) and simulated (by Eq. 6.7) graphs in the case of
n=0.5 and K
2
= 4.27 mm
-1
. It can be seen that the simulated curve matches reasonably with the
experimental data.
140

Figure 6.1 SEM image of porous polyaniline film.

0.0 0.1 0.2 0.3 0.4 0.5
0.6
0.9
1.2
1.5
1.8
Relative Resistance
C
/
C
o

&

R
/
R
o
Displacement (mm)
Relative Capacitance

Figure 6.2 Relative resistance-displacement and capacitance-displacement relationships for
the Ag/PANI/Al sensor: polyaniline films thickness is 80 m (solid line ) and 20 m (dashed
line).

141

In Figure 6.3 and Figure 6.4 deviation of simulated graphs from experimental graphs in the range
of lower displacement may be firstly due to the complexity of the structure of the polyaniline
films (Figure 6.1). Secondly, Eq.6.3, Eq.6.4 and Eq.6.7 probably can be used as a first
approximation only and these equations can be replaced by series [11].
Figure 6.2, Figure 6.3 and Figure 6.4 show resistance and capacitance dependence on total
displacement that is measured by micrometer. The total displacement is the sum of the
displacements of the spring (Figure 3.10 (8)), elastic rubber (Figure 3.10 (7)) and polyaniline
film Figure 3.10 (3)). The largest displacement values are those of the displacement of the spring
(Figure 3.10 (8)) and elastic rubber (Figure 3.10 (7)). Displacement of the polyaniline film
(Figure 3.10 (3)) can be considered lowest, as the modulus of elasticity of this material is
definitely larger than that of elastic rubber. The polyaniline is the only active material of the
displacement sensor. The resistance and capacitance of the PANI change under the pressure of
spring and elastic rubber and this pressure is created by the downward movement of micrometer.
Probably the key factors for the performance of the sensor are the following: sizes of PANI
clusters (Figure 6.1), solution preparation technique (solvent composition, time of stirring,
temperature etc), film thickness and, the size and properties of the spring and elastic rubber. It
can be assumed that the decrease in the height of spring or elastic rubber will make the graphs
shown in Figure 6.2, Figure 6.3 and Figure 6.4 steeper and vice-versa. The detailed investigation
of these parameters will be carried out in future work.
The large-area flexible pressure sensor matrix with organic field-effect transistors (OFETs)
based on pentacene were fabricated by Someya et al. [15, 16]

and it was found that the matrix
shows high pressure sensitivity and mechanical flexibility. The fabricated displacement sensor,
with PANI based resistance/capacitance sensing film, can be used as pressure sensor as well, if
the pressure is applied to the spring (8 in Figure 3.10) downward in vertical direction. As
experimental curves of relative resistance-displacement (Figure 6.2) and relative capacitance-
displacement relationship for the Ag/PANI/Al sensor are non-linear, these graphs can be
linearized by nonlinear op-amps [17].
6.1.4 Conclusions
The sandwich-type resistance and capacitance Ag/PANI/Al displacement sensor was designed,
fabricated and investigated. It is found that with increase in displacement, the resistance of the
142

sensor decreases and capacitance increases, which is attributed to the decrease in the thickness of
the film under the effect of squeezing by the micrometer or/and increase in conductivity of the
film due to decrease of the distances between the polyaniline molecules. For explanation of
conduction mechanism, the percolation theory is used. The polyaniline system is assumed as a
polymer system that shows high sensitivity towards the effect of squeeze. It is also concluded
that key factors for the performance of the sensor are the sizes of PANI clusters, solution
preparation technique, film thickness and, the size and properties of the spring and elastic rubber.

143

0.0 0.1 0.2 0.3 0.4 0.5
0.5
0.6
0.7
0.8
0.9
1.0
Experimental
Simulated
R
e
l
a
t
i
v
e

R
e
s
i
s
t
a
n
c
e
Displacement (mm)

Figure 6.3 Comparison of experimental and simulated relative resistance-displacement
relationships for the Ag/PANI/Al displacement sensor.
0.0 0.1 0.2 0.3 0.4 0.5
1.0
1.2
1.4
1.6
1.8
Experimental
Simulated
R
e
l
a
t
i
v
e

C
a
p
a
c
i
t
a
n
c
e
Displacement (mm)

Figure 6.4 Comparison of experimental and simulated relative capacitance-displacement
relationships for the Ag/PANI/Al sensor.
144

6.2 Carbon nanotubes-cuprous oxide composite based pressure sensors
6.2.1 Introduction
Pressure transducers are mostly used with resistance, capacitance, inductance and piezoelectric
sensors and with devices such as diaphragm and bellows [1, 2]. Due to excellent electronic,
mechanical and thermal properties carbon nanotubes and their composites have developed great
interest for their use in sensors and actuators [18, 19]. These sensing and actuating devices have
applications in electronic switches, nano-tweezers organic optoelectronic, photovoltaics, elements
for mechanical damage detection and electromechanical transducers [18, 20, 21].
Electronically, CNTs can be metallic, semiconducting, or small-gap semiconducting (SGS)
materials, depending on the orientation of the graphene lattice with respect to the axis of the tube
[22]. Various types of sensors have been fabricated and investigated on the basis of single-walled
carbon nanotubes (SWCNTs), double-walled (DWCNTs) and multi-walled carbon nanotubes
(MWCNTs) [23-25]. The interesting electromechanical properties of CNTs make them suitable
material for use as piezoresistors in mechanical sensors such as strain gauges, accelerometers and
pressure sensors [22, 26-30]. The use of SWCNTs as mechanical actuators and the comparison of
their performance with natural muscles were first reported by Baughman et al. [31]. A
piezoresistive pressure sensor based on multi-walled carbon nanotubes (MWCNTs) and
polydimethylsiloxane (PDMS) was fabricated by Hwang et al. [19]. The poly(3 hexylthiophene)
(P3HT) was also used for the homogenous dispersion of MWCNTs in the composite. The
reported results show that in response to change in pressure from 0-0.12 MPa the relative
resistance changes from 1-1.21. It is also recommended that due to extremely low operating
pressure this sensor can be used for finger sensing. Bautista-Quijano et al. [18] reported the
piezoresistive and electrical response of polymeric films of polysulfone (PSF) modified with
0.05-1.0 w/w MWCNTs. It is reported that with increasing CNTs content from 0.05 to 0.5 w/w
the gage factor increases from 0.48 to 0.74. The piezoresistance of CNTs on deformable thin-film
silicon nitride membranes have also been investigated [22] and it was found that the gauge factors
(R/R) were 400 and 850 for the semiconducting and SGS tubes, respectively, whereas the
maximum value of gauge factor in silicon was 200.
Despite the fact that ongoing research is mainly focused on SWCNTs, the multiwall carbon
nanotubes (MWCNTs) are more suited for macro size applications due to their rapidly growing
145

