Full Thesis

CHARACTERIZATION OF ZINC DOPED COPPER
OXIDE THIN FILMS SYNTHESIZED BY SPRAY

PYROLYSIS TECHNIQUE
MEHERUN NESA
MASTER OF SCIENCE IN PHYSICS
DEPARTMENT OF PHYSICS
BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY
DHAKA-1000, BANGLADESH
JUNE, 2016
CHARACTERIZATION OF ZINC DOPED COPPER
OXIDE THIN FILMS SYNTHESIZED BY SPRAY
PYROLYSIS TECHNIQUE
A dissertation submitted to the Department of Physics of Bangladesh

University of Engineering and Technology in partial fulfillment of the
requirements for the degree of Master of Science (M.Sc.) in Physics
by
MEHERUN NESA
ROLL NO.: 1014142504F
SESSION: OCTOBER/2014
DEPARTMENT OF PHYSICS
BANGLADESH UNIVERSITY OF ENGINEERING AND TECHNOLOGY (BUET)
DHAKA-1000, BANGLADESH
JUNE, 2016
i
CANDIDATE’SDECLARATION
It is hereby declared that this thesis or any part of it has not been submitted elsewhere
for the award of any degree or diploma.
Signature of the candidate
---------------------------
Meherun Nesa
Roll No.: 1014142504F
Session: October/2014
ii
DEDICATED
To
MY BELOVED PARENTS
iii
CONTENTS
Page No.
CANDIDATE’S DECLARATION i
DEDICATION ii
ACKNOWLEDGEMENTS vi
ABSTRACT vii
LIST OF FIGURES viii
LIST OF TABLES xi
LIST OF ABBREVIATIONS xii
CHAPTER 1
GENERAL INTRODUCTION 1 – 20
1.1 Introduction 2
1.2 Applications of Thin Films 3
1.3 Oxide Semiconductors 4
1.3.1 Copper Oxide 5
1.3.2 Crystal Structure of CuO 5
1.4 Zinc 6
1.5 Review of Earlier Research Works on Copper Oxide Thin Films 6
1.6 Objectives of The Present Work 17
1.7 Outline of This Thesis 18
References 19
CHAPTER 2 21- 38
THIN FILM DEPOSITION PROCESSES AND IT’S FORMATION
2.1 Introduction 22
2.2 Thin Film Deposition Processes 22
2.2.1 Physical deposition processes 23
2.2.1.1 Physical vapor deposition 23
2.2.1.2 Thermal evaporation 24
2.2.1.3 Sputtering 24
2.2.1.4 Pulsed laser deposition 25
2.2.2 Chemical deposition processes 26
2.2.2.1 Chemical vapor deposition 26
2.2.2.2 Chemical bath deposition 27
2.2.2.3 Sol-gel technique 28
2.2.2.4 Spray pyrolysis technique 30
2.3 Film formation 31
2.3.1 Different stages of film formation 31
2.3.2 Condensation 32
2.3.3 Nucleation 33
2.3.4 Growth 34
2.3.4.1 The island stage 34
2.3.4.2 The coalescence stage 34
iv
2.3.4.3 The channel stage 35

2.3.4.4 The continuous film stage 35
References 37
CHAPTER 3
THIN FILM CHARACTERIZATION TECHNIQUES 39 – 62
3.1 Structural Characterization 40

3.1.1 X-ray diffraction 40
3.2 Surface Morphology 42
3.2.1 Electron microscope 42
3.2.2 Field emission scanning electron microscopy 43
3.3 Elemental Analysis 44
3.3.1 Energy dispersive X-ray spectroscopy 44
3.4 Optical Characterization 45
3.4.1 Beer-Lambert law 46
3.4.2 Electronic transition 48
3.4.3 Direct and indirect optical transition 51
3.4.4 Absorption coefficient 53
3.4.5 Refractive index and extinction coefficient 54
3.5 Electrical Characterization 56
3.5.1 Direct method 56
3.5.2 Two point probe method 57
3.5.3 Four point probe method 57
3.5.4 Factors affecting resistivity measurement 58
3.5.5 Activation energy 59
3.6 Thickness measurement of thin film 59
References 62
CHAPTER4
SYNTHESIS OF COPPER OXIDE AND ZINC DOPED COPPER 63 – 72
OXIDE THIN FILMS
4.1 Introduction 64
4.2 Precursor Material 64
4.3 Doping Material 65
4.4 Experimental Details 65
4.4.1 Fabrication of masks 65
4.4.2 Air compressor 65
4.4.3 The design of the reactor 66
4.4.4 Heater 66
4.4.5 The Fume chamber 66
4.4.6 Spray head/ nozzle 66
4.5 Choice of substrate 67
4.6 Substrate cleaning 67
4.7 Preparation of working solution 68
4.8 Thin film deposition parameters 68
4.8.1 Substrate temperature 68
v
4.8.2 Spray rate 69

4.8.3 Thickness control 69
4.8.4 Sample deposition 69
4.9 Synthesized Sample 71
References 72
CHAPTER 5
RESULTS AND DISCUSSION 73 -109
5.1 Introduction 74
5.2 Surface Morphology 74
5.3 Elemental Analysis 84
5.4 X-ray Diffraction Analysis 88
5.5 Optical Properties 92
5.5.1 Transmittance 92
5.5.2 Absorbance 93
5.5.3 Absorption coefficient 94
5.5.4 Optical band gap 95
5.5.5 Refractive index 97
5.5.6 Extinction coefficient 98
5.5.7 Optical conductivity 99
5.5.8 Dielectric constants 100
5.5.9 Dielectric loss 102
5.6 Electrical Properties 103
5.6.1 Current - Voltage Characteristics 103
5.6.2 Electrical conductivity and activation energy 105
References 107
CHAPTER 6
CONCLUSIONS AND SUGGESTIONS FOR FUTURE WORK 110-112
6.1 Conclusions 111

6.2 Suggestions for future work 112
vi
ACKNOWLEDGEMENTS
First of all, I am very much grateful to Almighty Allah who has given me the strength and
opportunity to complete this research work.
It is a tough job to acknowledge all the people who made this M.Sc. thesis possible with a few
words. However, I would try to do my best to extend my great appreciation to everyone who
helped me scientifically and emotionally throughout this study.
I express my heartfelt gratitude to my honourable supervisor Professor Dr. Md. Abu
HashanBhuiyan, Department of Physics and Dean, Faculty of Engineering, Bangladesh
University of Engineering and Technology, (BUET) for his valuable suggestions, inspirations,
scholastic guidance, constant support and close supervision throughout the entire course of
my research work. His guidance helped me all the time during research work and writing of
this thesis. I am very lucky to have the opportunity to perform my thesis work under his
supervision.
I am thankful to Professor Mrs. FahimaKhanam, Head, Department of Physics, BUET, for
providing me necessary facilities to carry out this research work.
I express my profound and sincere thanks to Professor Dr. JibanPodder for giving me
permission to use the experimental set up of SPT and also for his valuable instructions.
I am also thankful to all of my teachers: Prof. Dr. Md. FerozAlam Khan, Prof. Dr. A. K. M.
Akther Hossain, Prof. Dr. Md. Mostak Hossain, Prof. Dr. Afia Begum, Prof. Dr. Md. Forhad
Mina, Prof. Dr. Rafi Uddin, Dr. NasreenAkter, Dr. Mohammed Abdul Basith, Dr. Mohammad
Abu SayemKaral, Dr. Mohammad Jellur Rahman, Dr. Muhammad Rakibul Islam, Mr. A. T.
M. ShafiulAzam, Dr. Parvin Sultana and Mr. Md. Mehdi Masud for their inspiration and
constructive suggestions.
I express my very sincere gratitude to dear teacher Mrs. MehnazSharmin, Assistant Professor,
Department of Physics, BUET, for her instructive discussions, valuable suggestions, sharing
knowledge, confidence, love and concern which helped me surmount difficult times.
I am thankful to the authority of BUET for giving me necessary permission and providing
financial support for this research work.
I am also thankful to the authority of Ministry of Science and Technology for giving me
National Science and Technology fellowship 2015-16 in the sake of elevating my research
work.
I would like to thank Dr. Md. Abdul Gafur, Principal Scientific Officer, PP & PDC, BCSIR,
Dhaka for UV-VIS spectroscopic measurements and XRD analysis.
I wish to thank Prof. Dr. Md. Fakhrul Islam, Head, Department of Glass and Ceramic
engineering, BUET, Dhaka for allowing to perform FESEM and EDX study.
I would like to thank Mrs. AfrujaNasreen, Mrs. NasimaBanu, Dr. Sonjit Sen Roy, Mr.
AhaduzzamanDeeraz, Mrs. Kishwar-E Hasin, Ms. Rabeya Rahman, Mr. Tanveer Ahmmed
and Mr. Md. Abdul Momin and also all the other research workers of the Materials Science
Laboratory, for their all-time cooperation.
I wish to thank the entire non-teaching staff members, Department of Physics, BUET, for
their timely help during my research work.
Finally, I take this opportunity to express the profound gratitude and love from my deep heart
to all of my family members for their constant support and encouragement during not only my
research period but also my whole life. This accomplishment would not have been possible
without them.
Meherun Nesa
June, 2016.
vii
Abstract
Copper oxide (CuO) thin films are deposited onto glass substrates at various substrate
temperatures (Ts) 300, 350, 370 and 400 °C by spray pyrolysis technique (SPT).Zinc
doped copper oxide (CuO: Zn)thin films are deposited at the Ts of 350 °C with various
concentrations of Zn, varied from 1 to 6 at%. The effect ofTs and Zn doping on
structure, morphology, optical and electrical properties ofCuO andCuO: Zn thin films
has been investigated in the present work. In field emission scanning electron
microscope images, nanoparticles are observed around the nucleation center. Energy
dispersive X-ray analysis reveals thatCuO andCuO: Zn thin films are stoichiometric
and typically comprised of Cu, O and Zn. X-ray diffraction analysis ofCuO andCuO:
Zn thin films indicates that the thin films have monoclinic structure with the preferred
orientation along (1 1 1) plane. Maximum value of crystallite size is found about
28.24 nm for 5 at% CuO: Zn thin film. UV-Vis-NIR spectroscopic investigation
shows thatCuO andCuO: Zn thin films are highly transparent in NIR region. The
maximum transmittance is about 87% for CuO thin films deposited at Ts= 350 °C
with 5 at% of Zn concentration.The direct band gap ofCuOthin films are found to be
from 1.81 to 2.64 eV. The direct band gapCuO: Zn thin films are found to be from
2.50 to 2.88eV.Refractive index ofCuO varies between 1.33 and 2.60 and that of CuO:
Zn thin films varies between 1.19 and 2.62. Dielectric constant of CuO thin films
decreases with increasing Ts up to 350 °C and that of CuO: Zn decreases with Zn
concentration up to 5 at%. The highest optical conductivity is found for 5 at% CuO:
Zn thin filmprepared at Ts = 350 °C. The lowest electrical resistivity at room
temperature is about1.51x103 ohm-m for 5 at% CuO: Zn thin films prepared at Ts =
350 °C. For CuO thin films the activation energy (ΔE) decreases as the Ts
increases.The value of ΔE is varied from 0.12 to 0.26 eV for CuO thin films.In lower
temperature region, Zn concentration has no significant effect on ΔE for CuO: Zn thin
films. In higher temperature region, ΔE decreases at 2 at% Zn concentration and then
it is increased slowly with increasing Zn concentrations. The value of ΔE varies from
0.06 to 0.39 eV for CuO: Zn thin films in both lower and highertemperature regions.
viii
LIST OF FIGURES
Figure 1.1 Crystal structure of monoclinic CuO. 6

Figure 2.1 A diagram of physical vapor deposition process. 23
Figure 2.2 Schematic diagram of thermal evaporation system. 24
Figure 2.3 A diagram of a sputtering system. 25
Figure 2.4 A diagram of a pulsed laser deposition system. 26
Figure 2.5 Schematic diagram of a CVD process. 27
Figure 2.6 Diagram of CBD system. 28
Figure 2.7 Generalized scheme of sol-gel technique. 29
Figure 2.8 A flow chart for block diagram of different steps in SPT. 31
Figure 2.9 I) Layer-by-layer mode II) Island growth mode 32
III) Layer-plus-island growth.
Figure 2.10 Different stages of thin film growth. 36
Figure 3.1 Reflection of X-rays from two planes of atoms in a solid. 41
Figure 3.2 Schematic diagram of an electron microscope. 43
Figure 3.3 A scanning electron microscope set up. 44
Figure 3.4 Scheme of X-ray excitations in EDX analysis. 45
Figure 3.5 A UV-visible spectrophotometer. 46
Figure 3.6 Mechanism of absorption of light. 47
Figure 3.7 Vibrational and rotational energy levels. 49
Figure 3.8 Possible electronic transitions. 49
Figure 3.9 Schematic presentation of direct and indirect transitions 51
between valance and conduction bands.
Figure 3.10 Refraction of light of the interface between two refractive 54
indices media.
Figure 3.11 Electrical resistivity measurement by two point probe method. 57
Figure 3.12 Electrical resistivity measurement by four point probe method. 58
Figure 3.13 Interferometer arrangements for producing reflection Fizeau 61
fringes of equal thickness.
Figure 4.1 Mask for the sample. 65
Figure 4.2 A schematic diagram of the experimental set up of the spray 67
pyrolysis technique.
Figure 4.3 Experimental set up of spray pyrolysis unit at the Department 70
of Physics, BUET.
Figure 5.1 (a) FESEM image (×5 k) of CuO thin film deposited at the T s of 74
300 °C.
Figure 5.1(b) FESEM image (×5 k) of CuO thin film deposited at the Ts of 75
350 °C.
Figure 5.1(c) FESEM image (×5 k) of CuO thin film deposited at the T s of 75
400 °C.
Figure 5.2(a) FESEM image (×50 k) of CuO thin film deposited at the T s of 76
300 °C.
Figure 5.2(b) FESEM image (×50 k) of CuO thin film deposited at the T s of 76
350 °C.
Figure 5.2(c) FESEM image (×50 k) of CuO thin film deposited at the T s 77
of400 °C.
Figure 5.3(a) FESEM image (×5 k) of CuO: Zn thin film deposited at T s = 77
350 °C with 1at% Zn concentration.
ix
Figure 5.3(b) FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 78

350 °C with 2 at% Zn concentration.
Figure 5.3(c) FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 78
Figure 5.3(d) FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 79
Figure 5.3(e) FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 79
Figure 5.3(f) FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 80
Figure 5.4 (a) FESEM image (×50 k) of CuO: Zn thin film deposited at T s = 80
Figure 5.4 (b) FESEM image (×50 k) of CuO: Zn thin film deposited at T s = 81
Figure 5.4 (c) FESEM image (×50 k) of CuO: Zn thin film deposited at Ts = 81
Figure 5.4 (d) FESEM image (×50 k) of CuO: Zn thin film deposited at T s = 82
Figure 5.4 (e) FESEM image (×50 k) of CuO: Zn thin film deposited at T s = 82
Figure 5.4 (f) FESEM image (×50 k) of CuO: Zn thin film deposited at T s = 83
Figure 5.5 Variations of average particle size for (a)CuO thin films with 83
Ts and (b) CuO: Zn thin films deposited at 350 ºC with Zn
concentration.
Figure 5.6 EDX spectrum of CuO thin films. 84
Figure 5.7 EDX spectra of CuO: Zn thin films deposited at 350 °C T s 85
with Zn concentrations of (a) 1 and (b) 2 at%.
Figure 5.7 EDX spectra of CuO: Zn thin films deposited at 350 °C Ts 86
with Zn concentrations of (c) 3 and (d) 4at%.
Figure 5.7 EDX spectra of CuO: Zn thin films deposited at 350 °C T s 87
with Zn concentrations of (e) 5 and (f) 6 at%.
Figure 5.8 XRD patterns of CuO thin films deposited at different Ts. 89
Figure 5.9 XRD patterns of CuO: Zn thin films deposited at the T s = 350 90
°C.
Figure 5.10 Transmittance vs. wavelength graph of CuO thin films 92
deposited at different Ts.
Figure 5.11 Transmittance vs. wavelength graph of CuO and CuO: Zn thin 93
films deposited at Ts = 350 °C.
Figure 5.12 Variation of absorbance with wavelength for (a) CuO thin 94
films deposited at various Ts (b) 0 to 6 at% CuO: Zn thin films
deposited at Ts = 350 °C.
Figure 5.13 Variation of absorption coefficient (α) with photon energy for 95
(a) CuO thin films deposited at various T s (b) 0 to 6 at% CuO:
Zn thin films deposited at Ts = 350 °C.
Figure 5.14 (a) Plots of (αhν)2 vs. hν for CuO thin films synthesized at 95
different Ts.
x
Figure 5.14 (b) Plots of (αhν)2 vs. hν for CuO: Zn thin films synthesized at T s 96
= 350 °C with 0 to 6 at% Zn concentration.
Figure 5.15 Variation of direct band gap (a) for CuO with T s and (b) for 96
CuO: Zn with Zn concentration (Ts = 350 ºC).
Figure 5.16 Variation of refractive index (a) for CuO thin films with 98
wavelength deposited at various Ts and (b) for CuO: Zn thin films
with wavelength at various Zn concentrations (Ts = 350 ºC).
Figure 5.17 Variation of extinction coefficient with wavelength (a) for CuO 99
thin films synthesized at various Ts and (b) for CuO: Zn thin
films with various Zn concentrations (T s = 350 ºC).
Figure 5.18 Variation of optical conductivity with photon energy for (a) 100
CuO thin films deposited at different Ts and (b) CuO: Zn thin
films deposited at Ts = 350 °C with 0 to 6 at% Zn
concentration.
Figure 5.19 Variation of real part of dielectric constant with wavelength (a) 101
for CuO thin films deposited at various T s and (b) for CuO: Zn
thin films with various Zn concentrations (T s = 350 ºC).
Figure 5.20 Variation of imaginary part of dielectric constant with 101
wavelength (a) for CuO thin films deposited at various T s and
(b) for CuO: Zn thin films with various Zn concentrations (T s
= 350 ºC).
Figure 5.21 Variation of dielectric loss with wavelength for (a) CuO thin 102
films synthesized at various Ts and (b) CuO: Zn thin films with
0 to 6 at% Zn concentration synthesized at T s = 350 °C.
Figure 5.22 (a) Plots of I-V characteristics for synthesized CuO thin films. 103
Figure 5.22 (b) Plots of I-V characteristics for synthesized CuO: Zn thin films 104
(Ts = 350 ºC)
Figure 5.23 Variation of resistivity of (a) CuO thin films with different T s 104
and (b) CuO: Zn thin films with different Zn concentrations (Ts
= 350 °C).
Figure 5.24 Variation of electrical conductivity with 1000/T (a) for CuO 105
thin films synthesized at different Ts and (b) for CuO: Zn thin
films with different Zn concentrations (Ts = 350 °C).
Figure 5.25 Variation of activation energy of CuO thin films (a) at different 106
Ts and (b) with different Zn concentration at Ts = 350 °C.
xi
LIST OF TABLES
Table 1.1 Thin Film Application 3

Table 2.1 Thin film deposition processes 22
Table 4.1 Synthesized Sample 71
Table 5.1 Elemental analysis data for CuO and CuO: Zn thin films 88
Table 5.2 Lattice constants for CuO and CuO: Zn thin films 91
Table 5.3 Structural parameters of CuO and CuO: Zn thin films for (111) 91
plane
xii
LIST OF ABBREVIATIONS
λ Wavelength
μ Mobility of Charge Carrier
θ Bragg angle
D Crystallite size
ε Microstrain
δ Dislocation density
β Full width half maximum
A Absorbance
T Transmittance
α Absorption coefficient
n Refractive index
k Extinction coefficient
 Frequency
h Planck’s constant
εr Real part of dielectric constant
εi Imaginary part of dielectric constant
ρ Electrical resistivity
σ Electrical conductivity
kB Boltzmann constant
∆E Activation energy
d Thickness
1
CHAPTER 1
GENERAL INTRODUCTION
2
CHAPTER 1
GENERAL INTRODUCTION
1.1 Introduction
The research in the field of material science and engineering have leading contribution
in innovating the novel materials with extraordinary combination of physical, chemical,
mechanical etc. properties. Thin film technology is the basis of outstanding
development in solid state electronics in modern technology. Thin film studies have
exploited the unique characteristics in the terms of thickness, structure and geometry of
the thin films [1]. Thin film processing also saves energy consumption in production
and is considered as an environmentally benign material technology for the next century
[2]. When a thin layer of solid material is formed on a solid substrate and if the layer
thickness becomes comparable in magnitude with mean free path of the conduction
electrons of solid material then this is termed as “thin film”. Thin films are something
different from their bulk material in structural, electrical and optical properties. Thin
film may consist of pure material, a composite or a layered structure. Thin film may be
thermally stable or unstable. Thin films may also be conductive or non-conductive. To
study the semiconductive nature of the material, they are chosen in the form of thin film
which enables us to characterize them optically and electrically too. There are some
factors which affect the physical, electrical, optical and other properties of a film. The
factors are the rate of deposition, the substrate temperature, environmental conditions,
residual gas and pressure in the system, purity of the material to be deposited [3].
Oxide semiconductors thin films have been an interesting topic in the field of materials
research in recent years. Among various oxide semiconductors, Copper oxide (CuO) is
a popular one due to its interesting structural, chemical, electrical, and optical
properties. Research work based on synthesis and characterization of pure CuO and Zn,
In, and Ga doped CuO are being encouraged more and more in recent years [4–6].
CuO is a low energy band gap p-type semiconductor [7], and it is one of the hardest
materials due to high melting and boiling points. It is non-toxic in nature. It can be
easily produced by Copper (Cu) oxidation since the natural abundancy of Cu. It has
different type of applications in electronic and optoelectronic devices. Zn is a transition
metal. When Zn is doped in CuO, concentration of charge carriers, chemical and
3
physical properties of CuO may change. A homogeneous and stoichiometric thin film
is expected to be grown by Zn doping in CuO thin films.
CuO thin films can be deposited using various deposition techniques such as
electrodeposition [4], chemical bath deposition [8], DC magnetron sputtering [9],
vacuum evaporation [10], pulsed laser deposition (PLD) [11] and spray pyrolysis
technique (SPT) [12], etc. Among these various techniques SPT is a very simple and
cost-effective technique [3]. In SPT, high quality substrate or chemical is not required.
Dense, porous and multilayered films can be easily produced by SPT. That is why SPT
is chosen to deposit CuO and Zn doped CuO (CuO: Zn) thin films.
1.2 Applications of Thin Films

Some applications of thin films in the present time are listed in the Table 1.1.
Table 1.1: Thin Film Applications
Category Typical Applications
Protective coatings to reduce corrosion and erosion
Engineering/ Hard coatings for cutting tools
Processing Surface passivation
Protection against high temperature corrosion
Antireflection coatings (Multicoated optics)
Optics Highly reflecting coatings (Laser mirrors)
Integrated optics
Optoelectronics Photodetectors and image transmission
Optical memories and LCD / TFT
Electronics Passive thin film elements and active thin film elements
Integrated circuits and charge coupled device (CCD)
Magnetic materials Audio, video and computer memories
Magnetic read/write heads
Sensor applications Data acquisition in aggressive environments and media
Telemetry and biological sensors
Biomedicine Biocompatible implant coatings and neurological sensors
Alternative energies Solar collectors and solar cells
Thermal management of architectural glasses and foils
4
1.3 Oxide Semiconductors

The word semiconductor is composed of two words – Semi and Conductor. Semi means
not completely while conductor mean something which can conduct electricity. A
semiconductor is a material that has intermediate conductivity between a conductor and
an insulator. It means that it has unique physical properties somewhere in between a
conductor like aluminum and insulator like glass. Semiconductors are especially
important because varying conditions like temperature and impurity content can easily
alter their conductivity. Because of their application in the computer and photovoltaic
industries in devices such as transistors, lasers and solar cells—the search for new
semiconductor materials and the improvement of existing materials is an important
field of study in materials science. By alloying multiple compounds, some
semiconductor materials are tunable, e.g., band gap or lattice constant. Materials
transparent to the generated wavelength of light are advantageous, as this allows more
efficient extraction of photons from the bulk of the material. That is, in such transparent
materials, light production is not limited to just the surface. Refractive index is also
composition-dependent and influences the extraction efficiency of photons from the
material.
Transparent electronics is today one of the most advanced topics for a wide range of
device applications. The key components are wide band gap semiconductors, where
oxides of different origins play an important role, not only as passive component but
also as active component, similar to what is observed in conventional semiconductors
like silicon. Transparent electronics has gained special attention during the last few
years and is today established as one of the most promising technologies for leading the
next generation of flat panel display due to its excellent electronic performance.
Oxide semiconductors have drawn attention of materials scientists as the next-
generation semiconductor material. There are different types of oxide semiconductors
i.e. copper (I) oxide (Cu2O), copper (II) oxide (CuO), zinc oxide (ZnO), titanium
dioxide (TiO2), tin dioxide (SnO2), bismuth trioxide (Bi2O3), etc. They have higher
transparency, wider band gap, higher electrical conductivity, excellent thermal stability
and good electrical and optical properties. They have different types of applications in
the field of electronics and optoelectronics. Next generation research will continue
diligently to create a new field of electronics through the development of oxide
semiconductor device technology.
5
1.3.1 Copper Oxide
CuO is an oxide semiconductor material. It is an important transition metal oxide. It has

excellent thermal stability, good electrical and optical properties. Some basic properties
of CuO are mentioned below:
 Molecular Formula : CuO

 Chemical Name : Copper (II) oxide, Cupric oxide
 Molar Mass : 79.54 g/mol
 Color : Black or brownish- black
 Appearance : Crystalline solid
 Melting Point : 1326 °C
 Boiling Point : 2000 °C
 Solubility in Water : Insoluble
 Semiconductor type : p-type
 Crystal Structure : Monoclinic
It has also many practical applications such as electrochemical cells, gas sensors,
magnetic storage media, solar cells, field emitters, high-Tc superconductors, nanofluid
and catalysts etc. [13-16].
1.3.2 Crystal Structure of CuO
CuO is the last compound in the series of the simplest oxides of transition metals with
an unfilled 3d-shell. CuO has a base-centered monoclinic crystalline lattice with the
space group C62h [17]. In the crystal the Cu atom is coordinated by four Oxygen (O)
atoms in an approximately square planar configuration is shown in Figure 1.1. Its lattice
parameters are a = 4.68370 Å, b = 3.42260 Å and c = 5.12880 Å and β = 99.54º [7, 18].
6
Figure 1.1: Crystal structure of monoclinic CuO.
1.4 Zinc
Zinc, commercially also known as spelter, is a chemical element with symbol Zn and
atomic number 30. It is the first element of group 12 of the periodic table. Zn is the 24th
most abundant element in Earth's crust and has five stable isotopes. Some important
characteristics of Zn are noted below :
 Atomic Mass : 65.37 g/mol

 Density : 7.11 g/cm3 at 20 °C
 Phase : Solid
 Melting Point : 420 °C
 Boiling Point : 907 °C
 Ionic Radius : 0.074 nm (+2)
 Crystal Structure : Hexagonal close-packed
1.5 Review of Earlier Research Works on Copper Oxide Thin Films
Dhanasekaran et al. [4] studied the CuO thin films deposited by electrodeposition
method. The film thickness increased linearly with deposition time and tends to attain
saturation after 40 minute of deposition. X-ray diffraction (XRD) analysis revealed that
CuO thin films were polycrystalline in nature belong to the cubic phase with a preferred
orientation along (111) direction (Figure 1.2). The pyramid shaped background with
amorphous nature grains covered the entire surface of the films and were estimated in
7
the range between 200 to 250 nm and also no well defined grain boundaries were
observed but uneven shaped grains were observed in Scanning Electron Microscopy
(SEM) images (Figure 1.3). Energy Dispersive Anaysis of X-ray (EDAX) report
showed that the near stoichiometric composition for films deposited at various bath
temperatures. Atomic Force Microscopy (AFM) of film deposited at low bath
temperature showd some valleys and hillocks in different shapes. When the bath
temperature increased valleys were found to decrease due to the formation of regular
shaped grains.
Figure 1.2: X-ray diffraction Figure 1.3: SEM micrographs of

patterns of electrodeposited CuO electrodeposited CuO thin films
thin films deposited at bath deposited at bath temperatures
temperatures (a) 45, (b) 60, (c) (a) 30, (b) 45, (c) 60, (d) 75 and
75 and (d) 90 °C [4]. (e) 90 °C [4].
Wanjala et al. [9] investigated the CuO thin films prepared by DC magnetron sputtering
technique at 350 W and 400 W deposition powers. Reflectance of less than 40% in the
wavelength range of 250-2500 nm was reported in all deposited films (Figure 1.4).
Band gaps obtained by simulation were 1.25 and 2.06 eV. These values of the band gap
show that the obtained CuO films are good absorbers. They also observed that the
deposited thin films exhibited high absorbance of above 80% in the Ultra-Violet (UV)
region of the electromagnetic spectrum which was decreased below 30% towards the
Near Infrared Region (NIR). Electrical resisitivity of CuO was reported to decrease
steadily to a value of 37.83 for the film prepare at 400 W and was in the range 37 – 119
Ω-cm (Figure 1.5).
8
Figure 1.4: Spectral plot of reflectance Figure 1.5: Electrical resistivity (ρ)
(%) against wavelength (nm) of CuO against power of CuO films [9].
thin films deposited using different
deposition powers [9].
Zeggar et al. [19] investigated CuO thin films deposited by spray pyrolysis technique
(SPT) from 0.05 M copper chloride (CuCl2.2H2O) aqueous solution. CuO thin films
were synthesized at the substrate temperature (Ts) 280, 300, 350 and 400 °C. From UV-
vis spectroscopy it was found that CuO thin films were transparent in the wavelength
range of 800-1100 nm (Figure 1.6). Refractive index of CuO thin films increased from
1.53 to 1.65 due to the increase of film thickness. Optical band gap (Figure 1.7) and
electrical conductivity increased with the increase of Ts.
Figure 1.6: UV-Visible transmittance spectrum of CuO thin films deposited at

different substrate temperatures [19].
9
Figure 1.7: Variation of optical band gap of CuO films [19].

with substrate temperature
Bari et al. [20] studied the spray pyrolized nanostructured CuO thin films for H2S gas
sensor. CuO thin films (CTFs) were deposited onto the glass substrates heated at 250 ±
5 °C by varying the deposition times of 10, 20, 30 and 40 min of 0.05M solution. XRD
analysis revealed that the CuO thin films were polycrystalline in nature (Figure 1.8)
and the average crystallite size was 29 nm. SEM images reported that the average grain
size was 30 nm and the particles were roughly spherical in shape (Figure 1.9).
Tunneling Electron Microscopy (TEM) images revealed that the grains were
nanostructured in nature and nearly spherical in shape, with smaller than 9 nm in size.
As reported, atomic percentage of Cu and O was 42.60 at% and 57.40 at% respectively,
showed a nonstoichimetric nature.
Figure 1.8: X-ray diffractogram of the most sensitive nanostructured CuO thin
film (sample S3) [20].
10
Figure 1.9: SEM images of the most sensitive nanostructured CuO thin film
(sample S3) [20].
Singh and Bedi [21] studied the correlation among the structural, electrical gas response
properties of aerosol spray deposited self assembled nanocrystalline CuO thin films
onto glass substrate at various substrate temperature (Ts) from 300 to 400 ºC using 0.2M
aqueous solution of trihydrate cupric nitrate (Cu(NO3).3H2O). TGA and DTA curves
expressed that the thermal decomposition of the dried gel took place in a single step
and which resulted in the evolution of gases in air atmosphere. XRD pattern revealed
that the film was polycrystalline in nature with preferred orientation (002) plane (Figure
1.10). The average crystallite size was lowest for the sample deposited at T s of 300 ºC
and its value increased to 38 nm with the rise in Ts to 350 °C. The SEM micrographs
reported that the films were smooth and crack free with nano-sized particle
agglomerates. The films activation energy were in the range 0.311 – 0.293 eV. Electrical
measurement expressed that the grain size was increased, the activation energy and
strain in films decreased due to the increase of Ts.
11
Figure 1.10: XRD pattern of the CuO

Figure 1.11: The variation of
films (a) C1, (b) C2 and (c) C3,
conductivity with temperature
respectively, for CuO film deposited
for CuO films (a) C2, (b) C2
at substrate temperature of 300, 350
and (c) C3 [21].
and 400 ºC [21].
Chaudhary et al. [22] studied the photoelctrochemical properties of CuO thin films
prepared by SPT from 0.1M Cu(NO3)2.2.5H2O precursor solution. XRD patterns
revealed that the films were polycrystalline and the average grain size was found in the
range of 60 – 90 nm (Figure 1.12). SEM confirmed that the size of the grains or particles
formed lying in the range of < 100 nm (Figure 1.13). The optical band gap was repoted
1.4 eV. The rise in photocurrent density with increased in spray time from 50 to 150 s
had been attributed to the increase in film thickness which was probably allowing the
film to absorb photons more efficiently. As mentioned, the film deposited at 350 °C
exhibited better photosense than deposited at 300 and 400 °C.
Figure 1.12: XRD patterns of CuO thin films deposited on conducting

glass at various deposition temperatures (Spray time 100 s) [22].
12
Figure 1.13: SEM photographs of CuO thin films at (a) 300, (b) 350 and (c) 400
ºC deposition temperatures (Spray time 100 s) [22].
Roy et al. [12] investigated the optical and electrical properties of CuO thin films
synthesized at different Ts from 250 to 450 °C by SPT. XRD analysis reveals that the
crystallininity of the thin films is improved at higher Ts and (111) is the prominent peak.
From trnsmission spectra it is seen that the thin films are highly transparent at visible
and near infrared regions (Figure 1.14). The value of highest transmittance is about 80%
for the thin film grown at Ts = 350 °C. The resistivity of the prepared CuO thin films
decreases with the increase of Ts due to the increase in free path of conduction (Figure
1.15).
13
Figure 1.14: Optical transmittance vs. Figure 1.15: Variation of resistivity

wavelength of CuO thin films at at room temperature for various Ts
various Ts [12]. [12].
Chafi et al. [23] investigaed the undoped CuO deposited by SPT with 0.05M, 0.058M
and 0.1M molar concentration at 350 °C Ts. In XRD analysis, two highly diffraction
peaks observed with preferred orientation respectively along the (1̅11) and (111) axis.
It also showed that all the samples were monoclinic in structure (Figure 1.16). AFM
analysis revealed that the formation of micro granular particles with pyramidal shapes
and irregular grain sizes. Optical transmission spectra showed that the transmittance
was decreased with increase in the molar concentration and it was around 60 to 70% in
the visible zone. This result was attributed to the increase in film thickness. The lowest
band gap value was 1.29 eV for CuO thin films of 0.1M concentration (Fgure 1.17). A
molar concentration of 0.1M was found to be optimum for preparing CuO thin films in
SPT.
Figure 1.16: XRD diffractograms of Undoped CuO sprayed thin films

deposited at 350 °C [23].
14
Figure 1.17: Band gap of undoped sprayed CuO at different concentrations

[23].
Kose et al. [5] studied some physical properties of Indium (In) doped copper oxide
(CuO: In) films produced by spray purolysis. They maintained the ultrasonic oscillator
frequency at 100 kHz and the droplet size at 20 µm. Cu(CH3COO)2.2H2O and
InCl3.2H2O liquid solution (0.05M) were used as starting spraying solution. The films
were produced at a Ts of 250 ± 5 °C. XRD patterns revealed that the low intensity and
high FWHM values of B13 (3 at% CuO: In) film, which had deformation in structure.
The films gone away from amorphous structure by the addition of In element at 1% and
2% (Figure 1.18). All films had the direct optical band gap. The band gap values of
CuO phase increased while those of Cu2O phase decreased with In doping (Figure
1.19).
Figure 1.18: XRD patterns of In Figure 1.19: (hn)2 vs h variations

doped copper oxide films [5]. of In doped copper oxide films [5].
15
Vidhya et al. [6] studied the influence of doping concentration on the properties of Ga
doped CuO thin films by SPT. CuO thin films prepared from 0.1 M aqueous solution
of Copper (II) chloride dihydrate (CuCl2.2H2O) and gallium (III) nitrate hydrate
(Ga(NO3)3. H2O) at 450 °C substrate temperature. XRD pattern showed that the
crystallinity of the film increasees as the Ga dopant increases (Figure 1.20). SEM study
exposed the grains are uniformly distributed over the entire scanned surface without
any patches for concentrated 2 ml Ga doping. The surface was reported to be smooth
without any undulation. The direct band gap was 2.24 to 2.79 eV for all synthesized
films (Figure 1.21).
Figure 1.20: XRD patterns for (a) pure Figure 1.21: Band gap plots of (a)
CuO and (b-e)Ga doped CuO [6]. pure CuO and (b-e) Ga doped CuO
[6].
Faiz et al. [11] prepared CuO: Zn thin films with 0, 1, 3, 4 and 5 atomic wt% Zn by
PLD technique. All the deposited fims annealed at 800 °C for 4 hours. The thickness of
the films was reported around 250 ± 5 nm. XRD patterns revealed that all the films
have poycrystalline structure with (002) and (200) orientations of monoclinic CuO
phase only. Due to high annealing temperature, the grains acquire enough energy to
orient in proper equilibrium sites resulting in an increase in the crystallinity of the thin
films (Figure 1.22). The 1% CuO: Zn thin films were found to minimum compressive
stress as compared to all other thin films. On further doping by Zn, a reduction in
compressive stress was observed by them. SEM images exposed that the 5% CuO: Zn
thin films have best smoothness among all the doped thin films (Figure 1.23). From
optical absorption data it was reported that the optical band gap (Eg) energy increases
from 0 to 3 atomic wt% and then Eg decreases for higher doping concentrations
16
Figure 1.22: XRD patterns of pure Figure 1.23: SEM micrographs of pure
and Zn doped CuO thin films. Inset and doped CuO thin films.(a) pure CuO,
shows variation of macrostrain with (b) 1 % Zn–CuO,(c) 3 % Zn–CuO, (d)
increasing zinc concentration [11]. 4 % Zn–CuO and (e) 5 % Zn–CuO at
×5 K [11].
Engin et al. [24] studied the Zn incorporated copper oxide (CuO: Zn) film deposited by
ultrasonic spray pyrolysis technique at a substrate temperature of 250 ± 5 °C. The
deposited films behaved as transparent materials at about 800 – 1100 nm wavelength
range. The band gap was 1.92 – 1.95 eV (Figure 1.24). Zn incorporation had no strong
effect on the band gaps of the undoped films due to low Zn incorporation. XRD pattern
showed that the crystallinity improved with Zn incorporation at 1% and 3% with
preferred orientation (110) plane (Figure 1.25). The half-width in radius and dislocation
density dereased, while grain size increased with Zn incorporation. EDS results of CuO:
Zn films reported that the expected elements exist in the solid elements and Zn was
really doped in the solid films. The conductivity of CuO: Zn films was reported almost
same as that the CuO films.
17
Figure 1.24: Plots of (h)2 versus Figure 1.25: Plots of (ahm)2 versus
h of CuO: Zn films [24]. h of CuO: Zn films [24].
1.6 Objectives of The Present Work
The aims of the peresent work are to prepare CuO and CuO: Zn thin films onto glass
substrate by locally fabricated Spray Pyrolysis set up and to investigate the structural,
electrical and optical properties of the deposited thin films. In CuO thin films effect of
Ts is to be investigated. And also in CuO: Zn thin films the effect of Zn concentration
at optimum Ts of CuO thin films is to be studied. Based on these research challenges,
the objectives of this work are as follows:
(1) To prepare CuO thin films at different Ts.