large scale production technology [18]. Keeping in view the technological and economic
advantages of MWCNTs, we designed, fabricated and investigated resistive pressure sensors
based on the composites of commercially produced CNTs and Cu
2
O. Cuprous oxide (Cu
2
O) is a
photosensitive p-type semiconductor (E
g
= 2.17 eV) with particular magnetic properties having
applications in electronics, magnetic storage, energy conversion sensors and field emission
devices [32-34]. Non-toxicity and simple fabrication process of Cu
2
O along with abundance of
copper in nature make it highly attractive for technical applications and fundamental research
[33, 34]. Fabrication of nanodots and nanostructure thin films of Cu
2
O are reported in [35, 36],
while the modification of MWCNTs by Cu, CuO and Cu
2
O is reported by Wang et al. [33] and
preparation of Cu
2
O/MWCNT (multi-walled carbon nanotubes) nano-composites by low
temperature fixture method is reported by Zhang et al. [37].
As is known fabrication of materials based on composites allows to modify their properties,
which include specific resistances and samples resistances as well. This modification is
controlled by changing the ratio of elements in composite. The fabrication of CNT-Cu
2
O
composite based pressure sensors and investigations of their properties would be useful from
practical point of view and for deepening of knowledge about the physical properties of the
constituents: it would be reasonable to investigate the resistance-pressure relationships.
6.2.2 Experimental
For making CNT-Cu
2
O composite the commercially produced CNTs nanopowder and Cu
2
O
micro-powder were purchased from Sun Nanotech Co Ltd., China and WINLAB UK
respectively. The diameter of multiwalled nanotubes (MWNTs) varied between 10-30 nm, while
the size of Cu
2
O micro particles was in the range of 3-4 m. The blend of CNTs (25 wt.%) and
Cu
2
O (75 wt.%) was prepared by using mortar and pestle. Tablets of 10 mm diameter and 4 0.1
mm thickness were fabricated by pressing CNT-Cu
2
O composites at a pressure of 353 MPa. In
order to make low resistance electric contacts the two sides of the tablets were covered by a
silver paste. Figure 6.5 shows the photographs of one of the samples.
146

For the measurement of DC resistance of the pressure sensors; ESCORT ELC-132A meter was
used. The detailed description about the setup for measurement of the influence of pressure on
the resistance of the sensors is given in [38]. The experimental setup for the investigation of
pressure sensors is shown in Figure 3.11. The setup is comprised of (1) support, (2) weight
holder (3) weights and CNT-Cu
2
O pressure sensor (4). The pressure can be changed by changing
weights, in the conventional laboratory setup Flexor: Cantilever Flexure Frame. Samples
were tested four times and results were found repeatable with a variation of 4%. The sensors
resistance and applied pressure were measured at 25
C.
Figure 6.6 shows resistance-pressure relationship of one of the CNT-Cu
2
O pressure sensors at
increase and decrease of pressure. It can be seen that sensor has low hysteresis (2.7 % on
average) for resistance-pressure relationship and good repeatability. The DC resistance of the
pressure sensors was decreased by 3.3 times as the pressure was increased upto 37 kN/m
2
. For
the observed resistance-pressure relationship, the increase in the conductivity of sensor is
probably due to densification of the CNT-Cu
2
O powder under the effect of pressure and
squeezing of the particles.
For the simulation of resistance-pressure relationship, exponential function given in Eq. 6.3 can
be used [11]:

6.10
where A is constant with value 1, p is the pressure, K is the resistance-pressure factor, R
o
and R
are the resistances of the sensor at atmospheric pressure and under uniaxial pressure respectively.
We modified above relation as

6.11
Where p
m
is the maximum pressure and K
m
is the resistance-pressure factor at maximum
pressure. From the experimental data shown in Figure 6.6, the value of K
m
was as 0.0323 m
2
/kN.
The experimental and simulated (using Eq.6.11) results are plotted in Figure 6.7 and are
147

observed in good agreement. The results of simulation coincide with experimental results with an
average variation of 2 %.
The mechanism of conductivity in CNT-Cu
2
O sensors can be considered as transitions between
spatially separated sites, or particles that can be attributed to the Percolation Theory [12, 13].
According to percolation theory the effective conductivity () of the CNT samples, can be
calculated by Eq. 6.5: With an increase in pressure, the CNT-Cu
2
O press-tablet which is between
silver electrodes will be squeezed that may result in (i) decrease of characteristic length (L) and
(ii) reduction of path resistance (Z). Consequently, with increase in pressure the conductivity
increases and the resistance of the sensor decreases accordingly, as can be observed from
experimental results (Figure 6.6). On the other hand, the resistance of the samples also decreases
due the increase in cross-sectional area of the CNT-Cu
2
O press-tablet (Eq. 6.2) under the effect
of pressure (Figure 3.11). The experimental results reveal that the conductivity which is an
intrinsic property changed under the effect of pressure, while the change in geometrical
parameters of the samples causes to change in resistance. It can be assumed that the conductivity
is increased not only due to the densification of samples but also due to increase in the
conductivity of nanoparticles.
Depending on the orientation of the graphene lattice with respect to the axis of the tube, the
CNTs electronically may be semiconducting, small-gap semiconducting (SGS) and metallic [22].
Our preliminary investigations [39] showed that the conductivity of CNTs used in this work
increases with an increase in temperature i.e. it showed semiconductive properties. At the same
time Cu
2
O is semiconductor as well. The charge carriers density (n
i
) is described by the
following equation [40]:

6.12
where N
o
is effective density of states, E
g
is energy gap, k is Boltzmann coefficient and T is
absolute temperature. In this case, it can be assumed that the charge carriers density increases
due to decrease in energy gap (E
g
) in the particles under the effect of pressure and the
conductivity increases accordingly (Eq.6.12). In principle, the mobility of charge carriers might
be increased as well due to decrease in activation energy of mobility [40] and / or scattering of
148

Figure 6.5 Photographs of sample from various angles.

-5 0 5 10 15 20 25 30 35 40
1
1.5
2
2.5
3
3.5
Increasing Pressure
Decreasing Pressure
R
e
s
i
s
t
a
n
c
e

(
O
)
Pressure (KN/m
2
)

Figure 6.6 Resistance-pressure relationship for the CNT-Cu
2
O pressure sensor.

Ag-Paste
CNT-Cu2O
CNT-Cu2O
Ag-Paste
Ag-Paste
Ag-Paste
149

charge carriers at transport process from atomic vibrations. The contribution of the mobility in
the conductivity can be investigated in future by measurement of Hall Effect [41]. Investigation
of the CNT (25 wt.%)-Cu
2
O (75 wt.%) composite based pressure sensors showed that these
sensors have adequate sensitivity for practical application. Moreover, the initial resistance of
sensors may be increased by increasing the amount of Cu
2
O in the composite and in future it will
be the matter of investigation for our group. This improvement in initial resistance will be
helpful to decrease the effect of metallic wires resistances to the sensitivity of sensors [27].
As the experimental resistance-pressure relationship for the CNT-Cu
2
O sensors (Figure 6.6) are
non-linear, it can be linearized by nonlinear op-amps [17]. The fluctuation of temperature may
also affect the resistance of CNT-Cu
2
O based pressure sensors; to compensate the effect of
temperature for the practical utilization of these sensors a Wheatstone bridge may be used [27].
Figure 6.8 shows Wheatstone bridge circuit that can realize by four kinds of connection. In case
1 R
1
is active resistance sensor, R
2
, R
3
and R
4
are ordinary resistors. This circuit is used if
temperature compensation is not required. In case 2 and case 3 R
1
is active resistance sensor, R
2

or R
3
is dummy, R
3
or R
2
and R
4
are ordinary resistors. The active and dummy sensors should be
placed in the same thermal environment, but active would be kept under pressure and dummy
sensor in pressure-free region. Detail analysis of these four cases is described by Yong et al.
[27].
6.2.4 Conclusions
The CNT (25 wt.%) and Cu
2
O (75 wt.%) composite based pressure sensors were investigated. It
was found that the DC resistance of the pressure sensors decreased by 3.3 times as the pressure
was increased upto 37 kN/m
2
. The resistance-pressure relationships were simulated. The
mechanism of conductivity in CNT-Cu
2
O sensors was discussed: it can be considered as
transitions between spatially separated sites, or particles that can be attributed to the Percolation
Theory. As resistance-pressure relationship was non-linear, it was proposed to linearize the
relationship by nonlinear op-amps. To compensate the effect of temperature on the resistance of
CNT-Cu
2
O based pressure sensors, use of Wheatstone bridge based circuit is proposed, which
will make the sensors ready for practical applications.

150

0 10 20 30 40
0.4
0.6
0.8
1
Experimental
Simulated
R
e
l
a
t
i
v
e

R
e
s
i
s
t
a
n
c
e

(
R
/
R
O
)
Pressure (kN/m
2
)

Figure 6.7 Experimental (solid lines for the sensors shown in Figure 6.6) and simulated
(dashed line) relative resistance-pressure relationships for the CNT-Cu
2
O pressure sensor
(R
o
and R are resistances at atmospheric pressure and under uniaxial pressure,
respectively).

Figure 6.8 Schematic diagram of the pressure sensors arrangement in the Wheatstone
bridge (V
o
= output voltage).

V V
o

R
1 R
2
R
3
R
4

151

6.3 Carbon nanotubes based strain sensors
6.3.1 Introduction
It is known [42-44] that electromechanical transducers are mainly fabricated on the basis of
piezoresistive effect. These transducers are produced in large quantities than temperature,
electrical and magnetic transducers. Therefore, for the development of this field of technology, it
is reasonable to fabricate new piezoresistive materials. Berlin et al. [45] fabricated the pellets of
ion-radical salts of tetracyanoquinodimethane (TCNQ), which is an organic semiconductor. They
investigated the piezoresistive properties of a number of TCNQ salts such as Li(TCNQ),
Na(TCNQ), K(TCNQ) and Cs
2
(TCNQ). It was found that resistance-strain relationships were
linear, and the piezoresistive sensitivity was dependent on the pressure used for the fabrication of
pellets. On increasing the fabrication pressure of Cs
2
(TCNQ)
3
pellets, their sensitivity increased
up to 20-50. Krivonosov et al. [46] reported one of the first pressure transducers fabricated on the
basis of the TCNQ ion-radical salt strain sensors. The ion-radical salts of TCNQ with
diquinolinium and phenantrolinium were used as an active material for the fabrication of strain
sensors. The piezoresistive sensitivity of the sensors was in the range of 150-300. In Ref. [47] the
characteristics of the pressure sensors based on TCNQ salts with dimethyldipiridilium and
methyltiuronium are described. These sensors are strain sensitive and have a lower sensitivity to
temperature changes. A probe for the measurement of pressure in the stomach was designed on
the basis of strain sensor [48]. The sensor was fabricated by using the composite of ion-radical
salts of TCNQ and trimethyl tiuronium TCNQ. The composite was deposited on a polymer
membrane. This composite showed good stability, and its conductivity was equal to 5 S/m, while
the strain sensitivity and resistance coefficient of the sensor were equal to 10 and >0.1 % C
-1

respectively. The diameter of the sensor was equal to 4 mm, and its maximum sensitivity was
equal to 2 mm of water column.
CNTs have impressive properties, which results because of their unique structure [22]. The
electromechanical properties of the CNTs are very interesting and could lead to their use as
piezoresistors in mechanical transducers such as pressure sensors and accelerometers [26-30].
The piezoresistance of CNTs on deformable thin-film silicon nitride membranes was
investigated by Grow et al. [22], and it was found that the sensitivities of the semiconducting and
small-gap semiconducting (SGS) tubes are up to 400 and 850, respectively, where as the
152