(2) To synthesize CuO: Zn thin fims with different Zn concentrations.
(3) To study the surface morphology of the deposited thin films by field emission
scanning electron microscopy (FESEM).
(4) To estimate the elemental composition of the prepared thin films by the energy
dispersive X-ray (EDX) analysis.
(5) To analyze the structure of the deposited films by XRD analysis.
(6) To determine transmittance, absorbance, optical absorption coefficient, optical
band gap, refractive index, dielectric constants, etc. from UV-Vis-NIR
spectroscopic measurements.
(7) To measure DC electrical conductivity by linear four point probe method.
18
(8) To calculate activation energies of carriers for electrical conduction of the

deposited thin films.
These findings will add new knowledge in spray pyrolyzed CuO and CuO: Zn thin
films, which may indicate some suitable applications of these materials in the elctrical
and optoelectrical devices.
1.7 Outline of This Thesis
Chapter 1 represents the General Introduction of this thesis.
Chapter 2 focuses the Thin Film Deposition Processes and It’s Formation.
Chapter 3 gives the Thin Film Characterization Techniques.
Chapter 4 discusses about the Synthesis of Copper Oxide and Zinc Doped Copper
Oxide Thin Films.
Chapter 5 contains the Results and Discussion of this research work.
Chapter 6 includes the Conclusions and Suggestions For Future Work.

19
References
[1]. West, A. R., “Solid State Chemistry”, John Willey and Sons, Singapore, 2003.
[2]. Wasa, K., Kitabatake, M. and Adachi, H., “Thin film materials technology
sputtering of compound materials”, William Andrew Inc. New York, 2004.
[3]. Perednis, D. and Gauckler, L. J., “Thin film deposition using spray pyrolysis”, J.
Electroceram., Vol. 14, pp. 103-111, 2005.
[4]. Dhanasekaran, V.,Mahal ingam, T., Chandramohan, R., Rhee J. K., Chu, J.P.,
“Electrochemical deposition and characterization of cupric oxide thin films”, Thin
Solid Films, Vol. 520, pp. 6608–6613, 2012.
[5]. Kose,S., Ketenci, E., Bilgin, V., Atay, F.,and Akyuz, I., “Some physical
properties of In doped copper oxide films produced by ultrasonic spray pyrolysis”,
Curr. Appl. Phys., Vol. 12, pp. 890-895, 2012.
[6]. Vidhya, S. N., Balasundarm, O. N. and Chandramohan, M., “Influence of doping
concentration on the properties of Ga doped CuO thin films by the spray pyrolysis
technique”, J. Optoelect. Adv. Materials, Vol. 17(7-8), pp. 963-967, 2015.
[7]. Marabelli, F., Parravicini, G. B. and Salghetti-Droili, F., “Optical gap of CuO”,
Phys. Rev. B, Vol. 52(3), pp. 1433-1436, 1995.
[8]. Nasser, Saadaldin, Alsolum, M. N and Hussain, N, “Preparing of copper oxides
thin films by chemical bath depositin (CBD) for using in environmental
application”, Energ. Procedia, Vol. 74, pp. 1459-1465, 2015.
[9]. Wanjala, K. S., Njoroge, W. K., Makori, N. E. and Ngaruiya, J. M., “Optical and
electrical characterization of CuO thin films as absorber material for solar cell
applications”, American J. Condensed Matter Phys., Vol. 6(1), pp. 1-6, 2016.
[10]. Papadimitropoulus, G., Vourdas, N., Vamvakas, V. E. and Davazoglu, D.,
“Deposition and characterization of copper oxide thin films”, J. Phys. Conf. Ser.,
Vol. 10, pp. 182 –185, 2005.
[11]. Faiz, H., Siraj, K., Rafique, M. S., Naseem, S. and Anwar, A. W., “Effect of zinc
induced compressive stresses on different properties of copper oxide thin films”,
Ind. J. Phys., Vol. 89(4), 353–360, 2015.
[12]. Roy, S. S., Bhuiyan, A. H. and Podder, J., “Optical and electrical properties of
copper oxide thin films synthesized by spray pyrolysis technique”, Sensor.
Transduc., Vol. 191, 21-27, 2015.
20
[13]. Hu, Y., Zhou, X., Cao, Q. and Huang., “Sensing properties of CuO-ZnO
heterojunction gas sensors”, Mater. Sci. Eng. B., Vol. 99, pp. 41-43, 2003.
[14]. Ishizuka, S., Maruyama, T. and Akimoto, K., “Thin film deposition Cu2O by
reactive radio-frequency magnetron sputtering”, Jpn. J. Appl. Phys., Vol. 39, pp.
786-788, 2000.
[15]. Cao, H. and Suib, S., L., “Highly efficient heterogeneous photooxidation of 2-
propanol to aceton with amorphous manganese oxide catalysts”, J. Am. Chem.
Soc., Vol. 116, pp. 5334-5342, 1994.
[16]. Derin, H. and Kantarli, K., “Optical characterization of thin thermal oxide films
on copper by ellipsometry”, Appl. Phys. A, Vol. 75, pp. 391-395, 2002.
[17]. Moskvin, A. S., Loshkareva, N. N., Sukhorukov, Yu. P., Sidorov, M. A.,
“Characteristic features of the electronic structure of copper oxide (CuO):
Initiation of the polar configuration phase and middle-IR optical absorption”, Zh.
Eksp. Teor. Fiz., Vol. 105, pp. 967-973, 1994.
[18]. Ghijsen, J., Tjeng, L. H., Elp, J. V., Eskes, H., Westerink, J., Sawatzky, G. A.,
Czyzyk, M. T., “Electronic structure of Cu2O and CuO”, Phys. Rev. B, Vol.
38(16), pp. 11322-11330, 1988.
[19]. Zeggar, M. L., Aida, M. S. and Attaf, N., “Copper oxide thin films deposition by
spray pyrolysis”, J. New Tech. Mater., Vol. 4(1), 86-88, 2014.
[20]. Bari, R., H, Patil, S., B and Bari, A., R, “Spray-pyrolyzd nanostructured CuO thin
films for H2S gas sensor”, Int. Nano Lett., Vol. 3(3), pp. 6 (1-5), 2013.
[21]. Singh, I. and Bedi, R. K., “Studies and correlation among the structural, electrical
and gas response properties of aerosol spray deposited self assembled
nanocrystalline CuO”, Appl. Surf. Sci., Vol. 257, 7592-7599, 2011.
[22]. Chaudhary, Y., S., Agrawal, A., Shrivastav, R., Satsangi, V., R., and Dass, S., “A
study on the photochemical properties of copper oxide thin films”, Int. J. Hyd.
Energ., Vol. 29, 131-134, 2004.
[23]. Chafi, F. Z., Hadri, A., Nassiri, C., Fares, B., Laanab. L., Hassanain, N. and
Mzerd, A., “Undoped CuO deposited by spray pyrolysis technique”, J. Mater.
Environ. Sci., Vol. 7(1), 170-175, 2016.
[24]. Engin, M., Atay, F., Kose, S., Bilgin, V and Akyuz, I., “Growth and
characterization of Zn-incorporated Copper oxide films”, J. Electronic Maters,
Vol. 38(6), pp. 787-796, 2009.
21
CHAPTER 2

22
CHAPTER 2
2.1 Introduction
Today thin films are ubiquitous and they are found more or less everywhere. Thin films
are applied to modify the surface of a material or to build functional devices. The
properties of a film and thereby its area of application is mainly determined by the
choice of material. But the structure of the film on a nanometer or micrometer scale can
also affect the film properties [1]. Thin film deposition process of insulating, conducting
and dielectric materials plays an important role in manufacturing, production, research
and applications.
2.2 Thin Film Deposition Processes
The act of applying a thin film to a surface is known as thin film deposition. The
methods employed for thin film deposition can be divided into mainly two broad
categories based on the nature of the deposition process such as physical and chemical
[2]. The different types of deposition techniques are given in Table 2.1.
Table: 2.1: Thin film deposition processes
Physical deposition processes Chemical deposition processes

Evaporation Sputtering Other deposition Gas phase Liquid phase
processes
 Thermal  DC  Pulsed laser  Chemical  Spray
 Electron  RF  Cathodic arc vapor pyrolysis
beam  AC  Plasma  Thermal  Sol-gel
 Laser  Ion  Molecular oxidation  Dip-coating
 Flash beam beam epitaxy  Chemical  Spin-coating
beam epitaxy  Electroplating
 Atomic layer  Anodization
epitaxy  Chemical
bath
23
Among various types of thin film deposition techniques some of the commonly used
techniques are described briefly in the following subsections.
2.2.1 Physical deposition processes
Physical deposition processes conduct mechanical, electromechanical or

thermodynamic means to produce a thin film of solid.
The material to be deposited is placed in an energetic, entropic environment, so that

particles of material escape its surface. Facing this source is a cooler surface which
draws energy from these particles as they arrive, allowing them to form a solid layer.
The whole system is kept in a vacuum deposition chamber, to allow the particles to
travel as freely as possible. Since particles tend to follow a straight path, films deposited
by physical means are commonly directional, rather than conformal.
2.2.1.1 Physical vapor deposition
Physical Vapor Deposition (PVD) is a collective set of processes used to deposit thin
layers of material, typically in the range of few nanometers to several micrometers.
Figure 2.1 shows the diagram of PVD process.
Figure 2.1: A diagram of physical vapor deposition process.
PVD process proceeds along the following sequence of steps:

a) The solid material to be deposited is physically converted to vapor phase;
24
b) The vapor phase is transported across a region of reduced pressure from the
source to the substrate;
c) The vapor condenses on the substrate to form the thin film.
2.2.1.2 Thermal evaporation
Evaporation or sublimation techniques are widely used for the preparation of thin
layers. A very large number of materials can be evaporated and, if the evaporation is
undertaken in vacuum system, the evaporation temperature will be very considerably
reduced; the amount of impurities in the growing layer will be minimized.
Although one of the oldest methods used for depositing thin films, thermal evaporation
or vacuum evaporation, is still widely used in the laboratory and in industry for
depositing metal and metal alloys [3]. Figure 2.2 shows the diagram of thermal
evaporation system. The material to be deposited is loaded into a heated container called
a crucible. The crucible is resistively heated by applying a large current. As the material
in the crucible becomes hot it gives of a vapor which atoms travel in straight lines until
they strike a surface where they accumulate as a film.
Figure 2.2: Schematic diagram of thermal evaporation system.
2.2.1.3 Sputtering
If a surface of target material is bombarded with energetic particles, it is possible to

cause ejection of the surface atom: this is the process known as sputtering. The ejected
atoms can be condensed on to a substrate to form a thin film. This method has various
advantages over normal evaporation techniques in which no container contamination
25
will occur. It is also possible to deposit alloy films which retain the composition of the
parent target material. Figure 2.3 shows the diagram of sputtering system. DC
sputtering, radio frequency (RF) sputtering and magnetron sputtering methods are the
oldest types of sputtering used [4]. High pressure oxygen sputtering and facing target
sputtering are the two new methods introduced for deposition of thin films for
applications in superconducting and magnetic films.
Figure 2.3: A diagram of a sputtering system.
2.2.1.4 Pulsed laser deposition
Pulsed laser deposition (PLD) is an improved thermal process used for the deposition
of alloys or compounds with a controlled chemical composition. In laser deposition, a
high-power pulsed laser (1 J/shot) is irradiated onto the target of source materials
through a quartz window. A quartz lens is used to increase the energy density of the
laser power on the target source. Atoms that are ablated or evaporated from the surface
are collected on nearby substrate surfaces to form thin films [5]. The target material is
locally heated to the melting point, melted, and vaporized in a vacuum. The laser pulse
may also provide photo-emitted electrons from the target to make a plasma plume and
the evaporation mechanism may be complex since the process includes the thermal
process and the plasma process. By optimizing various parameters such as ablation
energy, base vacuum level, background oxygen pressure, distance between target and
substrate and the temperature of substrates, one can have desired deposition rate and
structure quality. A diagram of PLD system is shown in figure 2.4.
26
Figure 2.4: A diagram of pulsed laser deposition system.
2.2.2 Chemical deposition processes
Here, a fluid precursor undergoes a chemical change at a solid surface, leaving a solid
layer. An everyday example is the formation of soot on a cool object when it is placed
inside a flame. Since the fluid surrounds the solid object, deposition happens on every
surface, with little regard to direction; thin films from chemical deposition techniques
tend to be conformal, rather than directional. Chemical deposition processes are mainly
classified into two types viz: gas phase techniques and liquid or solution phase
techniques.
2.2.2.1 Chemical vapor deposition
Chemical vapor deposition (CVD) can be defined as a material synthesis method in

which the constituents of vapor phase react together to form a solid film at a surface
[6]. The chemical reaction is an essential characteristic of this method; therefore,
besides the control of the usual deposition process variables, the reaction of the
reactants must be well understood. Various types of chemical reactions are utilized in
CVD for the formations of solids are pyrolysis, reduction, oxidation, hydrolysis,
synthetic chemical transport reaction etc. It has emerged one of the powerful techniques
of thin film growth. Among the reasons for the growing adoption of CVD methods is
the ability to produce a large variety of films and coatings of metals, semiconductors,
and compounds in a crystalline or amorphous form, possessing high purity and
desirable properties. Furthermore, the capability of controllably creating films of
widely varying stoichiometry makes CVD unique among deposition techniques. Other
27
advantages include relatively low cost of the equipment and operating expenses,
suitability for both batch and semi continuous operation, and compatibility with other
processing steps. Figure 2.5 shows the diagram of a CVD process. CVD has numerous
other names and adjectives associated with it such as Vapor Phase Epitaxy (VPE) when
CVD is used to deposit single crystal films, Metal-organic CVD (MOCVD) when the
precursor gas is a metal-organic species, Plasma Enhanced CVD (PECVD) when a
plasma is used to induce or enhance decomposition and reaction, and Low Pressure
CVD (LPCVD) when the pressure is less than ambient.
Figure 2.5: Schematic diagram of a CVD process.
2.2.2.2 Chemical bath deposition
Chemical bath deposition (CBD) is probably the simplest method available for this
purpose and it is also known as chemical solution deposition (CSD) or chemical
deposition (CD). It is not a new technique as early as in 1835 Liebig reported the first
deposition of silver, the silver mirror deposition using a chemical solution technique.
The deposition technique was first described in 1869. The only requirements of these
methods are a vessel to contain the solution (usually an aqueous solution of common
chemicals) and the substrate on which deposition is to be carried out. In addition to this
various complication such as some mechanism for stirring and a thermo stated bath to
maintain a specific and constant temperature are options that may be useful [7,8]. CBD
is a method of growing thin film of certain materials on a substrate immersed in an
aqueous bath containing appropriate reagents at temperatures ranging from room
temperature to 100 °C. Figure 2.6 shows the diagram of a CBD process. CBD involves
28
two steps, nucleation and particle growth. It also involves the controlled precipitation
from solution of a compound on a suitable substrate. The technique offers many
advantages over the more established vapor phase synthetic routes to semiconductor
materials, such as CVD and MBE etc. Varying the solution pH, temperature and reagent
concentration allies’ factors such as control of film thickness and deposition rate with
the ability of CBD to coat large areas in a reproducible and low cost process. In CBD
two processes are traditionally used for growth: single dip, where the substrate is
immersed in the reaction both only once, and multiple dips, where the same substrate
is repeatedly coated to obtain thicker film.
Figure 2.6: Diagram of a CBD system.
2.2.2.3 Sol – gel technique
The sol-gel method was developed in the 1960s mainly due to the need of new synthesis
methods in the nuclear industry. A method was needed where dust was reduced
(compared to the ceramic method) and which needed a lower sintering temperature. In
addition, it should be possible to do the synthesis by remote control. Sol-gel technique
is a wet chemical route for the synthesis of colloidal dispersions of oxides which can
be altered to powders, fibers, thin films and monoliths [9]. In general, sol-gel method
consists of hydrolysis and condensation reactions. Sol-gel coating is a process of
preparation of single or multi-component oxide coating which may be glass, glass
29
ceramic or crystalline ceramic depending on the process. Also, the nano-materials used
in modern ceramic and device technology require high purity and facilitate to control
over composition and structure. Figure 2.7 shows the diagram of sol-gel technique. The
sol- gel method is one of the interesting methods because it has many advantages [10].
Examples are as the followings:
 The chemical reactants for sol-gel process can be conveniently purified by

distillation and crystallization.
 All strong materials are mixed at the molecular level in the solution so that a
high degree of homogeneity of films can be expected.
 Organic or inorganic salts can be added to adjust he microstructure or to
improve the structural, optical and electrical properties of oxide films.
 The sol-gel method is almost exclusively applied for fabrication of transparent
layers with a high degree of planarity and surface quality.
Figure 2.7: Generalized scheme of sol-gel technique.

30
2.2.2.4 Spray pyrolysis technique
Spray pyrolysis technique (SPT) is a process in which a thin film is synthesized by

spraying a solution onto a heated surface, where the constituents react to form a
chemical compound [11]. The chemical reactants are selected such that the products
other than the desired compound are volatile at the temperature of deposition. Unlike
many other film deposition techniques, spray pyrolysis represents a very simple and
relatively cost-effective processing method especially with regard to equipment costs.
It offers an extremely easy technique for preparing films of any composition. SPT does
not require high quality substrate or chemicals. The method has been employed for the
deposition of dense films, porous films and for powder production. Even multi-layered
films can be easily prepared using this versatile technique [12]. Thereafter, due to the
simplicity of the apparatus and good productivity of this technique on a large scale it
offered a most attractive way for the formation of thin films of noble metals, metal
oxides, spinel oxides, calcogenides and superconducting compounds. In SPT process,
the quality and properties of thin films depend largely on the preparation conditions.
Recently, emphasis given to two aspects: (1) atomization techniques to control the
droplet size and their distribution more precisely and (2) use of starting compounds
such as organotin to obtain highly oriented thin films seems more promising.
Viguie and Spitz classified chemical spray deposition processes according to the type
of reaction. In process A, the droplet resides on the surface as the solvent evaporates,
leaving behind a solid that may further react in the dry state. In process B, the solvent
evaporates before the droplet reaches the surface and the dry solid impinges on the
surface, where decomposition occurs. In process C, the solvent vaporizes as the droplet
approaches the substrate; the solid then melts and vaporizes, and the vapor diffuses to
the substrate, there to be undergo a heterogeneous reaction. In process D, the entire
reaction takes place in the vapor state. In all processes, the significant variables are the
ambient temperature, carrier gas flow rate, nozzle-to-substrate distance, droplet radius,
solution concentration, solution flow rate, and - for continuous processes substrate
motion. Most spray pyrolysis depositions are type A or B. Figure 2.8 shows the flow
chart for block diagram of different steps in SPT.
31
Figure 2.8: A flow chart for block diagram of different steps in SPT.
2.3 Thin Film Formation
Thin films are fabricated by the deposition of individual atoms on a substrate. Sufficient
time interval between the two successive deposition of atoms and also layers are
required so that these can occupy the minimum potential energy configuration. Three
major steps that constitute a typical thin-film deposition process are [13]:
(i) production of the appropriate atomic, molecular, or ionic species

(ii) transport of these species to the substrate through a medium
(iii) condensation on the substrate, either directly or via a chemical and/or
electrochemical reaction, to form a solid deposit.
2.3.1 Different stages of film formation
There are three mechanisms of thin film condensation which can be distinguished,
depending on the strength of interaction between the atoms of the growing film and
between the atoms of the film and substrate. These are:
I. Layer-by-layer growth (Frank-van der Merwe mechanism): The adsorbate-

substrate interaction dominates the adsorbate-adsorbate interaction and thus a
new layer begins to grow only when the previous layer is completed.
II. Island growth (Vollmer-Weber mechanism): The adsorbate-adsorbate
interaction dominates and thus deposition produces multilayer islands.
III. Layer-plus-island growth (Dranski-Krastanov mechanism): It is a particular
interesting case that has recently been exploited in the production of nanometer
32
scale islands. After the formation of one or more compete monolayers three
dimensional islands nucleate and grow on top of the complete layer.
I II III
Figure 2.9: I) Layer-by-layer mode II) Island growth mode and III) Layer-plus-island
growth mode.
In most cases, mechanism II takes place and it is discussed in brief.
2.3.2 Condensation
Condensation simply means the transformation of a gas into a liquid or solid.

Thermodynamically, the only requirement for condensation to occur is that partial
pressure of the film material in the gas phase be equal or larger than its vapor pressure
in the condensed phase at that temperature. The condensation of a vapor atom is
determined by its interaction with the impinged surface. The impinging atom is
attracted to the surface by the instantaneous dipole and quadruple moments of the
surface atoms. As a result, the atom loses its velocity component normal to the surface
in a short time, provided the incident kinetic energy is not too high. The vapor atom is
then physically absorbed (called atom) but it may or may not be completely thermally
33
equilibrated [14]. It may move over the surface by jumping from one potential well to
the other because of thermal activation from the surface and its own kinetic energy
parallel to the surface. The adatom has a finite stay or residence time on the surface
during which it may interact with other adatoms to form a stable cluster and be
chemically absorbed with the release of the heat of condensation. If is not absorbed the
adatom re-evaporates or desorbs into the vapor phase. Therefore, condensation is the
net result of equilibrium between the adsorption and desorption processes.
The probability that an impinging atom will be incorporated into the substrate (surface)
is called the “condensation” or “sticking coefficient”. It is measured by the ratio of the
amount of material condensed on a surface to the total amount impinged. In fact, often
the sticking coefficient is so small that observation is not observed by ordinary
techniques. On the other hand, the sticking coefficient is found to be strongly dependent
on the total time during which the substrate was subject to impingement, and also on
the substrate temperature. A non-unity sticking coefficient is usually explained in terms
of monomers re-evaporation from the areas on the substrate which are outside the
capture zones around each stable nucleus [15].
2.3.3 Nucleation
Condensation is initiated by the formation of small cluster through the combination of

several adsorbed atoms. These clusters are called nuclei and the process of cluster
formation is called nucleation.
There are two types of nucleation occurs during the formation of a film: (i)
homogeneous nucleation and (ii) heterogeneous nucleation.
(i) Homogeneous Nucleation: The total free energy is used in the formation of a
cluster of adatoms [16].
(ii) Heterogeneous Nucleation: Particular shapes of clusters are formed by
collisions of atoms on the substrate surface, and in the vapor phase its saturation
is sufficiently high [17]. They initially developed within increase in free energy
until a critical size is reached above which growth continues with a decrease in
free energy. In atomistic theory, in low substrate temperature or very high super
saturations, the critical nucleus may be a single atom which will form a pair
with another atom by random occurrence to become a stable cluster and grow
spontaneously.
34
2.3.4 Growth
Growth is the final and completion stage of thin film formation. There are several stages
in the growth process from the initial nucleation of the deposits to the final continuous
three dimensional film formation states. These stages of film growth have been
observed by many workers from their electron microscopic and other studies. These are
valid not only for deposits condensing from the vapor phase but also for others, i.e. for
solutions, by electro deposition, chemical reaction, anodic oxidation etc. Even though
the controlling factors may differ slightly or widely in the individual case these stages
have been clearly distinguishes [18, 19]. Such as:
(i) The island stage
(ii) The coalescence stage
(iii) The channel stage
(iv) The continuous film stage
2.3.4.1 The island stage
When a substrate under impingement of condenses monomers is observed in the

electron microscope, the first evidence of condensation is a sudden burst of nuclei of
fairly uniform size. Growth of nuclei is three dimensional, but the growth parallel to
the substrate is greater than that normal to it. This is probably because growth occurs
largely by the surface diffusion of monomers on the substrate, rather by direct
impingement from the vapor phase. The tendency to form an island structure is
increased by (i) at high substrate temperature, (ii) at low boiling temperature, (iii) at
low deposition rate, (iv) at weak binding energy between film material and substrate,
(v) at high surface energy of the film material and (vi) at low surface energy of the
substrate.
2.3.4.2 The coalescence stage
The next stage in the process of film formation is the coalescence stage, in which the
small islands start coalescing with each other in an attempt to reduce the substrate
surface area. This tendency to form bigger islands is termed agglomeration and is
enhanced by increasing the surface mobility of the adsorbed species, by, for example,
increasing the substrate temperature. In some cases, formation of new nuclei may occur
on areas freshly exposed as a consequence of coalescence. As island increases their size
by further deposition and come close to each other, the larger ones appear to grow by
35
coalescence of the smaller ones. In addition, nuclei having well-defined

crystallographic shapes before coalescence become rounded during the event [20]. The
composite island takes on a crystallographic shape again if left for a sufficiently long
time before interacting with its neighbors.
2.3.4.3 The channel stage

As the coalescence continues with deposition there will be a resultant network of the
film with channels. These channels need not remain void and soon some secondary
nuclei start to grow within this void space in the channel. With further deposition these
nuclei will increase in size along with the film thickness in addition to formation of new
island stage and eventually join the main islands or aggregate thus bridging the gaps.
At last, most of the channels are eliminated and the film is continuous but contains
many small irregular voids. Secondary nucleation takes place on the substrate within
these voids and growing nuclei are incorporated into the continuous regions of the
deposit. The void contains many secondary nuclei which coalescence with each other
to form secondary islands, which then touch the edge of the void and coalesce with the
main film to leave clean void. Further, secondary nuclei then form and the process is
repeated until the void finally fills in.
2.3.4.4 The continuous film stage

The continuous film stage is the final stage of film growth. It is a slow process of filling
the empty channels, which requires a considerable amount of deposits. In channel stage
large areas are vacated by coalescence. These empty channels are filled by secondary
nucleation, growth and coalescence and in this way a continuous film is formed.
Different stages of the film growth are schematically shown in figure 2.10.
36
Figure 2.10: Different stages of thin film growth.

37
References
[1]. Ohring, M., “Materials Science of Thin Films”, Academic Press, San Diego, CA,
2nd edition, 2002.
[2]. Chopra, K. L., “Thin Film Phenomena”, McGraw Hill, New York, 1969.
[3]. Brown, R., Maissel, L. I. and Glang, R., “Handbook of Thin Film Technology”,
McGraw Hill, New York, 1970.
[4]. Behrisch, R., “Sputtering by Particle Bombardment”, Springer, Berlin, 1981.
[5]. Aziz, M. J., “Film growth mechanism in pulsed laser deposition”, Appl. Phys. A:
Mater. Sci. Proc., Vol. 93(3), pp. 579-587, 2008.
[6]. Dobkin, D. and Zuraw, M. K., “Principles of Chemical Vapor Deposition”,
Springer, Science & Business Media, 2003.
[7]. K.L. Chopra, R.C. Kainthla, D.K. Pandya and Thakoor, A.P., “In: Physics of Thin
Films”, Vol. 12, Academic Press, London, 1982.
[8]. Lokhande, C. D., “A chemical method for preparation of metal sulfide thin films”,
Mater. Chem. Phys., Vol. 28(1), pp. 145-149, 1991.
[9]. Hench, L. L. and West, J. K., “The sol-gel process”, Chem. Rev., Vol. 90(1), pp.
33-72, 1990.
[10]. Ilican, Caglar, M. and Caglar, Y., “The effect of deposition parameters on the
physical properties of CdxZn1-xS films deposited by spray pyrolysis method”, J.
Optoelectr. and Adv. Mater., Vol. 9, pp. 1414-1417, 2007.
[11]. Chamberlin, R. R. and Skarman, J. S., “Chemical spray deposition process for
inorganic films”, J. Electrochem. Soc., Vol. 113(1), pp. 86-89, 1966.
[12]. Perednis, D. and Gauckler, L. J., “Thin film deposition using spray pyrolysis”, J.
Electroceram., Vol. 14, pp. 103-111, 2005.
[13]. Hartnagle, H. L., Dawar, A. L., Jain, A. K. and Jagadis, C., “Semiconducting
Transparent Thin Films”, CRC Press, Bristol, 1995.
[14]. Zhang, Z. and Lagally, M. G., “Atomistic processes in the early stages of thin film
growth”, Science, Vol. 276, pp. 377-383, 1997.
[15]. Chopra, K. L., “Nucleation, growth and structure of films”, Thin Film
Phenomena, McGraw Hill, New York, pp. 110-137, 1969.
[16]. Waugh, M. R., “Characterization of Transparent Conducting Thin Films”,
University College, London, 2011.
38
[17]. Zhang, X. X. and Jiang, E. Y., “The nucleation and initial growth of iron films
deposited by facing targets sputtering”, J. Mag. Magn. Mater., Vol. 121(1-3), pp.
46-48, 1993.
[18]. Guo, X. L., Tabata, H. and Kawai, “Pulsed laser reactive deposition of p-type
ZnO film enhanced by an electron cyclotron resonance source”, J. Cryst. Growth,
Vol. 223(1-2), pp. 135-139, 2001.
[19]. Jensen, Havlin, P., “A fractal model for the first stage of thin film growth”,
Fractals, Vol. 4(3), pp. 321-329, 1996.
[20]. Ratsch, C. and Venables, J. A., “Nucleation theory and the early stages of thin
films growth”, J. Vac. Sci. Technol. A, Vol. 21(5), pp. 96-109, 2003.
39
CHAPTER 3
THIN FILM CHARACTERIZATION TECHNIQUES

40
CHAPTER 3
THIN FILM CHARACTERIZATION TECHNIQUES
The deposited CuO and CuO: Zn thin films are characterized for their structural, surface
morphological, electrical and optical properties. X-ray diffraction (XRD) is used for
studying the nature and structure, field emission scanning electron microscopy
(FESEM) is used to identify the surface morphology and energy dispersive X-ray
(EDX) spectroscopy is used to compositional study of the prepared films. The optical
parameters have been analyzed from the transmittance and absorbance spectra obtained
using UV-Visible spectrophotometer. The Four point probe technique is employed to
measure electrical resistivity of the films. The principle, functioning and importance of
each technique are briefly outlined in this chapter with related theory.
3.1 Structural Characterization
A rapidly increasing number of research topics and applications in science and

engineering rely on thin films, superlattice growth, and patterning down to the
submicrometer scale. In order to understand the structural properties of such
nanostructures, a thorough and detailed structural characterization is required. XRD
techniques allow us to probe the internal structure of the layers and the quality of the
interfaces between the different materials in a multilayer. XRD provides most definitive
structural information.
3.1.1 X-ray diffraction
The discovery of X-rays in 1895 enabled scientists to probe crystalline structure at the
atomic level. XRD has been used in two main areas, for the fingerprint characterization
of crystalline materials and the determination of their structure [1]. Each crystalline
solid has its unique characteristic X-ray powder pattern which may be used as a
"fingerprint" for its identification. Once the material has been identified, X-ray
crystallography may be used to determine its structure, i.e. how the atoms pack together
in the crystalline state and what the inter-atomic distance and angle etc.
The size and the shape of the unit cell for any compound and can be determined most
easily using XRD. X-rays are the electromagnetic waves of wavelength about 1Å.
When X-rays are incident on a crystal surface, they are reflected from it.
41
Figure 3.1: Reflection of X-rays from two planes of atoms in a solid.
The reflection obeys the following Bragg’s law,
2dsinθ = nλ (3.1)
where d is the distance between crystal planes, θ is the incident angle of X-ray, λ is the
wavelength of the X-ray and n is a positive integer. Bragg’s law also suggests that the
diffraction is only possible when λ< 2d.
From the width of the diffraction line, it is possible to estimate the average grain size
of the thin film [2]. Surface thickness in thin films are about 1000 Å, can be investigated
using XRD [3]. Thicker films can be characterized by reflection high-energy electron
diffraction (RHEED). Analysis of the diffraction patterns obtained by these techniques
and comparison with standard ASTM data can reveal the existence of different
crystallographic phases in the film, their relative abundance, the lattice parameters and
any preferred orientations.
Using ‘d’ values the set of lattice planes (h k l) are identified from the standard data and
the lattice parameters are calculated using the relations. For a monoclinic crystal
structure, the lattice parameters can be determined using the relation,
1 1 h2 k2 sin2 β l2 2hl cosβ

= sin2β ( a2 + + − ) (3.2)
𝑑2 b2 c2 ac
where, h, k and l are the indices of the crystal planes, d is the interplanar spacing and β
is the full-width half maximum.
42
Crystallite size (D) is the of the effective crystal domain. It contributes to the peak
broadening and as crystallite size decreases, the full width increases. The average D of
the film is determined by using Debye Scherrer formula [4],
kλ
D = β cosθ (3.3)
Where k is a constant known as shape factor and taken as 0.94, λ is the wavelength of
X-rays.
The origin of micro strain (ε) is calculated using the relation [5],
β cosθ
ε= (3.4)
4
The dislocation density (δ) is the dislocation lines per unit area of the crystal, can also
be evaluated from the crystallite size ‘D’ using the formula [6],
δ = 1/D2 (3.5)
3.2 Surface Morphology

Surface morphology is a subset of analytical imaging, which is an advanced form of
high spatial resolution imaging that uses sophisticated microscopes to produce images
of samples, objects and products that cannot be seen with the naked eye. Such images
originate from the exposed surface of the sample or product.
3.2.1 Electron microscope
The electron microscope is a type of microscope that uses a beam of electrons to create
an image of the specimen. It is capable of much higher magnifications and has a greater
resolving power than a light microscope, allowing it to see much smaller objects in finer
detail. Figure 3.2 shows the basic steps involved in all electron microscopes. Electron
microscopes use signals arising from the interaction of an electron beam with the
sample to obtain information about structure, morphology and composition. Electrons
are such small particles that, like photons in light, they act as waves. A beam of
electrons passes through the specimen, then through a series of lenses that magnify the
image. The image results from a scattering of electrons by atoms in the specimen. A
heavy atom is more effective in scattering than one of low atomic number, and the
43
presence of heavy atoms will increase the image contrast. The above procedures are
followed by all types of electron microscope.
Figure 3.2: Schematic diagram of an electron microscope.
3.2.2 Field emission scanning electron microscopy
Field emission scanning electron microscopy (FESEM) provides topographical and

elemental information at magnifications of 10x to 300,000x, with virtually unlimited
depth of field. Compared with conventional SEM, FESEM produces clearer, less
electrostatically distorted images with spatial resolution down to few nanometers –
three to six times better. In FESEM, electrons are liberated from a field emission source
and accelerated in a high electrical field gradient. Within the high vacuum column these
so-called primary electrons are focused and deflected by electronic lenses to produce a
narrow scan beam that bombards the object. As a result, secondary electrons are emitted
from each spot on the object. The angle and velocity of these secondary electrons relates
to the surface structure of the object. A detector catches the secondary electrons and
produces an electronic signal. This signal is amplified and transformed to a video scan-
image that can be seen on a monitor or to a digital image that can be saved and processed
further.
44
Figure 3.3: A field emission scanning electron microscope set up.
Figure 3.3 represents a FESEM of model JEOL JSM-7600F. This FESEM is used in
this research work.
3.3 Elemental Analysis
Elemental analysis is a process where a sample is analyzed for its elemental and
sometimes isotopic composition. Elemental analysis can be qualitative (determining
what elements are present) and it can be quantitative (determining how much of each
are present). Energy dispersive X-ray spectroscopy (EDS, EDX, or XEDS), sometimes
called energy dispersive X-ray analysis (EDXA) or energy dispersive X-ray
microanalysis (EDXMA), is an analytical technique used for the elemental
analysis or chemical characterization of a sample.
3.3.1 Energy dispersive X-ray spectroscopy
EDX is a chemical microanalysis technique used in conjunction with FESEM. EDX

can provide elemental analysis on areas as small as nanometer in diameter and it is used
to determine the elemental composition of individual points or to map out the lateral
distribution of elements from the imaged area. When an incident electron beam hits
atoms of the sample, secondary and backscattered electrons are emitted from the sample
45
surface. However, these are not the only signals emitted from the sample. When the
incident beam bounces through the sample creating secondary electrons, it leaves
thousands of the sample atoms with holes in the electron shells where the secondary
electrons used to be. If these "holes" are in inner shells, the atoms are not in a stable
state. To stabilize the atoms, electrons from outer shells will drop into the inner shells,
however, because the outer shells are at a higher energy state, to do this the atom must
lose some energy. It does this in the form of X-rays. The X-rays emitted from the sample
atoms are characteristic in energy and wavelength to, not only the element of the parent
atom, but which shells lost electrons and which shells replaced them, this permits the
elemental composition of the sample to be measured.
An EDX spectrum not only identifies the element corresponding to each of its peaks,
but also the type of X-ray to which it corresponds as well. For example, a peak
corresponding to the amount of energy possessed by X-rays emitted by an electron in
the L-shell going to the K-shell is identified as a K-alpha peak. The peak corresponding
to X-rays emitted by M-shell electrons going o the K-shell is identified as K-beta peak
(Figure: 3.4).
Figure 3.4: Scheme of X-ray excitations in EDX analysis.
3.4 Optical Characterization
Optical properties of thin films have been studied because of their applications in
various optical and opto-electrical devices. The optical properties of the thin films are
studied by UV-visible spectroscopic measurements. The optical study concerns with
transmission, absorption, reflection, refraction, polarization, interference and etc. From
these properties it is possible to calculate the optical constants such as: absorption
coefficient (), direct and indirect band gap, refractive index (n), extinction coefficient
46
(k), optical conductivity (opt), real and imaginary part of dielectric constant etc. UV-
visible transmission spectra have been recorded using a dual beam UV-visible
spectrophotometer (SHIMADZU UV-1601) in the wavelength range of 200-1100 nm
at room temperature (Figure 3.10). The transmission spectra have been recorded for
both the CuO at Ts of 300 °C, 350 °C, 370 °C and 400 °C and CuO: Zn at Ts of 350 °C
thin films of concentration 1-6 at%. A cleaned glass slide is used as the reference during
the optical absorption measurement of thin films.
Figure 3.5: A UV-visible spectrophotometer.
3.4.1 Beer-Lambert law
The Beer-Lambert law (or Beer's law) [7] is the linear relationship between absorbance
and concentration of an absorbing species. The general Beer-Lambert law is usually
written as:
A = abc (3.6)
where ‘A’ is the measured absorbance, ‘a’ is a wavelength-dependent absorptivity

coefficient, b is the path length, and c is the analyze concentration.
When working in concentration units of molarity, the Beer-Lambert law is written as:
A = ԑbc (3.7)
where ‘ԑ’ is the wavelength-dependent molar absorptivity coefficient with units of
(M cm) -1 .
47
Experimental measurements are usually made in terms of transmittance (T), which is

defined as:
T = I / Io (3.8)
where I is the light intensity after it passes through the sample and Io is the initial light
intensity. The relation between A and T is:
A = -log T = - log (I / Io) (3.9)
Modern absorption instruments can usually display the data as either transmittance, %-
transmittance, or absorbance.
The Beer Lambert law can be derived from an approximation for the absorption
coefficient for a molecule by approximating the molecule by an opaque disk whose
cross-sectional area, σ, represents the effective area seen by a photon frequency ν. If
the frequency of the light is far from resonance the area is a maximum. Taking an
infinitesimal slab, dz, of sample:
Figure 3.6: Mechanism of absorption of light.
Figure 3.6 shows the mechanism of absorption of light.
Io is the intensity entering the sample at z=0, Iz is the intensity entering the infinitesimal
slab at z, dI is the intensity absorbed in the slab, and I is the intensity of light leaving
the sample. Then, the total opaque area on the slab due to the absorbers is σNA dz.
Then, the fraction of photons absorbed will be σNA dz / A. So,
48
dI
= -σNdz (3.10)
Iz
Integrating this equation from z = 0 to z = b gives:
ln (I) – ln (Io) = -σ N b
or, - ln (I / Io) = -σ N b
Since N (molecules/cm3) (1 mole/6.023x1023 mlecules) 1000 cm3 / liter = c (moles/liter)

and 2.303*log(x) = ln(x)
Then,
- log(I / Io) = σ(6.023x1020 / 2.303) cb
or, A = ԑbc = -log(I/Io) (3.11)
Where, ԑ = σ (6.023x1020 / 2.303) = σ(2.61x1020), and ԑ is called molar absorptivity.
Thus the intensity of the transmitted light can be expressed as I = Io e –αd where d is the
path length through the sample and α is the absorption coefficient. This equation can
be written as,
2.303 A
α= (3.12)
d
3.4.2 Electronic transitions
The absorption of UV or visible radiation corresponds to the excitation of outer

electrons. There are three types of electronic transition which can be considered;
1. Transitions involving π, σ and n electrons