maximum value of sensitivity of silicon is 200. Cao et al. [26] investigated the small band-gap
semiconducting (or quasimetallic) nanotubes and found that they exhibit piezoresistive
sensitivity from 600 to 1000 under axial strain that is much larger than in metallic nanotubes.
The fabrication of SWNT thin-film transistor on plastic substrates was described in ref. [30]. It is
reported that the resistance of 14 and 16 SWNTs layers thin films decreases by 38.2% and 47.1%
respectively with the increase in the bending of elastic substrates, which are higher by an order
of magnitude than in silicon. Regoliosi et al. [28] studied the piezoresistive effect in the pristine
CNT films, and the sensitivity was found 65 under 500 microstrains at room temperature. The
sensitivity increased with increase temperature. Mechanical deformation-conductivity
relationships of free standing membranes of SWCNTs have been investigated by Stampfer et al.
[29], and it was found that the piezoresistive sensitivity of nanotubes is 2.3-2.5 times larger than
that of the Si substrate. The nano electromechanical piezoresistance sensors based on SWNTs
were investigated by Yong et al. [27], and it was shown theoretically and experimentally that
ballistically conducting SWNTs exhibit nonlinear piezoresistive sensitivities of up to 1500
(applied strain was equal to 1%). Fabrication of the resistive strain sensors and investigations of
their properties would be useful from practical point of view and for the deepening of knowledge
about the physical properties of the CNT: it would be reasonable to investigate the resistance-
strain relationships.
6.3.2 Experimental
Commercially produced (Sun Nanotech Co Ltd., China) CNTs powder was used for making of
press-tablets of the CNT at a pressure of 200 and 300 MPa. The diameter of multiwalled carbon
nanotubes (MWNTs) varied between 10-30 nm. The nominal thickness of the CNTs pressed-
tablets was 1.0 0.1 mm. The inter-electrodes distance (length) and width of the surface-type
samples were in the range of 10-12 mm and 5-6 mm, respectively.
For the investigation of the tensity resistive effect and calibration of the sensors; a lever system
to create uniaxial tension, mechanisms for the creation of pressure with needles and devices with
bending elastic beams are used [1, 49, 50]. For the investigation of organic semiconductor thin
and fragile crystals or thin films, the use of bending elastic beams as substrates for the
153

deformation of the samples is the most acceptable. The devices with bending elastic beam and
with elastic membrane are described in ref. [51] and [52], respectively. The simplified schematic
diagram of the elastic beam of constant resistance to bending with and without load is shown in
Figure 3.12, and its concrete setup is given in ref. [53]. The longitudinal strain (or deformation)
can be determined using expression (Eq. 6.13) given in refs. [49, 53]:

6.13
where L is length (150 mm), b
o
is the width at foot of beam (30 mm), h is thickness of the beam
(2 mm), E is modulus of elasticity and P is load. Depending on the measurements of above
mentioned parameters, the accuracy of epsilon was found equal to 5%.
Figure 6.9 shows the resistive strain sensor installed on the elastic beam. The CNT pressed-
tablets were glued on the surface of the elastic beams that were fabricated from poly-methyl
methacrylate (PMMA). The average modulus of elasticity of the beam was 2.71 GPa.
Figure 6.10 shows the resistance-strain relationships under tension for sample 1 and 2 fabricated
at a pressure of 300 and 200 MPa, respectively. It can be seen that the sample prepared at higher
pressure shows better performance. Indeed, strain sensitivity (S) is given by Eq. 6.14 [1]:

6.14
where R and R are change in the sensors resistance and initial resistance (at =0), respectively.
The strain sensitivity is equal on average to 70 and 60 for sample 1 and 2, respectively. Initial
resistance was in the range of 6-9 for different samples. The thickness of the samples was
equal to 1 mm. The resistance of the samples increased under tension and decreased under
compression. During compression, the character of the resistance-strain relationships was
approximately the same.
The value of strain sensitivity is dependent on pressure that was used for the fabrication of the
samples: it was higher for the samples fabricated at higher pressures, and lower for the samples
fabricated at lower pressures.
154

Figure 6.9 CNT based resistive strain sensor installed on the elastic beam.

0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.00
0.04
0.08
0.12
0.16
0.20
Sample-1
Sample-2
A
R
/
R
c

x10
3

Figure 6.10 Resistance-strain relationships under tension for the sample 1 and 2 fabricated
at a pressure of 300 and 200 MPa, respectively.

CNTs
Silver paste
Beam
Glue
155

The change in samples resistance (R) can be explained; firstly, due to the change in geometrical
parameters like inter-electrode distance (L) and cross-sectional area (A), secondly, due to change
in the intrinsic parameters as resistivity ():

6.15
Usually, the change of the geometrical parameters only, as in metal, provides strain sensitivity on
average around 2 [1], whereas the change of the resistivity, for example, in Si strain sensors,
results in the sensitivity that is around 200 [1, 53]. Preliminary investigations of resistance-
temperature relationships of the CNT done by us [39] show that the resistance decreases with an
increase in temperature, i.e. this CNT powder has the semiconductive behavior. Therefore, we
can assume that as a result of tension; the charge concentration decreases due to increase in the
energy gap, and mobility decreases due to increase in potential barriers and, probably the
hopping length.
As the resistance of CNT based strain sensors can be changed due to change in temperature as
well. For practical utilization of these strain sensors, the temperature compensation circuits
should be used. The Wheatstone bridge circuit shown in Figure 6.8 can also be used for the
utilization of strain sensors [1]. This circuit can be realized four kinds of connection [1]. In case-
1 R
1
is an active resistance strain sensor, while R
2
, R
3
and R
4
are ordinary resistors. This circuit is
used if temperature compensation is not required. In case-2 and case-3 R
1
is active resistance
strain sensor, and R
2
or R
3
is a dummy, while R
3
or R
2
and R
4
are ordinary resistors. The active
and dummy sensors should be pasted by the same adhesive material on the beams and be placed
in the same thermal environment. However the active sensor should be under the strain and
dummy sensor in the stress-free region. In case-4 the circuit contains only active strain sensors:
R
1
and R
4
should be under tension, while R
2
and R
3
under compression. This circuit has a double
sensitivity with respect to circuits 1, 2 and 3, and provides the temperature compensation as well
[1]. Detail analysis of these four cases is given by Dally et al. [1].
6.3.4 Conclusions
The carbon nanotubes (CNTs) based strain sensors were fabricated by making the press-tablets
of CNT at a pressure of 200 and 300 MPa and investigated. The DC resistance of the strain
sensors increased under tension and decreased under compression. Strain sensitivity on average
156

was in the range of 50-80. The value of strain sensitivity depends on pressure that was used for
the fabrication of the samples: it was higher for the samples fabricated at higher pressures, and
lower for the samples fabricated at lower pressures. The physical mechanism involved in the
change of resistance under the effect of strain is also discussed. The circuits based on
Wheatstone bridge for practical utilization of the strain sensors and compensation of the effect of
temperature is presented.