2. Transitions involving charge-transfer electrons
3. Transitions involving d and f electrons (not covered in this Unit).
When an atom or molecule absorbs energy, electrons are promoted from their ground
state to an excited state. In a molecule, the atoms can rotate and vibrate with respect to
each other. These vibrations and rotations also have discrete energy levels, which can
be considered as being packed on top of each electronic level as shown in Figure 3.7.
49
Figure 3.7: Vibrational and rotational energy levels.
Absorbing species containing π, σ and n electrons
Absorption of ultraviolet and visible radiation n organic molecules is restricted to

certain functional groups (chromophores) that contain valence electrons of low
excitation energy. The spectrum of a molecule containing these choromophores is
complex. This is because the superposition of rotational and vibrational transitions on
the electronic transitions gives a combination of overlapping lines. This appears as a
continuous absorption band.
Possible electronic transitions of π, σ and n electrons are discussed below in Figure 3.8.
Figure 3.8: Possible electronic transitions.

50
σ σ* Transitions
An electron in a bonding σ orbital is excited to the corresponding antibonding orbital.

The energy required is large. For example, methane (which has only C-H bonds, and
can only undergo σ σ* transitions) shows an absorbance maximum at 125 nm.
Absorption maxima due to σ σ* transitions are not seen in typical UV-Vis. Spectra
(200 – 700 nm).
n σ* Transitions
Saturated compounds containing atoms with lone pairs (non-bonding electrons) are
capable of n σ* transitions. These transitions usually need less energy than σ to
σ* transitions. They can be initiated by light whose wavelength in the range 150 – 250
nm. The number of orange functional group with n σ* peaks in the UV region is
small.
n σ* and π π* Transitions
Most absorption spectroscopy of organic compounds is based on transitions of n or π

electrons to the π* excited state. This is because the absorption peaks for these
transitions fall in an experimentally convenient region of the spectrum (200 – 700 nm).
These transitions need an unsaturated group in the molecule to provide the π electrons.
Molar absorbitivities from n π* transitions are relatively low, and range from 10
to 100 L mol-1 cm-1. π π* transitions normally give molar absorbtivities between
1000 and 10,000L mol-1 cm-1. The solvent in which the absorbing species is dissolved
also has an effect on the spectrum of the species. Peaks resulting from n π*
transitions are shifted to shorter wavelengths (blue shift) with increasing solvent
polarity. This arises from increase of the lone pair, which lowers the energy of the n
orbital. Often (but not always), the reverse (i.e. red shift) is seen for π π* transitions.
This is caused by attractive polarization forces between the solvent and the absorber,
which the lower energy levels of both the excited and unexcited states. This effect is
greater for the excited state, and so the energy difference between the excited and
unexcited states is slightly reduced - resulting in a small red shift. This effect also
influences the n π* transitions but is overshadowed by the blue shift resulting from
the salvation of lone pairs.
51
3.4.3 Direct and indirect optical transition
In solid state physics and related applied fields, the band gap, also called an energy gap
or stop band, is a region where a particle or quasiparticle is forbidden from propagating.
For insulators and semiconductors, the band gap generally refers to the energy
difference between the top of the valence band and the bottom of the conduction band
as shown in Figure 3.9. Fundamental absorption refers to the annihilation or absorption
of photons by the excitation of an electron from the valence band up into the conduction
band, leaving a hole in the valence band. Both energy and momentum must be
conserved in such a transition.
In the case of an indirect-band gap semiconductor, the minimum energy in the

conduction band and the maximum energy in the valence band occur at different values
of crystal momentum. Photon energies much larger than the forbidden gap are required
to give direct transitions of electrons from the valence to the conduction band. However,
transitions can occur at lower energies by a two-step process involving not only photons
and electrons but also a third particle, a phonon.
Figure 3.9: Schematic presentation of direct and indirect transitions between valence
and conduction bands.
To estimate the nature of absorption a random phase model is used where the k
momentum selection rate is completely relaxed. The integrated density of states N(E)
has been used and defined by
52
+∞
N(E) = ∫−∞ g(E)dE (3.13)
The density of states per unit energy interval may be represented by
1
g(E) = 𝑣 Σ δ (E-En) (3.14)
Where, V is the volume, E is the energy at which g(E) is to be evaluated and E n is the
energy of the nth state.
If gν ∝ Ep and gc ∝ (E-Eopt), where energies are measured from the valence band
mobility edge in the conduction band (mobility gap), and substituting these values into
an expression for the random phase approximation, the relationship obtained
ν2 I2 (ν) ∝ (hν-E0)p+q+1, where I2 (ν) is the imaginary part of e complex permittivity. If

the density of state of both band edges is parabolic, then the photon energy dependence
of the absorption becomes
αhν ∝ ν2I2(ν) ∝ (hν-Eopt)2 (3.15)
So, for higher photon energies the simplified general equation which is known as Tauc
relation is,
αhν = B (hν - Eopt)n (3.16)
where hν is the energy of absorbed light, n is the parameter connected with distribution
of the density of states and B, a constant or Tauc parameter and here n = ½ for direct
and n = 2 for indirect transitions [8].
The above equation can be written as
𝑑[ln(𝛼ℎ𝜈)] 𝑛
= hν−E (3.17)
𝑑[ℎ𝜈] opt
When finding the n, type of transition can be obtained from the absorption spectrum. A
discontinuity in the d[ln(αhν)]/d(hν) versus hν plot at the band gap energy (Eopt or Eg),
i.e. at hν = Eg can be observed. The discontinuity at a particular energy value gives the
band gap Eg.
53
Thus from the straight-line plots of (αhν)2 versus hν and (αhν)1/2 versus hν the direct
and indirect energy gaps of thin films material can be determined.
3.4.4 Absorption coefficient
When a semiconductor is illuminated by light, a photon strikes the surface, a fraction

of photons are reflected and the remaining photons enter the semiconductor. Some of
these are absorbed within the semiconductor and the remainder transmitted into the
semiconductor. The absorption of radiation by any medium occurs through the
excitation of electrons and photons. For semiconductor, it is convenient to consider
several types of absorption arising from
I. Electronic transitions between different energy bands.

II. Electronic transitions within energy band.
III. Electronic transitions to localized states of impurity atoms.
IV. Lattice vibrations
V. Vibrations of impurity atoms.
In the fundamental absorption region the transmission T is given by
4πkt
T = A exp (- ) (3.18)
λ
Where ‘A’ is constant, ‘k’ is the extinction co-efficient and ‘t’ is the thickness. For k2
≪ n2, the principle variation of T occurs in the exponential term and pre-exponential
term A. Therefore,
T ≈ exp (-αt) (3.19)
4𝜋𝑘
Where α = is the absorption co-efficient of the film. Thus the value of absorption
𝜆
co-efficient may be calculated from the relation
lnT
α=- (3.20)
t
54
3.4.5 Refractive index and extinction coefficient
The refractive index (n) of a substance is a measure of the speed of light in that
substance. n is defined as the ratio of the velocity of light through a vacuum to the
velocity of light through the medium. A simple mathematical description of the
refractive index is as follows:
n = speed of light in a vacuum / speed of light in the medium
n=c/v
Figure 3.10: Refraction of light at the interface between two media of different
refractive indices.
In materials where an electromagnetic wave can lose its energy during its propagation,
n becomes complex. The real part is usually n and the imaginary part is called the
extinction coefficient (k). In this section, n and k will be presented in detail along with
some dispersion relations. Using above and Maxwell’s equations, one obtains the well-
known Maxwell’s formula for n of substance as n= √εμr where ε is the static dielectric
constant or relative permittivity and μr is the relative permeability. As μr = 1 for
nonmagnetic substances, one gets, n = √ε, which is very useful in relating the dielectric
properties to optical properties of materials at any particular frequency of interest. As ε
depends on the wavelength of light, n also depends on the wavelength of light, and this
dependence is called dispersion. In addition to dispersion, an electromagnetic
propagating through a medium experiences attenuation, which means it loses it energy,
due to various loss mechanisms such as the generation of phonons (lattice waves), photo
generation, free carrier absorption, scattering, et. In such materials, the refractive index
becomes a complex function of the frequency of the light wave. The complex refractive
55
index, denoted by n*, with real part n, and imaginary part k, called the extinction
coefficient, is related to ε by:
n* = n – jk = √ε = √εr – jεi (3.21)
Where εr and εi are, respectively, the real and imaginary parts of ε. Equations (3.21)
n2 – k2 = εr and 2nk = εi (3.22)
In explicit terms, n and k can be obtained as:
n = (1/21/2) [(εr2 + εi2) + εr ]1/2 (3.23)
k = (1/21/2) [(εr2 + εi2) - εr ]1/2 (3.24)
The optical constants n and k can be determined by measuring the reflectance from the
surface of a material as a function of polarization and the angle of incidence. For normal
incidence, the reflection coefficient, r, is obtained as
r = (1 – n*) / (1 + n*) = (1 – n + jk) / (1 + n - jk) (3.25)
The reflectance R is then defined by:
1−n+jk 2
R = |𝑟|2 = |1 +n −jk| = {(1 – n)2 + k2} / {(1+ n)2 + k2} (3.26)
And refractive index can be calculated by using following equation
1+R 4R
n = (1−R) + √((1−R)2 − k 2 ) (3.27)
Notice that whenever k is large, for example over a range of wavelengths, the
absorption is strong, and the reflectance is almost unity. The light is then reflected, and
any light in the medium is highly attenuated.
Extinction coefficient can be determined from the relation as follows
αλ
k = 4π (3.28)
56
And the optical conductivity of the thin films is calculated by using the following
equation
αnc
σopt = (3.29)
4π
3.5 Electrical Characterization
Electrical characterization methods for the analysis of thin films include the
measurement of the electrical resistivity (ρ). ρ is a key physical property of all materials.
It is often necessary to accurately measure the value of ρ of a given material. There are
four methods commonly used for the measurement of resistivity such as:
a) Direct method
b) Two point probe method
c) Four point probe method
d) Van der Pauw method
3.5.1 Direct method
The resistivity of a thin film can be measured easily by direct method using the relation
bt
ρ=R (3.30)
L
Where, b and t are the breath and thickness of the sample. For simplicity, if we consider
b = L, the above equation becomes
ρ = Rt (3.31)
Electrical conductivity of a material is reciprocal of resistivity of the material.

Conductivity is denoted by σ and defined as
σ = 1/ρ (3.32)
Measuring the resistance, R and thickness, t one can easily determine the resistivity and
the conductivity.
57
3.5.2 Two point probe method
This is the simplest method of measuring resistivity and is illustrated in Figure 3.11. In
this method, voltage drop V across the sample and current through the sample I are
measured. Then the resistivity is given as
VA
ρ= (3.33)
IL
Where L is the specimen length and A is the cross-sectional area of the specimen. This
method is useful when the sample has large resistance.
Thin Film
I
E
Figure 3.11: Electrical resistivity measurement by two point probe method.
3.5.3 Four point probe method
The four point probe method has proven to be a convenient tool for the resistivity
measurement of small size (of the order of mm) specimen. This method is applicable
when the distance between the probes is small compared to the smaller dimension of
the sample, and provided none of the probe is too close to an edge of the sample. The
arrangement of four point probes is shown in Figure 3.12.
58
Figure 3.12: Electrical resistivity measurement by four point probe method.
In the case of a four point probe on a sheet, the two outside current points represent the
dipole. Therefore, the resistivity in this case can be given by [9]
VD
ρ= 2πS (3.34)
I
Here, the distance between all the four points is equal. I, is the current flowing through
the sample, VD is produced voltage across two inner points and S is the distance
between the adjacent points. If the distance between contact points is not equal and it
is given as S1, S2 and S3 respectively, then the resistivity is given as
V 2𝜋
ρ= [ 1 1 1 1 ] (3.35)
I ( + − − )
𝑆1 𝑆3 𝑆1 + 𝑆2 𝑆2 + 𝑆3
Where, V is the floating potential difference between the inner probes, and I is the
current through outer pair of probes.
For all the deposited samples ρ is measured by this four point probe method.
3.5.4 Factors affecting resistivity measurement
The effects of the following factors are remarkable in the measurement of resistivity:
a) Length to breadth ratio, L/b of the film

b) Current electrodes
c) Current density
d) Microscopic inhomogenity of the film
59
e) Sensitivity of the measuring devices

f) Electrical contact resistivity
3.5.5 Activation energy
The energy required to transfer charge from one initially neutral island to another is
known as activation energy and denoted by ΔE. This is equivalent to the electrostatic
binding energy of the charge of the island. When these charge carriers are excited to a
least this energy from the Fermi-level, there will be tunneling from one island to
another. These islands or small particles are called crystallites. The activation energy is
related with film conductivity and given by the relation
∆E
σ = σo exp(− ) (3.36)
2kB T
where σo is the conductivity at 273K, kB is the Boltzmann constant and T is the absolute
temperature. Equation (3.36) can be written as
∆E
lnσ = - 2k + lnσo (3.37)
BT
Equation (3.45) is equivalent to a straight line equation, y = mx + c. So that ∆E can be

1
determined from the slope of the straight line. From the graph of lnσ vs. T, ∆E can be
calculated by using the relation
lnσ
∆E = - ( 1 ) × 2kB (eV) (3.38)
T
3.6 Thickness measurement of thin film
Film thickness is defined as the perpendicular distance from any point on a surface to
the other end of the film. It plays an important role on the properties of thin film and
also it is one of the most significant film parameter. Therefore, the thickness should be
measured with great care as far as possible to have an accurate value. There are several
methods for thin film thickness measurement, for instance, weighing, X-ray
fluorescence, stylus profiler technique and multiple-beam interferometry technique
[10]. Multiple-beam interferometry technique is employed for the measurement of
thickness of the thin films. In this method two reflecting surfaces are brought into close
proximity to produce interference fringes. Nowadays it is a well-developed and
60
standard method [11]. When two reflecting surfaces are brought into close proximity,
interference fringes are produced, the measurement of which makes possible a direct
determination of film thickness and surface topography with high accuracy. In this
method, two types of fringes are utilized for thickness measurement. The first produces
Fizeau fringes of equal thickness, using a monochromatic light source. The second uses
a light source and produces fringes of equal chromatic order. The second method is
prepared for thinner films. The Fizeau fringes method is used in the present work for
the measurement of film thickness. For the experimental set up a low power
microscope, a monochromatic source of light, a glass plate and an interferometer are
required. To make the Fizeau fringes of equal thickness visible in a multiple beam
interferometer formed by a thin absorbing film on a glass substrate, generally and
auxiliary reflecting coating on the film surface is required. But if the experimental
sample is transparent with a very smooth surface no such auxiliary coating is necessary.
The film whose thickness is to be measured is required to form a step on a glass
substrate and over it another plane glass plate is placed. This illuminated with a parallel
monochromatic beam of light a fringe system is produced and is viewed with low power
microscope. The fringe spacing and fringe displacement (step height) across the step
are measured and used to calculate the film thickness. The thickness of the film “d” can
then be determined by the relation,
λ b
d=2 × (3.39)
a
Where, λ = wavelength, b = step height and a = fringe spacing.
In general, the sodium light is used, for which λ = 5893 Å. Figure 3.13 shows the
diagram of multiple-beam interferometer thickness measurement method.
61
Image plane
Microscope
Monocromatic
source
Glass plate
Collimating lens
Reference plate
(Half silvered)
Film to be measured
Glass plate
Step height (b) Fringe spacing (a)
Figure 3.13: Interferometer arrangement for producing reflection Fizeau fringes of

equal thickness.
62
References
[1]. Kang, S. J., Joung, Y. H. and Yoon, Y. S., “ Effect of substrate temperature on
structural, optical and electrical properties of ZnO thin films deposited by pulsed
laser deposition”, J. Mater. Sci.: Mater. Electron, Vol. 1, pp. 1073-1078, 2008.
[2]. Raviprakash, Y., Kasturi, Bangera, V., Shivakumar, G. K., “Preparation and
characterization of CdZn1-xS thin films by spray pyrolysis technique for
photovoltaic applications”, Solar Energ., Vol. 83, pp. 1645-1651, 2009.
[3]. Gupta, B. K. and Agnihotri, O. P., “Structural investigations of spray-deposited
CdS films doped with Cu, In and Ga”, Philos. Mag. (b), Vol. 37, pp. 631-633,
1978.
[4]. Warren, B. E., “X-ray Diffraction”, Addision Wesley Publishing Co.: London,
1969.
[5]. Zhao, Y. and Zhang, J., “Microstrain and grain-size analysis from diffraction peak
width and graphical derivation of high-pressure thermomechanics”, J. Appl.
Cryst., Vol. 41, pp. 1095-1108, 2008.
[6]. Szekely, F., Groma, I. and Lendvai, J., “Characterization of self-similar
dislocation structures by X-ray diffraction”, Mater. Sci. Engn., A, Vol. 324, pp.
179-182, 2002.
[7]. Swinehart, D. F., “The Beer-Lambert law”, J. Chem. Edu., Vol. 39(7), pp. 333-
335, 1962.
[8]. Davies, E. A and Mott, N. F, “Conduction in non-crystalline system, optical
absorption and photoconductivity in amorphous semiconductor”, Philos. Mag.,
Vol. 22, pp. 903-922, 1970.
[9]. Singh, Y., “Electrical resistivity measurements: a review”, Int. J. Mod. Phys.:
Conf. Series, Vol. 22, pp. 745-756, 2013.
[10]. Pliskin, W. A. and Stelvio, J., Z., “Thin Film Technology”, McGraw Hill, New
York, 1970.
[11]. Tolanasky, S., “Multiple Beam Interferometry”, Oxford University Press,
London, 1948.
63
CHAPTER 4
SYNTHESIS OF COPPER OXIDE AND ZINC DOPED COPPER OXIDE THIN FILMS
64
CHAPTER 4
SYNTHESIS OF COPPER OXIDE AND ZINC DOPED COPPER OXIDE THIN FILMS
4.1 Introduction
A thin film can be defined as a quasi-two-dimensional material created by condensing,

atomic/molecular/ionic species of matter. Thin film preparation is a sequential process.
SPT is the most commonly used technique adopted for the synthesis of thin film of
transparent, conducting oxide, calcogenides, etc. compounds [1]. In this chapter, the
details about precursor and doping materials, design and construction of different
experimental apparatus and preparation of CuO and CuO: Zn thin films onto glass
substrate by SPT are discussed briefly.
4.2 Precursor Material
To synthesis CuO and CuO: Zn thin films copper (II) acetate monohydrate
[Cu(CH3COO)2.H2O] is used as a precursor material. Cu(CH3COO)2.H2O is non-toxic
and non- flammable. It is manufactured by MERCK, KGaA, 64271 Darmstadt,
Germany and is collected from local market. Its some typical properties are discussed
below:
 Chemical Name : Copper (II) acetate, Cupric acetate
 Molar Mass : 199.65 g/mol
 Appearance : Dark green crystalline solid
 Density : 1.88 g/cm3
 Melting Point : 115 °C
 Boiling Point : 240 °C
 Crystal Structure : Monoclinic