157

6.4 Strain sensors based on carbon nanotubes-cuprous oxide composite
6.4.1 Introduction
The sensing mechanism of CNT composites is based on piezoresistivity which results in change
of electrical resistance in response to mechanical deformation [54]. Chung [55] defines
piezoresistivity for the carbon based materials and their composite as a description of
electromechanical behavior of the bulk.
CNTs impressive properties results due to its unique structure [22]. The electromechanical
properties of the CNT are interesting and could lead to their use as piezoresistors in mechanical
transducers such as pressure sensors, and accelerometers [26-30]. For single- and multi-walled
carbon nanotubes a significant and reversible correlation between the mechanical deformation
and electrical resistance was discovered by [56, 57]. This discovery revealed that carbon
nanotubes might be used as accurate nano-scale strain sensor [58]. Stampfer et al. [29]
investigated a nano electromechanical piezoresistance sensors based on SWNTs. They showed
experimentally and proved theoretically that ballistically conducting SWNTs have nonlinear
piezoresistive sensitivities of up to 1500 (for 1% applied strain).
Flexible strain sensitive composite materials were prepared by 5 to 50 wt.% MWCNTs, ethylene
propylene diene M-class rubber (EPDM) and organo-clay [54]. These composites showed non-
symmetric linear resistance change under deformation. Rein et al [58] studied the effect of
applied strain on the electrical resistance of carbon nanotube buckypaper (BP) films which were
encapsulated in various types of epoxy resins. The BP film preparation processes completed in
several steps which include dispersion of CNT in a solvent followed by consecutive filtration
steps and drying. It was reported that the resistivity of both SWCNTs and MWCNTs BPs were
double than their intrinsic resistivity. The strain sensitivity of the BP sensors was found 2.2 and
0.88 respectively for SWNTs and MWCNTs.
Cuprous oxide (Cu
2
O) is a photosensitive p-type semiconductor with a band gap of 2.17 eV [32,
34]. Cu
2
O is nontoxic and cheaper due to simple fabrication process and due to abundance of
copper in nature. Fabrication of nanodots and nanostructure thin films of Cu
2
O are reported in
refs. [35, 36].
158

It is well known that the fabrication of composite materials allows changing their properties
particularly specific resistances and samples resistances by changing the composition i.e. the
ratio of the constituents of the composite.
Fabrication of the resistive strain sensors and investigations of their properties would be useful
from practical point of view and for deepening of the knowledge about the physical properties of
the CNT and Cu
2
O: it would be reasonable to investigate the resistance-strain relationships.
6.4.2 Experimental
Commercially produced CNTs and Cu
2
O micropowder were purchased from Sun Nanotech Co
Ltd., China and WINLAB UK respectively. The diameter of multiwalled nanotubes (MWNTs)
varied between 10-30 nm. The sizes of Cu
2
O micro particles were in the range of 3-4 microns.
For making composite 25 wt.% CNT and 75 wt.% Cu
2
O powders were thoroughly blended by
using mortar and pestle. The composite was pressed in form of tablets at a pressure 353 MPa by
using hydraulic press. The nominal thickness of the press-tablets was 1.0 0.1 mm. The samples
were installed on the polymer elastic beam by glue as shown in Figure 6.11. The electric contacts
to the samples were made by the silver paste. The inter-electrode distance (length) and diameter
of the surface-type samples were in the range of 6-8 mm and 10 mm respectively.
A simplified schematic diagram of the elastic beam of constant bending stiffness with and
without load is shown in Figure 3.12. For the determination of longitudinal strain (or
deformation) Eq. 6.13 is used [49, 53]: A lever system to establish the uniaxial tension,
mechanisms for the creation of pressure through needles and devices with bending elastic beams
are used for the investigation of tensity resistive effect and the calibration of strain and pressure
sensors [1, 49, 50]. For the deformation of organic semiconductor thin and fragile crystals or thin
films, and to investigate the effect of strain, the bending elastic beams are most acceptable
substrates. Vaganov [51] described the devices with bending elastic beam.
6.4.3 Results and discussions
Figure 6.12 shows the resistance-strain relationships under tension and compression for one of
the samples fabricated at a pressure of 353 MPa. It can be seen that the DC resistance of the
159

strain sensor increases at tension and decreases at compression. The strain sensitivity (S) [1] is
calculated by the Eq.6.14: It is found, that the strain sensitivities are on average in the range of
44-46 at tension and 24-28 at compression. Initial resistances are in the range of 11-13 for
different samples. By considering the dependence of strain on geometrical parameters and
mechanical properties of elastic beam and applied load (as given in Eq.1), the accuracy of the
measurement of strain sensitivity is estimated as 5 %.
The change in samples resistance (R) can be explained, firstly, due to the change in geometrical
parameters like inter-electrode distance (L) and cross-sectional area (A), secondly, due to change
in the intrinsic parameters as resistivity () as given in Eq. 6.15. In the metals the change of
geometrical parameters provides strain sensitivity on average around 2, while it is around 200 for
silicon strain sensors [1, 53]. As both CNTs and Cu
2
O (2.17 eV gap in energy band diagram)
have semiconductive behavior. Therefore we can assume that as a result of tension; the charge
concentration decreases due to increase in energy gap, and mobility decreases due to increase in
potential barriers and, probably the hopping length.
The experimental results which are shown in Figure 6.12 are simulated by using the function
given in Eq. 6.16 is used [11].

6.16
The above function is modified for the simulation of tension and compression behavior of the
sensor as

6.17
where R is the change in samples resistance, R is the instantaneous resistance and are
instantaneous strain, while k is the resistance strain factor. From the experimental data shown in
Figure 6.12 the average values of k was determined as 44.8 and 25.5 respectively for tension and
compression, while c is the constant with a value of zero. The experimental and simulated results
of tension and compression (by using Eq. 6.17) are shown in
Figure 6.13. Simulated results of tension and compression behavior coincided well with
experimental results with an accuracy of 6.5% and 5% respectively.
160

As the resistance of CNT-Cu
2
O based strain sensors can be changed due to change in
temperature as well, for practical utilization of these strain sensors the temperature compensation
circuits should be used. The Wheatstone bridge can be used for the proper utilization of strain
sensors [1].
Investigation of the CNT (25 wt.%)-Cu
2
O (75 wt.%) composite based strain sensors shows that
these sensors have sufficient sensitivity for practical application. At the same time the initial
resistances of the sensors can be increased by decreasing the CNT content in the composite, and
accordingly increasing the Cu
2
O content, for example, up to the range of 5-15 wt.% CNT and
85-95 wt.% Cu
2
O. This increase in the initial resistance will allow to decrease the influence of
metallic wires resistances on the sensitivity of strain sensors [1]. It will be the matter of
investigation for our group in future.
6.4.4 Conclusions
The carbon nanotubes (CNT) and Cu
2
O composite based strain sensors are fabricated by making
the press-tablets of CNT-Cu
2
O at a pressure of 353 MPa. Investigations show that the DC
resistance of the strain sensors is increased under tension and decreased under compression. It is
found that resistance-strain relationships show quasi-linear behavior. Average sensitivity of the
sensor is 44 to 46. The physical mechanism involved in the change of resistance under the effect
of strain is also discussed. The results were simulated for the tension and compression behavior,
which are coincided with experimental results with an accuracy of 6.5% and 5%
respectively.

161

Figure 6.11 CNT-Cu
2
O composite resistive strain sensor installed on the elastic beam.

-3 -2 -1 0 1 2 3
-9
-6
-3
0
3
6
9
12
Compression
Tension
c X 10
3
(
A
R
/
R
)
1
0
2

Figure 6.12 Resistance-strain relationships under tension and compression for the sample
fabricated at 353 MPa.

CNT-Cu
2
O
Silver paste
Elastic Beam
Glue
162

-3 -2 -1 0 1 2 3
-9
-6
-3
0
3
6
9
12
c x10
3
Tens-Experimental
Tens-Simulated
Comp-Experimental
Comp-Simulated
Compression
Tension
(
A
R
/
R
)
1
0
2

Figure 6.13 Comparison of Experimental and Simulated results

163

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169

Chapter-7
Summary and Future Work
7 8
7.1 Summary
The important results obtained from the research work presented in this dissertation are the
following
1. The Au/PANI/Ag humidity sensors have been fabricated and investigated. It was found
that the sensing mechanism is based on the impedance and capacitance variations with
very small hysteresis. For change in Relative Humidity (RH) from 36 to 90%, the change
in sensors capacitance and impedance is 167 and 471 times, respectively. It is also
observed that annealing enhanced the sensitivity of the sensor by two times, which may
be attributed to the structural changes. Response (
res
) and recovery (
rec
) times are 8 and
27 seconds respectively. Results are examined by simulation and found in good
agreement with experimental data.
2. The Ag/OD-PANI/Ag sensors have been fabricated and investigated. The sensing
mechanism is based on the impedance and capacitance variations due to the
absorption/desorption of water vapors. With increase in relative humidity (RH) from 30%
to 90%, the impedance decreases by 5.2 x 10
4
and 8.8 x10
3
times for the frequency of
120Hz and 1 KHz respectively. This is because of the developed surface of the film due
to the presence of polyaniline particles i.e. area increases that in combination with orange
dye make the film very sensitive to humidity. Annealing results in increase in sensitivity
up-to 2.5 times, while the measured response and recovery times are 34 and 450 second
respectively. The simulation of impedance-humidity relationship is well matched.
3. The Cu/Cellulose-PEPC/Cu humidity sensors have been fabricated and investigated. It is
found that the capacitance of the sensor increases and the impedance decreases by 21 and
61 times respectively with change in Humidity from 45%-89% RH. The impedance-
humidity relationship demonstrated more uniform changes in this range of humidity as
compared to the capacitance and resistance-humidity relationships. Simulated results are
coincided with experimental results within the accuracy of 10%.
170

4. The temperature sensors have been designed and fabricated by the sequential deposition
of thin layers of glue and CNT nanopowder on a paper substrate. The results revealed that
the DC resistance of the sensors decreases in average by 1020% as the temperature
increases from 20 to 75 C. For the explanation of a conduction mechanism, the
percolation theory is used. The average temperature sensitivity of the samples was -
0.24% C
-1
which is higher than that of hydrogenated multiwalled carbon nanotubes
temperature sensor.
5. The surface-type Al/CNT/Al flexible temperature sensors have been designed, fabricated
and investigated. The resistance-temperature relationship has semiconductive behavior
and the average temperature sensitivity of the samples is -1.26%
C
-1
. The simulated
results of resistance-temperature relationship of the sensor are in coincided with
experimental data with an accuracy of 2 percent. The CNT system is assumed as a bulk
hetero system that results to a high sensitivity of the CNT layers to the effect of
temperature. The temperature sensors show good repeatability, and as the CNT layer is
encapsulated in flexible elastic casing the effect of humidity to the electric properties of
the sensors is neglected.
6. The V2O4-PEPC composite based temperature sensors have been designed and
fabricated by drop-casting the blend of V2O4-PEPC microcomposite into thin films
between the gap of preliminary deposited electrodes on a glass substrates. Investigations
show that with increase in temperature from 33 C to 90 C, the AC resistance of the
samples decreases by 10-12 times. The resistance temperature coefficients of the samples
were in the range of -2.3 -3.5 %
C
-1
at 33
C. The resistance-temperature relationships