65
4.3 Doping Material
To prepare CuO: Zn thin films zinc acetate [Zn(CH3COO)2.2H2O] is used as doping

material. It is manufactured by MERCK, KGaA, 64271 Darmstadt, Germany and is
collected from local market. Some typical properties of Zn(CH3COO)2.2H2O are
discussed below:
 Appearance : White solid
 Molar Mass : 219.50 g/mol
 Density : 1.73 g/cm3
4.4 Experimental Details
4.4.1 Fabrication of masks
The direct deposition of thin film pattern requires a suitably shaped aperture, commonly
referred to as a mask. For the purpose of various experimental studies, film of specific
size and shape are required. Mask was made from stainless steel plate with the desired
pattern cut into it. The aperture was made in a lathe machine.
Figure 4.1: Mask for the sample.
The mask is placed in proximity to the substrate, thereby allowing condensation of the
evaporant only in the exposed substrate areas. The mask is prepared in such a way that
the edge of the mask is smooth so that it is helpful for determining the film thickness
accurately (Figure 4.1).
4.4.2 Air compressor
An air compressor is a machine that converts power usually from an electric energy
into kinetic energy by pressurizing and compressing air. It is a reservoir type electrical
air compressor. At the outlet of the tank a pressure gauge is attached which records the
66
pressure of the air at the time of supplying it from the tank. There is a bypass control
valve which can keep the output pressure constant.
4.4.3 The design of the reactor
The design of the reactor is shown in Figure 4.2. It is a vertical batch type reactor
composed of a heater ‘H’ and heat susceptor ‘G’. For the rapid expulsion of the by-
product gases there are opening at the side and at the top of the reactor. It helps focusing
the incoming sprayed solution towards the substrate and also provides a chimney action
to the exhaust gas upwards.
4.4.4 Heater
The heater ‘H’ is an ordinary hot plate 1.5 kW nichrome wire heater. The top of the
plate is covered with a piece of asbestos sheet having a small open area at the center
where a mica sheet is attached. A thick stainless steel plate ‘G’ (Figure 4.2) is placed on
this mica sheet. Substrate is placed on this susceptor ‘G’ to have a uniform temperature
throughout the substrate surface. An electrical voltage variac controls the heater power.
4.4.5 The fume chamber
It is a large box type chamber with a slanting top and is provided with a chimney. There
is an exhaust fan with regulated power supply fitted at the top of the chimney to remove
the unused gases from the chamber. The slanting top and the sidewalls are made of glass
and wood. There are airtight doors in the front side. The chamber has purging facilities.
The whole spray system and the reactor are kept inside the fume chamber at the time
of film deposition because of the safety grounds and to check air current disturbances
at the deposition site. These two points just stated are very important for the spray
process when decomposition is carried out in open-air atmosphere.
4.4.6 Spray head / nozzle

The single spray nozzle consists of capillary tubes (stainless steel) fitted at
perpendicular to the other tube as shown in Figure 4.2. When compressed air is passed
rapidly through the upper tube ‘P’ in direction tangential to the mouth of the lower tube
‘A’ whose other end is kept immersed in the spray liquid. Due to this partial vacuum
the liquid rises up through the tube ‘A’ and the compressed air drives it away in the
67
form of the fine spray particles (aerosol). The thinner spray nozzle would give the finer
spray particles. A very fine needle shaped capillary tube is used for the spray nozzle.
Fine spray through the nozzle depends on the bore of the nozzle and it may vary from
nozzle to nozzle.
Lower Tube, A
Air
Tub er
e, P
Upp
d
Beaker Filled
rize
ssu
with Solution, F
Pre
Air Compressor
Substrate, S
Graphite
Block, G
Heater,H Thermocouple, T.C
Figure 4.2: A schematic diagram of the experimental set up of the spray pyrolysis
technique.
4.5 Choice of substrate
Thin film deposition is made on some solid substrates such as glass, quartz, ceramics,
alloys, mica, minerals, metals, semiconductors, insulators, organic materials such as
cellulose, plastic, polymer, rubber, etc. The substrate chosen must be flat and smooth,
and also should have adequate adhesion to the deposited film [2]. The absence of
chemical reaction with the deposited film is necessary. In the present study, the
microscope glass slides having 5 cm long, 2 cm wide and 0.1 cm thickness is used as
substrates, which are non-conducting and amorphous in nature.
4.6 Substrate cleaning
The cleaning of substrate has a major influence on the properties of the thin film
deposited onto them. Surface contaminations manifest it in pinholes, which can cause
open resistor or localized high resistance. The following procedures are used for
substrate cleaning. The gross contamination of each of the substrates are first removed
by lukewarm aqueous solution of sodium carbonate and washed with distilled water.
After washing in distilled water, the substrates are dipped at first into nitric acid for
68
some time and again washed in distilled water. These are then dipped into chromic acid
for some time. Taking them out of chromic acid bath one by one and then these are
washed and thoroughly rinsed with deionized water for several times. Finally, these are
dried in hot air and preserved for use. During the whole process the substrates are
always held by slide holding forceps [3].
4.7 Preparation of working solution
The working solution is prepared by taking Cu(CH3COO)2.H2O as a source material.

The most commonly used solvents are distilled water and ethanol. As
Cu(CH3COO)2.H2O dissolves in water at room temperature, water is taken as solvent.
Since, the spray system used in the present experiment operates via a partial vacuum
path as the mouth of the spray nozzle, the concentration of the solution prepared by the
solvent is made in such a way that it could be at least be drawn by the nozzle. Higher
the concentration, lower the spray rates. A typical value of solution concentration 0.1
M is used in this work. In order to prepare the CuO and CuO: Zn thin films, the aqueous
solution of copper acetate and copper acetate: zinc acetate are used as the precursor
solution respectively. In the case of CuO: Zn thin films, the atomic percentage of Zn
in solution are varied from 1 to 6 at%.
4.8 Thin film deposition parameters
The properties of thin film deposited in SP technique depend on various deposition

parameters. Deposition parameters like substrate temperature (Ts), spray rate (Sr),
nature and concentration of the solution (C), deposition time (td), quality of the substrate
material, size of the atomized particles, substrate to spray outlet distance (ds), carrier
air pressure, etc. effect on the film properties. The effect of some important spray
parameters is discussed here.
4.8.1 Substrate temperature
Substrate temperature plays a major role in determining the properties of the films
formed. It is generally observed that higher substrate temperature results in the
formation of better crystalline films [4]. Grain size is primarily determined by initial
nucleation density and recrystallization. The composition and thickness are affected by
changes in substrate temperature which consequently affect the properties of deposited
films. In this work the CuO thin films are deposited at various Ts of 300, 350, 370 and
69
400 °C and CuO: Zn thin films are deposited at Ts of 350◦C, which is optimized Ts for
CuO thin films.
4.8.2 Spray rate
Spray rate is yet another parameter influencing the properties of films formed. It has
been reported that properties like crystallinity, surface morphology, resistivity and even
thickness are affected by changes in spray rate [5]. It is generally observed that lower
spray rate favors formation of better crystalline films. Lower spray rate requires higher
deposition time for obtaining films of the same thickness prepared at higher spray rate.
The rate of flow of the working solution can be controlled by a suitable nozzle ‘A’ and
adjusting the airflow rate. In this research work spray rate is almost kept at constant
0.08 ml/min.
4.8.3 Thickness control
Thickness plays an important role in the film properties of thin films unlike a bulk
material [6,7]. In the present SPT, the deposition time is the main thickness controlling
factor, provided the other parameters remain constant. Since the deposition is carried
out in normal atmosphere a direct and insitu control of thickness is not so easy. To
control the film thickness therefore calibration chart may be used. The charts are
generally plots of deposition time versus thickness, and can be prepared at different
constant substrates temperatures prior to the preparation of particular experimental
samples using the different solution and deposition variables. Since the rate of
deposition in the present set up is rather small, the thickness control is therefore not
difficult.
4.8.4 Sample deposition
It has been studied earlier that SPT is a cost-effective method for preparing CuO and
CuO: Zn thin films [8], which consist basically of spraying solution on a heated glass
substrate. The apparatus needed to carry out the chemical spray process consists of a
device to atomize the spray solution and a substrate heater. Figure 4.2 shows a
schematic diagram of SPT unit and Figure 4.3 shows the experimental setup for SPT
used in this work. A considerable amount of (about 100 ml) solution is taken in the
container ‘F’ fitted with the spray nozzle ‘A’. The clean glass substrate with a suitable
mask is put on the susceptor of the heater ‘H’. The distance between the tip of the nozzle
70
and the surface of the glass substrate is kept 25 cm. Before supplying the compressed
air the substrate temperature ‘Ts’ is to be kept at a level slightly higher than the required
TS because at the onset of spraying a slight fall of temperature is likely. Ts is controlled
by controlling the heater power using a variac. Ts is measured by placing a copper
constantan thermocouple on the substrate. When compressed air is passed through ‘P’
at constant pressure of 1 bar, vacuum is created at the tip of the nozzle and the solution
is automatically carried to the reactor zone in the form of spray and film is deposited
on the heated substrate [9, 10]. The working solution is adjusted such that about 5
minutes of spray produces CuO and CuO: Zn thin films of thickness about 144 to 190
nm. The possible chemical reaction that takes place on the heated substrate to produce
CuO and CuO: Zn may be as follows:
Cu(CH3COO)2.H2O + H2O CuO + CH4 + CO2 + Steam
Cu(CH3COO)2.H2O
+ Cu1-xZnxO + CO2 + CH4 + Steam
Zn(CH3COO)2.2H2O
+ H2O
Exhaust Fan
Solution
Spray Nozzle
Hot Plate
Heater
Variac
Air Compressor
Figure 4.3: Experimental set up of spray pyrolysis unit at the Department of Physics,
BUET.
71
4.9 Synthesized Sample

Samples synthesized in the various condition for investigations are presented in Table
4.1.
Table 4.1: Synthesized Sample
Sample Solution Concentration (M) Ts (°C) Zn Concentration (at%)
CuO 0.1 300, 350, 370 ……….

and 400
CuO: Zn 0.1 350 1, 2, 3, 4, 5 and 6

72
References
[1]. Antonaia, A., Meena, P., Addonizio, M. L. and Crocchiolo, M., “Transparent
properties of polycrystalline tin oxide films”, Solar Energy Mater. Solar Cells,
Vol. 28(2), pp. 167-173, 1992.
[2]. Brown, R., Maissel, L. I. and Glang, R., “Handbook of Thin Film Technology”,
McGraw Hill, New York, 1970.
[3]. Choudhury, C. and Sehgal, H.K., “Properties of spray deposited cobalt oxide
selective coating on aluminum and galvanized iron substrate”, Appl. Energy, Vol.
10, pp. 313-324, 1982.
[4]. Soliman, L I, Afify, H H and Battisha I K, “Growth impedance of pure CdS
films”, Ind. J. Pure Appl. Phys., Vol. 42, pp. 12-17, 2004.
[5]. Sebastian, T., Jayakrishnan, R., Kartha, C. S. and Vijayakumar, K. P.,
“Characterization of spray pyrolysed CuInS2”, The open Surf. Sci., Vol. 1, pp. 1-
6, 2009.
[6]. Kadam, L. D. and Patil, S. H., “Thickness-dependent propertie of sprayed cobalt
oxide thin films”, Mater. Chem. Phys., Vol. 68, pp. 225-232, 2001.
[7]. Korotcenkov, G., Brinzari, V. and Boris, I., “(Cu, Fe, Co, Ni) doped tin oxide
films deposited by spray pyrolysis: doping influence on film morphology”, J.
Mater. Sci., vol. 43, pp. 2761-2770, 2008.
[8]. Chamberlin, R. R. and Skarman, J. S., “Chemical spray deposition process for
inorganic films”, J. Electrochem. Soc., Vol. 113(1), pp. 86-89, 1966.
[9]. Elangovan, E. and Ramamurthi, K., “Studies on optical properties of
polycrystalline SnO2: Sb thin films prepared using SnCl2 precursor”, Cryst. Res.
Technol., Vol. 38(9), pp. 779-784, 2003.
[10]. Kose, S., Ketenci, E., Bilgin, V., Atay, F. and Akyuz, I., “Some physical
properties of In doped Copper oxide films produced by ultrasonic spray
pyrolysis”, Curr. Appl. Phys., Vol. 12, pp. 890-895, 2012.
73
CHAPTER 5
RESULTS AND DISCUSSION

74
CHAPTER 5
RESULTS AND DISCUSSION
5.1 Introduction
The objectives of this study are to characterize CuO and CuO: Zn thin films
synthesized by SPT. Different characterizations of CuO and CuO: Zn thin films have
been performed by FESEM, EDX, XRD, UV-visible spectroscopy and DC electrical
measurements. Results and discussion on the findings by different characterizations
are outlined in this chapter.
5.2 Surface Morphology

The surface morphology of CuO thin films deposited at the Ts of 300, 350 and 400 ºC
is shown in Figures 5.1 and 5.2. The surface morphology of 1-6 at% CuO: Zn thin
films deposited at Ts = 350 °C is shown in Figures 5.3 and 5.4. For both cases FESEM
images are taken at ×5 k and ×50 k magnifications.
(a)
Figure 5.1(a): FESEM image (×5 k) of CuO thin film deposited at the Ts of 300 °C.
75
(b)
Figure 5.1(b): FESEM image (×5 k) of CuO thin film deposited at the Ts of 350 °C.
(c)
Figure 5.1(c): FESEM image (×5 k) of CuO thin film deposited at the Ts of 400 °C.
76
(a)
Figure 5.2(a): FESEM image (×50 k) of CuO thin film deposited at the Ts of 300 °C.
(b)
Figure 5.2(b): FESEM image (×50 k) of CuO thin film deposited at the Ts of 350 °C.
77
(c)
Figure 5.2(c): FESEM image (×50 k) of CuO thin film deposited at the Ts of 400 °C.
(a)
Figure 5.3(a): FESEM image (×5 k) of CuO: Zn thin film deposited at Ts = 350 °C
with 1at% Zn concentration.
78
(b)
Figure 5.3 (b): FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 350 °C with
2 at% Zn concentration.
(c)
Figure 5.3 (c): FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 350 °C with
79
(d)
Figure 5.3 (d): FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 350 °C with
(e)
Figure 5.3 (e): FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 350 °C with
80
(f)
Figure 5.3 (f): FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 350 °C with
(a)
Figure 5.4 (a): FESEM image (×50 k) of CuO: Zn thin film deposited at Ts = 350 °C
with 1 at% Zn concentration.
81
(b)
Figure 5.4 (b): FESEM image (×50 k) of CuO: Zn thin film deposited at Ts = 350 °C
(c)
Figure 5.4 (c): FESEM image (×50 k) of CuO: Zn thin film deposited at Ts = 350 °C
82
(d)
Figure 5.4 (d): FESEM image (×50 k) of CuO: Zn thin film deposited at Ts = 350 °C
(e)
Figure 5.4 (e): FESEM image (×50 k) of CuO: Zn thin film deposited at Ts = 350 °C
83
(f)
Figure 5.4 (f): FESEM image (×50 k) of CuO: Zn thin film deposited at Ts = 350 °C
For CuO and CuO: Zn thin films, FESEM micrographs reveal that sprayed particles
are adsorbed onto the glass substrate into clusters as the primary stage of nucleation.
Nanoparticles are observed in both CuO and CuO: Zn thin films. These figures show
that the amorphous nature grains covered the entire surface of the film and no well-
defined grain boundaries are observed. It is seen that the films are crack free with
nano-sized particle agglomerates.
50
8 (a) (b)
Average Particle Size (nm)
Average Particle Size (nm)
40
7
30
6
20
5
10
4
300 350 400
0
0 1 2 3 4 5 6 7
Substrate Temperature, Ts (°C) Zn Concentration (at%)
Figure 5.5: Variations of average particle size for (a) CuO thin films with Ts and (b)
CuO: Zn thin films deposited at 350 ºC with Zn concentration.
84
Figure 5.5 shows the average particle size for CuO and CuO: Zn thin films which is
calculated by ImageJ software using FESEM images. The average particle size is
around 5.41 nm for CuO thin films and 13.68 nm for CuO: Zn thin films. In Figure
5.5 (a) it is seen that the average particle size, 7.61 nm for CuO thin film synthesized
at 350 °C is larger, which may be due to more uniformity of the thin film than others.
From Figure 5.5 (b) it is seen that the average particle size is increased with
increasing Zn concentrations. Larger average particle size is 48.49 nm found for 5 at%
CuO: Zn thin film. Bari et al. [1] reported that the average grain size of spray
pyrolyzed CuO is about 30 nm. Similar features about CuO thin films synthesized by
electroplating and aerosol spraying are also reported in two publications [2, 3].
5.3 Elemental Analysis
The elements in CuO and CuO: Zn thin films are confirmed by EDX analyses and the
EDX spectra are shown in Figures 5.6 and 5.7, respectively. In the EDX spectrum for
CuO thin films in Figure 5.6, two strong peaks are observed corresponding to Cu and
O that confirms the formation of CuO thin films. In Figure 5.7 not only Cu and O
peaks are present but also small peaks are present for Zn impurity that confirms the
formation of CuO: Zn thin films.
Figure 5.6: EDX spectrum of CuO thin films.