have also been simulated and the results are matched with 8.5 percent accuracy.
7. The fabrication and investigation of temperature sensing properties of the organic-on-
inorganic Ag/p-CuPc/n-GaAs/Ag cells has been presented. The forward and reverse bias
resistances-temperature relationships for the Ag/p-CuPc/n-GaAs/Ag cells are investigated
in the temperature range of 33-75 C. It is found that the resistance temperature
coefficients (RTC) for the reverse and forward bias resistances are equal to -2.0% C
-1

and -1.5% C
-1
respectively.
8. The displacement sensors with polyaniline films as an active material have been designed
and fabricated. The thicknesses of the PANI films are in the range of 20-80 3 m. The
171

investigations show that, on average, the AC resistance of the sensor decreases by 2 times
and the capacitance accordingly increases by 1.6 times as the displacement changes in the
range of 0 mm-0.5 mm. The polyaniline is the only active material of the displacement
sensor. The resistance and capacitance of the PANI changes under the pressure of spring
and elastic rubber, and this pressure is created by the downward movement of the
micrometer.
9. The carbon nanotubes (CNTs) and Cu
2
O composite based pressure sensors have been
designed, fabricated. The press-tablets of CNT-Cu
2
O composite (25:75 by wt.) are
fabricated at a pressure of 353 MPa. The average diameter and the average thickness of
the press-tablets are equal to 10 mm and 4.0 mm respectively. In order to make low
resistance electric contact, the two sides of the press-tablet are covered by silver paste.
The DC resistance of the pressure sensor decreases 3.3 times as the pressure increases up
to 37kN/m
2
. Simulation result of resistance-pressure relationship is in good agreement
with experimental result with an average variation of 2 %.
10. The carbon nanotubes (CNT) based strain sensors have been designed and fabricated by
pressed CNTs tablets and elastic polymer beam. The tablets of multiwalled CNTs having
nominal thicknesses in the range of 0.5-2.0 mm were pressed at a pressure of 160, 200
and 300 MPa. The DC resistance of the sensors having the strain sensitivity in the range
of 50-80 in average increased under tension and decreased under compression. The value
of strain sensitivity depends on pressure that was used for the fabrication of the samples:
it was higher for the samples fabricated at higher pressures, and lower for the samples
fabricated at lower pressures.
11. The strain sensors based on carbon nanotubes-cuprous oxide (CNT-Cu
2
O) composite
have designed and fabricated. The press-tablets were fabricated from the blend of CNT
(25 wt %) and Cu
2
O (75 wt.%) at a pressure of 353 MPa. The nominal thickness of the
press-tablets was in the range of 0.5-1.5 mm; which were installed on the polymer elastic
beam by glue. The DC resistance of the strain sensors was increased under tension and
decreased under compression, while the average strain sensitivity was in the range of 44-
46 and 24-28 for tension and compression, respectively. The simulation of the
experimental results in tensile and compression mode is well matched with accuracy of
6.5 % and 5 % respectively.
172

7.2 Future Work
No doubt, there are several points in the dissertation that can be further investigated to explore
additional potentialities. Here few recommendations are presented for the future research work,
which are the following
1. In this work we used PANI as the only active material of the displacement sensors. The
resistance and capacitance of the PANI change under the pressure of the spring and
elastic rubber, and this pressure is created by the downward movement of the
micrometer. Probably, the key factors for the performance of the sensor are the
following: size of PANI clusters (clusters in microstructure), solution preparation
technique (solvent composition, time of stirring, temperature, etc.), film thickness, and
size and properties of the spring and elastic rubber. The detailed investigation of above
mentioned parameters will be helpful for optimizing the sensors response.
2. Investigation of the CNT (25 wt.%)-Cu
2
O (75 wt.%) composite based pressure sensors
showed that these sensors have adequate sensitivity for practical application. Moreover,
the initial resistance of sensors may be increased by increasing the amount of Cu
2
O in the
composite and in future it will be the matter of investigation for our group. This
improvement in initial resistance will be helpful to decrease the effect of metallic wires
resistances to the sensitivity of sensors.
3. In case of pressure sensors the conductivity of CNTs-Cu
2
O sensors increases. The
contribution of the mobility in the conductivity can be investigated in future by
measurement of Hall Effect.
4. Pellets of CNTs or its composites, which are used as active materials in pressure and
strain sensors, have been fabricated by cold compaction technique. The study of the
effect of sintering on the performance of sensor is very important.

173

Appendix
The data tables are given in the appendix and the abbreviation used in these tables are the
following
H: Humidity Z: Impedance
Z/Z: Relative impedance R: Resistance
R/R: Relative resistance C: Capacitance
C/C: Relative capacitance T: Temperature
D: Displacement P: Pressure
: Strain R
R
: Reverse bias
R
F
: Forward bias

Table-1: Experimental and simulated data of polyaniline based humidity sensor
H (%RH) Z (M) Z/Z Simulated Z/Z
36 667.664 1 1
40 656.461 0.98322 0.75534
45 404.083 0.60522 0.50462
50 278.414 0.41699 0.31985
55 122.571 0.18358 0.19339
60 65.786 0.09853 0.11207
65 27.972 0.04189 0.0625
70 14.397 0.02156 0.03367
75 7.805 0.01169 0.01757
80 3.903 0.00585 0.00891
85 2.255 0.00338 0.0044
90 1.418 0.00212 0.00212
174

Table-2: Experimental and simulated data of orange dye-polyaniline based humidity sensor
H (%RH) Z (K) Z/Z Simulated Z/Z
30 1034713.01 1 1
35 543180.98 0.52496 0.60242
40 383310.71 0.37045 0.32829
45 153768.46 0.14861 0.16365
50 91521.02 0.08845 0.07534
55 34275.66 0.03313 0.0323
60 11785.80 0.01139 0.01298
65 3649.99 0.00353 0.00493
70 1593.06 0.00154 0.00177
75 245.89 2.38E-04 6.08E-04
80 56.84 5.49E-05 2.00E-04
85 30.82 2.98E-05 6.31E-05
90 19.82 1.92E-05 1.92E-05