85
(a)
(b)
Figure 5.7: EDX spectra of CuO: Zn thin films deposited at 350 °C Ts with Zn
concentrations of (a) 1 and (b) 2 at%.
86
(c)
(d)
concentrations of (c) 3 and (d) 4 at%.
87
(e)
(f)
concentrations of (e) 5 and (f) 6 at%.
88
Table 5.1: Data of elemental analysis for CuO and CuO: Zn thin films
Elements in at%
Sample
Cu O Zn
CuO 44.72 55.28 -----
1at%CuO: Zn 27.71 72.05 0.24
2 at% CuO: Zn 24.02 73.80 2.18
3 at% CuO: Zn 23.47 73.50 3.03
4 at% CuO: Zn 10.58 89.39 4.02
5 at% CuO: Zn 8.03 86.55 5.42
6 at% CuO: Zn 15.49 80.41 4.10
Data of elemental analysis for prepared thin films is documented in Table 5.1. From
Table 5.1 it is seen that the deposited thin films are stoichiometric. The atomic
percentage of Cu is decreased with the increase of Zn concentrations up to 5 at% and
then it is increased for 6 at%. EDX report reveals that the highest value of Zn atomic
percentage is 5.42 for 5 at% Zn concentration. The prominent presence of O is
observed in the synthesized films which plays major role in changing the structure
and properties of these thin films.
5.4 X-ray Diffraction Analysis
Figure 5.8 shows the XRD patterns of CuO thin films deposited at the Ts of 300, 350
and 400 °C. XRD patterns of CuO: Zn thin films with Zn concentration of 0, 2, 4, 5
and 6 at% deposited at the Ts of 350 °C are shown in Figure 5.9. In XRD patterns the
characteristic peaks are identified from the JCPDS card no. 01-073-6023 for CuO.
The fundamental peaks are identified as (1̅11) and (111) planes for CuO and CuO: Zn
thin films which indicate the monoclinic structure of CuO. From Figure 5.8 it is seen
that the thin film synthesized at 400 °C has two phases i.e. CuO phase and Cu2O
phase.
89
CuO (111) Ts = 300 ºC

(111)
Intensity (a.u.) (200)
Ts = 350 ºC
(111) Ts = 400 ºC
Cu2O
(200)
30 35 40 45 50 55 60
2 (degree)
Figure 5.8: XRD patterns of CuO thin films deposited at different Ts.
It is seen from Figure 5.8 that the peak intensity hence crystallinity increases with
increasing Ts. Morales et al. [4] noted that the crystallinity increased with increasing
Ts as well as deposition time. It implies that the crystallinity of the CuO thin films is
improved at higher Ts. This may be due to the gain of enough energy by the
crystallites to orient in proper equilibrium sites at high Ts [5, 6].
90
(111) (111) 0 at% Zn

(200)
2 at% Zn
Intensity (counts)
4 at% Zn
5at% Zn
6 at% Zn
30 40 50 60
2 (degree)
Figure 5.9: XRD patterns of CuO: Zn thin films deposited at the Ts = 350 °C.
In Figure 5.9 no corresponding peak for Zn impurity is observed. It may be due to the
replacement of Cu2+ ions in the lattice structure by Zn2+ ions since the ionic radii of
Cu2+ (0.73 Å) and Zn2+ (0.74 Å) are nearly same. Sonia et al. [7] reported that Cu2+ is
replaced by Zn2+ in CuO: Zn nanoflowers prepared by hydrothermal synthesis.
It is also observed from Figure 5.9 that as the Zn concentration increases, the intensity
of the peaks decreases due to less crystallinity, which may have occurred because of
different crystal structures of CuO (monoclinic) and ZnO (wurtzeit). Table 5.2
represents the values of the lattice constants for CuO and CuO: Zn thin films.
91
Table 5.2: Lattice constants for CuO and CuO: Zn thin films
Substrate Temperature, a (Å) b (Å) c (Å) a/b c/b

Ts (°C)
300 4.6847 3.5423 4.7873 1.3225 1.3514
350 4.6847 3.4585 5.0603 1.3545 1.4631
400 (CuO) 4.6847 3.3234 5.2947 1.4096 1.5931
400 (Cu2O) 4.2608 4.2608 4.2608
Zn concentration
2 4.6847 3.4585 5.0603 1.3545 1.4631
4 4.6847 3.4585 5.0603 1.3545 1.4631
5 4.6847 3.4585 5.0603 1.3545 1.4631
6 4.6847 3.3964 5.4291 1.3793 1.5984
The values of lattice parameters a, b and c are unequal for CuO and CuO: Zn thin
films which confirm the monoclinic crystal structure of CuO. For Cu2O phase. CuO
thin film deposited at 400°C has the equal values lattice constants which confirm the
cubic crystal structure of Cu2O. Table 5.2 also represents that all the values of lattice
parameters of CuO: Zn thin films are same as those of CuO thin films prepared at Ts
of 350 °C. The structural parameters of CuO and CuO: Zn thin films like crystallite
size (D), microstrain (ϵ) and dislocation density (δ) of (1̅11) planes are calculated
using equations (3.3), (3.4) and (3.5), respectively and are shown in Table 5.3.
Average values of D are 10.45 nm and 11.34 nm for CuO and CuO: Zn thin films,
respectively.
Table 5.3: Structural parameters of CuO and CuO: Zn thin films for (1̅11) plane
Substrate Crystallite Size, Microstrain, Dislocation

Temperature, Ts (°C) D (nm) ϵ × 10-3 Density,
δ (103/nm2)
300 7.37 6.20 18.37
350 7.90 4.58 16.01
400 18.12 1.99 3.04
Zn concentration (at%) D (nm) ϵ × 10-3 δ (103/nm2)
2 7.53 4.80 17.62
4 10.07 3.42 9.85
5 28.24 1.28 1.25
6 12.23 2.95 6.67
92
From Table 5.3 it is observed that D increases with increasing Ts. ϵ and δ decrease
with increasing Ts for CuO thin films. It implies that crystallization process improved
and smaller crystallites agglomerated with increasing Ts to cause a change in D
distribution towards larger crystallites. In CuO: Zn thin films D increases with
increase of Zn concentration up to 5 at% and ϵ and δ exhibit the reverse behavior of
D. It is observed that the maximum value of D is about 28.24 nm and minimum
values of ϵ and δ are about 1.28 × 103 and 1.25 x 10-3/nm2, respectively for 5 at% of
Zn concentration. Larger D indicates the less dislocation per unit area and minimum
strain inside the crystallite. Decrease of ϵ and δ with Zn concentration indicates less
deformation of the crystallites at higher Zn concentration [8].
5.5 Optical Properties
5.5.1 Transmittance
90
Ts= 300 C
80
Ts= 350 C
70
Transmittance, T (%)
Ts= 370 C
60 Ts= 400 C
50
40
30
20
10
-10
300 450 600 750 900 1050 1200
Wavelength,  (nm)
Figure 5.10: Transmittance vs. wavelength graph of CuO thin films deposited at
different Ts.
Figure 5.10 shows the optical transmittance (T in %) of CuO thin films synthesized at
Ts of 300, 350, 370 and 400 °C. The highest value of T, 77.72%, is found for Ts = 350
°C at 1100 nm. A relatively higher T value for the CuO thin film deposited at Ts of
350 °C may be attributed to less scattering due to the decrease of the degree of
93
irregularity in the particle size distribution. In the visible region, T of CuO thin films
increases sharply with the increase of wavelength. Cho reported that degree of
irregularity was decreased due to less scattering at high T value [9]. Roy et al.
reported that the highest value of T was about 80% for the CuO thin films grown at Ts
= 350 °C [10].
90
80
70
Transmittance, T (%)
60
50
40
30 CuO
1at% Zn
20 2at% Zn
3at% Zn
10 4at% Zn
0 5at% Zn
6at% Zn
-10
300 450 600 750 900 1050 1200
Wavelength,  (nm)
Figure 5.11: Transmittance vs. wavelength graph for0 to 6 at% CuO: Zn thin films
deposited at Ts = 350 °C.
Figure 5.11 represents the optical transmittance vs. wavelength graph for 0 to 6 at%
CuO: Zn thin films deposited at Ts = 350 °C. In the visible region of Figure 5.11 the
value of T increases with the increase of doping concentration up to 5 at% and
decreases at 6 at% of Zn. The decrease of T may be due to decrease of free carrier.
CuO: Zn thin films are highly transparent in NIR region and the maximum T is about
87% for 5 at% Zn concentration.
5.5.2 Absorbance
Figure 5.12 shows the variation of absorbance (A) with wavelength for (a) CuO thin
films deposited at different Ts and (b) 0 to 6 at% CuO: Zn thin films deposited at Ts =
350 °C. In Figure 5.12, it is seen that the absorption starts at wavelength ~ 700 nm.
Figure 5.12 (a) shows that the value of A is highest for the CuO thin films deposited at
94
Ts = 400 °C and lowest for that deposited at Ts = 350 °C of CuO thin films in visible –
NIR region. In Figure 5.12 (b) it is seen that the value of A decreases with the increase
of Zn concentration up to 5 at% and then it increases for 6 at% Zn. However in CuO:
Zn thin films the absorption starts at lower wavelength region ~ 800 nm. This
observation provides the information about the direct band gap.
2.5 2.5
Ts= 300 C CuO
Ts= 350 C 1at% Zn
2.0 2.0 2at% Zn
Ts= 370 C 3at% Zn
Absorbance, A
Absorbance, A
Ts= 400 C 4at% Zn
1.5 1.5 5at% Zn
6at% Zn
1.0 1.0
0.5 0.5
(a) (b)
0.0 0.0
300 450 600 750 900 1050 1200 300 450 600 750 900 1050 1200
Wavelength,  (nm) Wavelength,  (nm)
Figure 5.12: Variation of absorbance with wavelength for (a) CuO thin films
deposited at various Ts (b) 0 to 6 at% CuO: Zn thin films deposited at Ts = 350 °C.
Chaudhary et al. [11] reported that the absorption starts at λ ~ 860 nm in CuO thin
films synthesized at Ts of 350 °C. From Figure 5.12, it is clear that A decreases for
both types of films with the increase in wavelength. This decrease in the absorption
indicates that the presence of optical band gap in the material [12].
5.5.3 Absorption coefficient
Absorption coefficient (α) is calculaed from the A data of Figure 5.12 using the
equation (3.12). Figure 5.13 repesents the variation of α with the photon energy (hν)
for the prepared CuO and CuO: Zn thin films. In both cases initially α increases
slowly at the low energy region and then at high energy region it increases sharply.
But Figure 5.13 (b) indicates that the value of α is high for pure CuO thin film. α is
minimum at lower energy region and increases with increasing hν. Kumar et al. [13]
reported similar behavior of α in case of chemically sprayed CuO thin films.
95
5 5
4x10 4x10
Ts= 300 C
Absorption coefficient,  (cm-1)

CuO
Absorption Coefficient,  (cm-1)

Ts= 350 C
1at% Zn
5
Ts= 370 C 5 2at% Zn
3x10 3x10
Ts= 400 C 3at% Zn
4at% Zn
5at% Zn
5 5 6at% Zn
2x10 2x10
5 5
1x10 1x10
(a) (b)
0 0
1.0 1.5 2.0 2.5 3.0 3.5 4.0 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Photon Energy, h (eV) Photon Energy, h (eV)
Figure 5.13: Variation of absorption coefficient with photon energy for (a) CuO thin
films synthesized at different Ts (b) 0 to 6 at% CuO: Zn thin films synthesized at
Ts = 350 °C.
5.5.4 Optical band gap

The variation of α with hν is analysed following the Tauc relation, equation (3.16), to
evaluate optical band gap of CuO and CuO: Zn thin films. To obtain optical band gap,
(αhν)2 vs. hν plots for CuO thin films synthesized at different Ts and for CuO: Zn thin
films synthesized at Ts = 350 °C with 0 to 6 at% Zn are shown in Figure 5.14.
1.2
Ts= 300 °C
1.0 Ts= 350 °C
Ts= 370 °C
(eV/cm)2
0.8 Ts= 400 °C
0.6
-11
(h) 10
0.4
2
0.2
(a)
0.0
1.0 1.5 2.0 2.5 3.0 3.5
Photon Energy, h (eV)
Figure 5.14 (a): Plots of (αhν)2 vs. hν for CuO thin films synthesized at different TS.
96
0.8
CuO
1at% Zn
2at% Zn
0.6
(eV/cm)2
3at% Zn
4at% Zn
5at% Zn
6at% Zn
0.4

(h) 
2
0.2
(b)
0.0
1.0 1.5 2.0 3.0 3.52.5 4.0
Figure 5.14 (b): Plots of (αhν)2 vs. hν for CuO: Zn thin films synthesized at Ts = 350 °C
with 0 to 6 at% Zn concentration.
From Figure 5.14 the intercept after extrapolation of the linear portion of the curves in
the hν axis at zero α is taken to find out the direct band gap (Eg) of CuO and CuO: Zn
thin films. Eg of CuO and CuO: Zn thin films is presented in Figure 5.15.
2.8 2.9
2.6
Direct Band Gap, Eg (eV)
Direct Band Gap, Eg (eV)
2.8
2.4
2.7
2.2
2.6
2.0
1.8 2.5
(a) (b)
1.6
300 325 350 375 400 2.4
Substrate Temperature, Ts (C) 0 1 2 3 4 5 6 7
Zn Concentration (at%)
Figure 5.15: Variation of direct band gap (a) for CuO with Ts and (b) for CuO: Zn
with Zn concentration (Ts = 350 oC).
97
Figure 5.15 shows that the value of Eg of CuO thin films with Ts and CuO: Zn thin
films with Zn concentration is varied between 1.81 and 2.63 eV and 2.69 and 2.88 eV,
respectively. It is reported that the value of Eg of CuO thin films obtained by chemical
deposition is varied from 1.80 to 2.40 eV [14] and that prepared by RF plasma
sputtering is found from 2.10 to 2.55 eV [15]. Eg of CuO: Zn thin films deposited by
PLD and SPT techniques is reported to be 1.95 to 2.50 eV [16] and 1.92 to 1.95 eV
[17], respectively. In Figure 5.15(a) , for CuO thin films the value of Eg decreases
with the increase of Ts. When the value of Ts increases the amplitude of atomic
vibrations also increases leading to larger interatomic spacing. The interaction
between the lattice phonons and the free electrons and holes may also affect the Eg to
a smaller extent. One of the mechanisms for electrons to be excited to the conduction
band is due to thermal energy and the conductivity of semiconductors is strongly
dependent on the Ts of the thin films [18]. Eg is slightly increased with doping
concentration increase up to 5 at% Zn and then it is dereases for 6 at% Zn. Increase of
Eg may be attributed to the Burstein-Moss (B-M) shift [19]. B-M effect states that in a
heavily doped semiconductor the donor electrons occupy energy levels at the bottom
of the conduction band. Pauli principle prevents energy states from being doubly
occupied. Thus the valence electrons require an additional energy to be excited to the
higher energy states in the conduction band to conserve linear momentum, as a result
Eg is shifted.
5.5.5 Refractive Index
The refractive index (n) has been calculated using the equation (3.27) from the
reflectance and extinction co-efficient obtained from absorbance data. The variation
of n with wavelength for CuO and CuO: Zn thin films are shown in Figure 5.16. n is
found to be 1.33 - 2.60 for CuO and those are 1.19 - 2.62 for CuO: Zn thin films.
98
2.8 2.8
2.4 2.4
Refractive Index, n
2.0
Refractive Index, n
2.0
1.6 1.6
CuO
1.2 1.2 1at% Zn
2at% Zn
Ts= 300 C 3at% Zn
0.8 Ts= 350 C 0.8 4at% Zn
Ts= 370 C 5at% Zn
0.4 0.4 6at% Zn
Ts= 400 C (a) (b)
0.0 0.0
600 800 1000 1200 400 600 800 1000 1200
Figure 5.16: Variation of refractive index (a) for CuO thin films with wavelength
deposited at various Ts and (b) for CuO: Zn thin films with wavelength at various Zn
concentrations (Ts = 350 ºC).
It is evident from Figure 5.16(a) that n has lowest values for Ts = 350 °C in the
wavelength range of 750 – 1100 nm. When the incident light interacts with a material
which has low number of particles, the refraction is low, and thus the refractivity of
the film decreases [20]. Figure 5.16(b) also exhibits that n decreases with the increase
of Zn incorporation up to 5 at% in the wavelength range 750 – 1100 nm. In that
wavelength region, higher n is found for 6 at% CuO: Zn thin films. Lower value of n
in CuO: Zn thin film with higher concentration of Zn reveals that light moves faster
through these thin films.
5.5.6 Extinction coefficient
Extinction coefficient (k) is calculated using equation (3.28) from absorption

coefficient data. The variation of k with wavelength for deposited thin films is shown
in Figure 5.17.
99
1.0 1.0
Ts= 300 C CuO
Ts= 350 C 1at% Zn
Extinction coefficient, k
Extinction coefficient, k
0.8 0.8 2at% Zn
Ts= 370 C 3at% Zn
Ts= 400 C 4at% Zn
0.6 0.6 5at% Zn
6at% Zn
0.4 0.4
0.2 0.2
(a) (b)
0.0 0.0
300 450 600 750 900 1050 1200 300 450 600 750 900 1050 1200
Figure 5.17: Variation of extinction coefficient with wavelength (a) for CuO thin films
synthesized at various Ts and (b) for CuO: Zn thin films with various Zn
Figure 5.17 shows that k decreases with increaseing wavelength. The values of k vary
between 0.14 and 0.93. The high value of k indicates the high surface roughness of
the deposited samples. The rise and fall in k is directly related to the absorption of
light. The fall in k may be due to the absorption of light at the grain boundaries. This
result is very close to the reported value by others [21]. In figure 5.17 (a), the lower
value of k is observed for CuO thin film synthesized at 350 °C. In Figure 5.17 (b), the
k decreases due to Zn doping and lower values of k is found for 5 at% CuO: Zn thin
film up to 800 nm and above that the lower values of k are observed for 4 at% CuO:
Zn thin film.
5.5.7 Optical conductivity