Table-3: Experimental and simulated data of cellulose-PEPC based humidity sensor
H (%RH) R (M) R/R Simulated R/R
45 435 1 1
50 422 0.97011 0.98504
55 411.849 0.94678 0.96617
60 391.844 0.90079 0.88816
65 243 0.55862 0.60115
70 126 0.28966 0.25314
75 20.801 0.04782 0.08779
80 3.08 0.00708 0.03184
83 0.4052 9.31E-04 0.01818
86 0.3493 8.03E-04 0.01077
89 0.2502 5.75E-04 0.0066

175

Table-4: Experimental and simulated data of carbon nanotubes based temperature sensor
T (C)
Heating Cooling
R/R
Simulated
(R/R)
R/R
Simulated
(R/R)
20 1 1 1 1
25 0.9955 0.99534 0.99101 0.98069
30 0.98921 0.98886 0.95504 0.96354
35 0.98112 0.98059 0.94065 0.94821
40 0.97212 0.97057 0.92896 0.93442
45 0.96133 0.95887 0.91817 0.92196
50 0.94604 0.94554 0.90827 0.91065
55 0.92626 0.93065 0.90018 0.90032
60 0.90558 0.9143 0.89119 0.89087
65 0.88849 0.89655 0.88219 0.88218
70 0.8741 0.87751 0.8741 0.87417
75 0.86241 0.85727 0.86241 0.86675

Table-5: Experimental and simulated data of carbon nanotubes based flexible temperature sensor
T (C) R/R Simulated (R/R)
20 1 1
25 0.94186 0.90805
30 0.85689 0.85149
35 0.80054 0.81326
40 0.78533 0.78572
45 0.78086 0.76495
50 0.74776 0.74873
55 0.74061 0.73571
60 0.72272 0.72504
65 0.71288 0.71613
70 0.70841 0.70857
176

Table-6: Experimental and simulated data of V
2
O
4
-PEPC composite based temperature sensor
Heating Cooling
T (C) R/R
Simulated
(R/R)
T (C) R/R
Simulated
(R/R)
34 1 1 34 1 1
35 0.9698 0.96754 35 0.88255 0.91393
38 0.87919 0.87634 36 0.82215 0.83946
40 0.83557 0.82037 38 0.74832 0.71779
42 0.79362 0.76797 40 0.63926 0.62344
44 0.76174 0.71892 42 0.58993 0.54881
46 0.71812 0.67301 44 0.54597 0.48875
48 0.68456 0.63002 45 0.52852 0.46301
50 0.63926 0.58978 47 0.48238 0.41842
52 0.6057 0.55211 50 0.46225 0.36495
54 0.56711 0.51685 52 0.38708 0.33609
56 0.53356 0.48384 54 0.36309 0.3114
58 0.49497 0.45294 56 0.32097 0.29011
60 0.45638 0.42401 58 0.29312 0.27159
62 0.40604 0.39693 60 0.26812 0.25538
64 0.35738 0.37158 63 0.23909 0.23457
66 0.33221 0.34784 65 0.22567 0.22262
68 0.29698 0.32563 70 0.19832 0.1979
70 0.27685 0.30483 75 0.17685 0.17871
75 0.23826 0.25846 80 0.15789 0.16345
80 0.19463 0.21915 85 0.1443 0.15107
85 0.15772 0.18582 90 0.13423 0.14086
90 0.13423 0.15755

177

Table-7: Experimental and simulated data of organic-inorganic Ag/CuPc/n-GaAs/Ag cell
T (C)
R
R
R
F

R/R
Simulated
(R/R)
R/R
Simulated
(R/R)
33 1 1 1 1
36 0.93447 0.92987 0.9434 0.93836
40 0.86165 0.84211 0.89623 0.8604
45 0.75243 0.74134 0.79245 0.7696
50 0.68447 0.65008 0.68868 0.68603
56 0.56311 0.5524 0.56604 0.59493
60 0.5 0.49402 0.4717 0.53954
65 0.41505 0.42814 0.32075 0.24406
70 0.35194 0.36959 0.18868 0.19113
75 0.2767 0.31779 0.12264 0.1487

Table-8: Experimental and simulated data of polyaniline film based displacement sensor
D (mm) R/R Simulated (R/R) C/C Simulated (C/C)
0 1 1 1 1
0.05 0.92 0.96 1.115 1.095
0.1 0.83 0.88 1.23 1.19
0.15 0.8 0.82 1.33 1.27
0.2 0.76 0.76 1.43 1.35
0.25 0.7 0.71 1.46 1.43
0.3 0.64 0.66 1.5 1.5
0.35 0.61 0.61 1.565 1.55
0.4 0.59 0.58 1.63 1.6
0.45 0.55 0.55 1.7 1.68
0.5 0.52 0.52 1.77 1.77

178

Table-9: Experimental and simulated data of CNTs-Cu
2
O composite based pressure sensor
P (KN/m
2
) R/R Simulated (R/R)
0 1 1
4.1 0.55556 0.60061
11.4 0.41667 0.42091
22.3 0.34722 0.34293
36.7 0.30556 0.30562

Table-10: Experimental and simulated data of CNTs-Cu
2
O composite based strain sensor
Tension Compression
R/R
Simulated
R/R
R/R
Simulated
R/R
0 0 0 0 0 0
0.42 1.98 1.88478 -0.42 -1 -1.06937
0.84 3.96 3.76956 -0.84 -2 -2.13874
1.16 5.445 5.205584 -1.16 -2.835 -2.9535
1.48 6.93 6.641607 -1.48 -3.67 -3.76826
1.855 8.365 8.324446 -1.855 -4.835 -4.72306
2.23 9.8 10.00729 -2.23 -6 -5.67785
2.585 10.8 11.60037 -2.585 -6.96 -6.58173
2.94 11.8 13.19346 -2.94 -7.92 -7.4856

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Fabrication and Investigation of Organic and Nano

Materials Based Sensors

C [16-18] where semiconductor to metal

) [18]. Another form of polarizability due to transfer of charge carriers

C. It can be seen in Figure 5.2 that there is hysteresis in heating-

C. The effects of temperature to the sensors resistances were

C the value of S is -1.26%

C [28-30] where semiconductor to metal transition takes place.

C, the AC resistance of the samples decreases by

C are -2.3 and -3.5 %/

C, respectively. The values

C. The resistance-temperature relationships

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