Optical conductivity (σopt) is calculated from equation (3.29). Figure 5.18 exhibits the
variation of σopt with h for the deposited thin films. σopt is increased at high photon
energies due to the high absorbance in that region. This is may be due to the increase
of band gap [2]. It is a frquency dependent quantity which is inversely related to the
Eg values. As 5 at% CuO: Zn thin film has high Eg, it shows minimum conductivity at
lower photon energy region.
100
0.5
-11
Optical Conductivity, opt (s )10
0.4
-1
0.3
Ts= 300 C
0.2 Ts= 350 C
Ts= 370 C
Ts= 400 C
0.1
(a)
0.0
1.0 1.5 2.0 2.5
0.5
-11
Optical Conductivity, opt (s ) 10
0.4
-1
0.3
CuO
0.2 1at% Zn
2at% Zn
3at% Zn
4at% Zn
0.1 5at% Zn
6at% Zn
(b)
0.0
1.0 1.5 2.0 2.5 3.0 3.5
Figure 5.18: Variation of optical conductivity with photon energy for (a) CuO thin
films deposited at different Ts and (b) CuO: Zn thin films with 0 to 6 at% Zn
concentrations deposited at Ts = 350 °C.
5.5.8 Dielectric constants
The dielectric constant is a fundamental intrinsic material property. The real εr and
imaginary εi parts of the dielectric constant are determined using the formula (3.22).
101
The variation of the real (εr) and imaginary (εi) parts of the dielectric constant are
illustrated in Figures 5.19 and 5.20, respectively for CuO and CuO: Zn thin films.
8 8
Dielectric Constant, r
Dielectric Constant, r
6 6
4 4
Ts= 300 C
Ts= 350 C CuO
1at% Zn
2 Ts= 370 C 2 2at% Zn
Ts= 400 C 3at% Zn
4at% Zn
(a) 5at% Zn (b)
6at% Zn
0 0
600 750 900 1050 1200 300 450 600 750 900 1050 1200
Figure 5.19: Variation of real part of dielectric constant with wavelength (a) for CuO
thin films deposited at various Ts and (b) for CuO: Zn thin films with various Zn
2.4 2.0
CuO
1at% Zn
Dielectric Constant, i
Dielectric Constant, i
2.0
1.6 2at% Zn
3at% Zn
1.6 4at% Zn
1.2 5at% Zn
6at% Zn
1.2
0.8
0.8
Ts= 300 C
Ts= 350 C 0.4
0.4
Ts= 370 C (b)
(a)
Ts= 400 C
0.0 0.0
600 750 900 1050 1200 300 450 600 750 900 1050 1200
Figure 5.20: Variation of imaginary part of dielectric constant with wavelength (a) for
CuO thin films deposited at various Ts and (b) for CuO: Zn thin films with various Zn
εr represents the magnitude of polarization of a material i.e. it is associated with the
property of slowing down the speed of light in the material. If the frequency of the
incoming light resonates with the oscillatory frequency of the atoms or electrons of
the medium, resonant oscillations occur and light is absorbed by the medium. As a
102
result, εr shows a peak value for the particular frequency or wavelength. The variation
of εr depends upon the frequency of the incoming light. εr shows the maximum value
of about 6.685 at 720 nm for CuO thin films deposited at Ts = 350 °C. εi shows the
same behavior as that of the εr, the only difference is that these values seem to be very
low as compared to that of εr values. For CuO thin films deposited at various Ts, εi
increases up to 620 nm except for CuO thin films synthesized at Ts = 400 °C then
decreases slowly. Also, εr increases with increasing wavelength up to 720 nm, then
begins a downward thereafter and εr decreases with Zn doping up to 5 at% and
increases for 6 at% Zn doping in CuO thin films. Similar type of dielectric properties
is reported for CuO thin films synthesized by CBD by other researchers [22]. From
both Figures 5.19 and 5.20 it is seen that all the films have nearly equal values of
dielectric constant.
5.5.9 Dielectric Loss
Dielectric loss is a loss of energy that goes into heating a dielectric material in a
varying electric field. The dielectric loss tangent (tanδ) has been calculated using the
relation tanδ = εi/εr. tanδ of CuO and CuO: Zn thin films are plotted against
wavelength in Figure 5.21.
1.0 1.0
Ts= 300 C CuO
Ts= 350 C 1at% Zn
0.8 0.8 2at% Zn
Ts= 370 C
3at% Zn
Ts= 400 C
4at% Zn
0.6 0.6 5at% Zn
tan
6at% Zn
tan
0.4 0.4
0.2 0.2
(a) (b)
0.0 0.0
600 750 900 1050 1200 300 450 600 750 900 1050 1200
Figure 5.21: Variation of dielectric loss with wavelength for (a) CuO thin films
synthesized at different Ts and (b) CuO: Zn thin films with 0 to 6 at% Zn
concentration synthesized at Ts = 350 °C.
103
Figure 5.21(a) shows that the lowest value of tanδ is found for CuO thin film
synthesized at Ts of 350 °C. In Figure 5.21 (b), for CuO: Zn thin films tanδ decreases
with the increase of Zn doping up to 5 at% and then it increases in the case of 6 at%
Zn concentration. From tanδ vs. wavelength curves it is also observed that the values
of tanδ gradually decrease with the increase of wavelength.
5.6 Electrical Properties
5.6.1 Current – Voltage characteristics
Figure 5.22 shows the current-voltage (I-V) characteristics of CuO and CuO: Zn thin
films. The I-V characteristics data are taken over the range of applied voltage 1-20 V
at the room temperature. All the samples show ohmic nature.
-6
5.0x10
-6
4.0x10
Current, I (A)
-6
3.0x10
-6 Ts= 300 °C
2.0x10
Ts= 350 °C
Ts= 370 °C
-6
1.0x10 Ts= 400 °C
(a)
0.0
0.0 0.5 1.0 1.5
Voltage, V (V)
Figure 5.22 (a): Plots of I-V characteristics for synthesized CuO thin films.
104
-6
5.0x10
-6
4.0x10
Current, I (A)
-6
3.0x10
-6 CuO
2.0x10 1at% Zn
2at% Zn
3at% Zn
-6
1.0x10 4at% Zn
5at% Zn
(b) 6at% Zn
0.0
0.0 0.5 1.0
Voltage, V (V)
Figure 5.22 (b): Plots of I-V characteristics for synthesized CuO: Zn thin films (Ts =
350 ºC)
12 5
Resistivity,  x 10-3 (-m)
Resistivity,  x 10-3 (-m)
4
8
4
2
(a)
(b)
0 1
300 325 350 375 400 0 1 2 3 4 5 6
Substrate Temperatue, Ts (C) Zn Concentration (at%)
Figure 5.23: Variation of resistivity of (a) CuO thin films with different Ts and (b)
CuO: Zn thin films with different Zn concentrations (Ts = 350 °C).
Room temperature resistivity (ρ) of CuO and CuO: Zn thin films are shown in Figure
5.23. It is seen that the CuO thin film prepared at Ts of 350 °C has the lowest value of
ρ which is 1.54 x 103 Ω-m. Over this optimum Ts ρ increases due to the absorption of
oxygen from air. For the thin films or nanoparticles prepared by SPT reported that
105
oxygen becomes one of the most important background impurities that are easily
diffusing the crystal lattice during the deposition of the films or annealing process in
air at elevated temperatures [23]. The value of ρ increases with increase in Zn
concentration up to 4 at% in CuO: Zn thin films. It can be explained as i) the
concentration of free carriers in p-type CuO films are compensated with Zn
incorporation because Zn acts as an donor atom, i.e., when the free electron
concentration in the conduction band increases with Zn incorporation, the free hole
concentration in the valance band decreases to provide charge valence; ii) scattering
of the carriers at grain boundaries seems to be plausible, because this scattering
mechanism is responsible for the decrease of carrier mobility and hence the increase
of resistivity [17]. The lowest value of ρ is found to be 1.51 x 103 Ω-m for 5 at%
CuO: Zn thin film. Increase of Zn content in the CuO: Zn films beyond 5 at% results
in a degradation of ρ. This is probably attributed to the solubility limit of Zn into the
CuO lattice.
5.6.2 Electrical conductivity and activation energy
Temperature dependent electrical conductivity (σ) is evaluated from the calculation of

ρ using equation (3.35). The variations of σ with inverse of absolute temperature (1/T)
for CuO and CuO: Zn thin films are presented in Figure 5.24.
-2 -2
10 10
-1
Electrical Conductivity,(m)-1
Electrical Conductivity,  (m)
-3 -3
10 10
1at% Zn
(b)
2at% Zn
Ts= 300 C 3at% Zn
4at% Zn
Ts= 350 C 5at% Zn
Ts= 370 C 6at% Zn
-4 -4
10 Ts= 400 C 10
2.2 2.4 2.6 2.8 -1 3.0 3.2 3.4 2.2 2.4 2.6 2.8 3.0 3.2 3.4
1000/T (K ) 1000/T (K-1)
Figure 5.24: Variation of electrical
(a)conductivity with 1000/T (a) for CuO thin films
synthesized at different Ts and (b) for CuO: Zn thin films with different Zn
concentrations (Ts = 350 °C).
106
0.28 0.5
 E in lower temperature region
E in higher temperature region
Activation Energy, E (eV)

Activation Energy, E (eV)
0.24
0.4
0.3
0.20
0.2
0.16 (b)
0.1
(a)
0.12
300 325 350 375 400 0.0

1 2 3 4 5 6
SubstrateTemperature, Ts (C) Zn Concentration (at%)
Figure 5.25: Variation of activation energy of CuO thin films (a) at different Ts and
(b) with different Zn concentrations at Ts = 350 °C.
The slopes of the curves of Figure 5.24 are used to calculate ΔE using equation (3.38).
Figure 5.25 illustrates ΔE values of CuO and CuO: Zn thin films. Figure 5.25 (a)
shows that ΔE of CuO thin films decreases with the increase of Ts. The value of ΔE is
found between 0.12 and 0.26 eV for CuO thin films. Figure 5.25 (b) shows that ΔE for
CuO: Zn thin films are divided into two regions i.e. lower temperature region and
higher temperature region. In the lower temperature region, Zn concentration has no
significant effect on ΔE. All the films have nearly equal value of ΔE. In higher
temperature region, ΔE is decreased for 2 at% CuO: Zn thin films and then it is
increased with increasing Zn concentration. Higher value of ΔE indicates that reaction
is very sensitive to temperature. The low values of ΔE with the localized levels due to
the absorption of carriers from acceptor level to the valence band. The values of ΔE
are found to be from 0.06 to 0.39 eV for CuO: Zn thin films in both lower and higher
temperature regions. In lower temperature region, the conduction mechanism may
occur due to impurity scattering and at higher temperature region, the conduction
mechanism may be due to free band transition in semiconductor [24].
107
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properties of electroplated CuO thin films”, J. Nanosci. Nanotech., Vol. 13, pp.
250-259, 2013.
[3]. Singh, I. and Bedi, R. K., “Studies and correlation among the structural,
electrical and gas response properties of aerosol spray deposited self assembled
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pyrolysis in lithium cells”, Thin Solid Films, Vol. 474, pp. 133-140, 2005.
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40(1), pp. 49–54, 2007.
[6]. Ghosh P. K., Maity R., and Chattopadhyay K. K., “Electrical and optical
properties of highly conducting CdO:F thin film deposited by sol–gel dip
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[7]. Sonia, S., Annsi, I., J., Kumar, P., S., Mangalaraj, D. and Viswanathan, C.,
“Hydrothermal synthesis of novel Zn doped CuO nanoflowers as an efficient
photodegradation material for texile dyes”, Mater. Lett., Vol. 144, pp. 127-130,
2015.
[8]. Jabbar, R. H., Elttayef, A. K., Jabor, A. A. and Hashim, A. H., “Structural
properties of boron doped zinc oxide films prepared by spray pyrolysis
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[9]. Cho, S., “Optical and electrical properties of CuO thin films deposited at several
growth temperatures by reactive RF magnetron sputtering”, Met. Mater. Int.,
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copper oxide thin films synthesized by spray pyrolysis technique”, Sensor.
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[12]. Rejith, S. G. and Krishnan, C., “Optical characterizations of Zn-doped CuO
nanoparticles”, Sciencia Acta Xaveriana, Vol. 4(1), pp. 91-98, 2013.
[13]. Kumar, A. S., Perumal, K. and Thirunavukkarasu, P., “Structural and optical
properties of chemically sprayed CuO thin films”, Opt. Adv. Mater. – R. Com.,
Vol. 4(6), pp. 831-833, 2010.
[14]. Johan, M., R., Suan, M., S., M., Hawari, N., L. and Ching, H., A., “Annealing
effects on the properties of copper oxide thin films prepared by chemical
deposition”, Int. J. Electrochem. Sci., Vol. 6, pp. 6094-6104, 2011.
[15]. Adnan, R., Elttayef, A., K. and Zubaidi, A., K., A., A., “Optical properties of
(CuO) thin films prepared by (R.F.) plasma sputtering”, Wassit. J. Sci. Med.,
Vol. 7(4), pp. 265-276, 2014.
[16]. Faiz, H., Siraj, K., Rafique, M. S., Naseem, S. and Anwar, A. W., “Effect of
zinc induced compressive stresses on different properties of copper oxide thin
films”, Ind. J. Phys., Vol. 89(4), pp. 353–360, 2015.
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38(6), pp. 787-796, 2009.
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J.P., “Electrochemical deposition and characterization of cupric oxide thin
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[23]. Banyamin, Z., Y., Kelly, P., J., West, G. and Boardman, J., “Electrical and
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110
CHAPTER 6
CONCLUSIONS AND SUGGESTIONS FOR FUTURE WORK
111
CHAPTER 6
CONCLUSIONS AND SUGGESTIONS FOR FUTURE WORK
6.1 Conclusions
In this research work, CuO thin films are deposited on glass substrates at different Ts,
300, 350, 370 and 400 °C and CuO: Zn thin films are deposited at Ts of 350 °C by SPT.
The concentration of Zn in CuO thin films is varied between 1 and 6 at%. Thickness of
the films is measured in the range of 144 to 190 nm. The influence of Ts on structural,
optical and electrical properties of CuO thin films and the effect of Zn concentration on
the same properties of CuO: Zn thin films are investigated. The results of the present
work are summarized and the following noteworthy conclusions are drawn.
In FESEM micrographs, both CuO and CuO: Zn thin films nanoparticles are observed
for. It is seen that the particles covered the entire surface of the film and no well-defined
grain boundaries are observed. Larger size nanoparticles are observed for CuO thin
films deposited at 350 °C. Highest nanoparticle size, 48.49 nm is found for 5 at% Zn
concentration of CuO: Zn thin films. EDX analysis reveals that the all synthesized films
are stoichiometric.
XRD patterns confirm that the films are monoclinic in structure with preferred
orientation of (1̅11) plane. In CuO thin films crystallinity improved with increasing Ts.
For CuO: Zn thin films no corresponding peak for Zn impurity is observed. It is also
observed that the crystallinity decreases as the Zn concentration increases. Maximum
value of crystallite size is found about 28.24 nm for 5 at% CuO: Zn thin film.
From UV-Vis-NIR spectroscopic measurements, it is seen that all the synthesized films
are highly transparent in the NIR region. 77.72% is the highest value of T for CuO thin
films deposited at Ts = 350 °C and the maximum T is about 87% for 5 at% CuO: Zn
thin films. Direct band gap of CuO thin films decreases with increasing Ts and it
increases with increasing Zn concentration up to 5 at% in CuO: Zn thin films. n
decreases with increasing Ts up to 350 °C in CuO thin films and also increases with Zn
concentration up to 5 at% in CuO: Zn thin films in the NIR region. k decreases with
increasing Ts up to 350 °C in CuO thin films and with Zn concentration up to 5 at% in
CuO: Zn thin films.
The lowest room temperature ρ at is about 1.54x103 ohm-m for CuO thin film prepared
at Ts = 350 °C and that for1.51x103 ohm-m for 5 at% CuO: Zn thin film. For CuO thin
112
films ΔE decreases as the Ts increase. In lower temperature region, Zn concentration

has no substantial effect on ΔE for CuO: Zn thin films. In higher temperature region,
ΔE decreases at 2 at% and then it is increased slowly with increasing Zn concentrations
in CuO: Zn thin films.
From the investigations of the optical and electrical properties, it can be seen that the
band gap can be increased keeping electrical resistivity similar to that of the pure CuO.
Thus, it can be inferred from the outcome of this research work that the films may be
useful in solar cell, gas sensors and optoelectronic devices.
6.2 Suggestions for Future Work
More investigations are needed to explain different characteristics elaborately, which

will help to find out the suitable applications of CuO: Zn thin films. For further
understanding of this material the following studies may be carried out:
1) Study of the surface roughness by Atomic Force Microscopy.

2) Study of the composition analysis by X-ray Photoelectron Spectroscopy.
3) Study of the variation of the structural, optical and electrical properties of the
CuO: Zn thin film with annealing temperature and deposition time.
4) Study of Hall effect and temperature dependence of hall mobility and carrier
concentration.
5) Study of the magnetic properties i.e. magnetic susceptibility, paramagnetic
resonance, etc.

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CHARACTERIZATION OF ZINC DOPED COPPER

OXIDE THIN FILMS SYNTHESIZED BY SPRAY

A dissertation submitted to the Department of Physics of Bangladesh

Signature of the candidate

2.3.4.3 The channel stage 35

3.1 Structural Characterization 40

4.8.2 Spray rate 69

6.1 Conclusions 111

Figure 1.1 Crystal structure of monoclinic CuO. 6

Figure 5.3(b) FESEM image (×5k) of CuO: Zn thin film deposited at Ts = 78

Table 1.1 Thin Film Application 3

1.2 Applications of Thin Films

1.3 Oxide Semiconductors

1.3.1 Copper Oxide

CuO is an oxide semiconductor material. It is an important transition metal oxide. It has

 Molecular Formula : CuO

1.3.2 Crystal Structure of CuO

Figure 1.1: Crystal structure of monoclinic CuO.

 Atomic Mass : 65.37 g/mol

1.5 Review of Earlier Research Works on Copper Oxide Thin Films

Figure 1.2: X-ray diffraction Figure 1.3: SEM micrographs of

Figure 1.6: UV-Visible transmittance spectrum of CuO thin films deposited at

Figure 1.7: Variation of optical band gap of CuO films [19].

Figure 1.10: XRD pattern of the CuO

Figure 1.12: XRD patterns of CuO thin films deposited on conducting

Figure 1.14: Optical transmittance vs. Figure 1.15: Variation of resistivity

Figure 1.16: XRD diffractograms of Undoped CuO sprayed thin films

Figure 1.17: Band gap of undoped sprayed CuO at different concentrations

Figure 1.18: XRD patterns of In Figure 1.19: (hn)2 vs h variations

1.6 Objectives of The Present Work

(1) To prepare CuO thin films at different Ts.

(8) To calculate activation energies of carriers for electrical conduction of the

1.7 Outline of This Thesis

Chapter 1 represents the General Introduction of this thesis.

Chapter 3 gives the Thin Film Characterization Techniques.

Chapter 5 contains the Results and Discussion of this research work.

Chapter 6 includes the Conclusions and Suggestions For Future Work.

THIN FILM DEPOSITION PROCESSES AND IT’S FORMATION

THIN FILM DEPOSITION PROCESSES AND IT’S FORMATION

2.2 Thin Film Deposition Processes

Table: 2.1: Thin film deposition processes

Physical deposition processes Chemical deposition processes

2.2.1 Physical deposition processes

Physical deposition processes conduct mechanical, electromechanical or

The material to be deposited is placed in an energetic, entropic environment, so that

2.2.1.1 Physical vapor deposition

Figure 2.1: A diagram of physical vapor deposition process.

PVD process proceeds along the following sequence of steps:

2.2.1.2 Thermal evaporation

Figure 2.2: Schematic diagram of thermal evaporation system.

If a surface of target material is bombarded with energetic particles, it is possible to

Figure 2.3: A diagram of a sputtering system.

2.2.1.4 Pulsed laser deposition

Figure 2.4: A diagram of pulsed laser deposition system.

2.2.2 Chemical deposition processes

2.2.2.1 Chemical vapor deposition

Chemical vapor deposition (CVD) can be defined as a material synthesis method in

Figure 2.5: Schematic diagram of a CVD process.

2.2.2.2 Chemical bath deposition

Figure 2.6: Diagram of a CBD system.

2.2.2.3 Sol – gel technique

 The chemical reactants for sol-gel process can be conveniently purified by

Figure 2.7: Generalized scheme of sol-gel technique.

2.2.2.4 Spray pyrolysis technique