Morphology control of ZnO nanorods by chemical bath

deposition

Muhammad Ikram

DIVISION OF SCIENCE & TECHNOLOGY

UNIVERSITY OF EDUCATION
LAHORE
2017
 Morphology control of ZnO nanorods by chemical bath
deposition

MUHAMMAD IKRAM
MSCPHYS-F15-M12
MSc. Physics -2017

A thesis submitted in partial fulfillment of the requirements for the award

of the degree of M.Sc. Physics.

DIVISION OF SCIENCE & TECHNOLOGY

UNIVERSITY OF E0DUCATION
LAHORE
2017
I hereby declare that I have read this thesis and in my opinion this thesis is sufficient in
terms of scope and quality for the award of the degree of M.Sc. Physics.

Signature: _____________________________

Name of supervisor: Dr. Muhammad Saeed Akhtar

Date:
 I

DECLARATION

I declare that this thesis entitled “Morphology Control of ZnO Nanorods By

Chemical Bath Deposition” is the result of my own research except as cited in the
references. The thesis has not been accepted for any degree and not concurrently
submitted in candidature for any other degree.

Signature: ___________________________

Name: MUHAMMAD IKRAM

Date:
 II

ACKNOWLEDGEMENT

I would like to thank my Supervisor Dr. Muhammad Saeed Akhtar who guided me
throughout this research project “Morphology control of ZnO Nanorods By
Chemical Bath Deposition” work. Without his motivation and keen interest, I was not
able to do this project. He is a Competent faculty member of Division of Science and
Technology. Secondly, I would like to thank the department of Physics and Division of
Science and Technology of University of Education which gave me this opportunity
and facilitate me for the project work.

Muhammad Ikram
 III

ABSTRACT

The ZnO thin films were grown onto glass substrate by chemical bath deposition(CBD)
from solutions containing Zinc nitrate hexahydrate and Hexamethylenetetramine with
continuous stirring in the circulating water bath. Structural and morphological analysis
of the films was studied. X-ray diffraction results showed polycrystalline wurtzite
hexagonal structure with (0 0 2) preferred orientation. Scanning electron microscopy
(SEM) results showed compactly aggregated nanorods with increasing diameter as we
increase the concentration of the precursor. The ZnO thin films have attracted
considerable attention because of their typical properties such as wide direct band gap
and high optical transparency in the visible range. Zinc oxide has direct optical energy
band gap which is large enough to transmit most of useful solar radiation. Besides ZnO
is a transparent semiconductor in both the visible and a part of the UV ranges.
Furthermore, it is inexpensive because of abundance in the nature. ZnO nanorod thin
films may also be applied in photovoltaic devices due to its larger band gap than that
of the bulk material.
 IV

Table of Contents
DECLARATION ________________________________________________________ I
ACKNOWLEDGEMENT _________________________________________________ II
ABSTRACT __________________________________________________________ III
LIST OF FIGURES _____________________________________________________ VI
LIST OF TABLES _____________________________________________________ VII
LIST OF ABBREVIATIONS _____________________________________________ VIII
1.1. Beginning of Nanotechnology _____________________________________ 1
1.2 One-dimensional nanomaterials ___________________________________ 2
1.3 Importance of 1-D ZnO Nanomaterials ______________________________ 2
1.4 Properties of ZnO________________________________________________ 3
1.4.1 Mechanical Properties of ZnO (1-D) Nanomaterial ______________________ 3
1.4.2 Electrical Properties of ZnO Nanomaterial _____________________________ 4
1.4.3 Optical Properties of ZnO (1-D) Nanomaterial __________________________ 5
1.5 Synthesis of ZnO Nano-materials ___________________________________ 5
1.6 Application of ZnO nanomaterials __________________________________ 6
1.6.1 ZnO based Sensors _______________________________________________ 7
1.6.2 Spintronics ______________________________________________________ 7
1.6.3 Piezoelectricity __________________________________________________ 7
1.7 Objective of the Thesis ___________________________________________ 8
1.8 Organization of the thesis _________________________________________ 8
Chapter 2 Literature review _______________________________________ 9
2.1 Literature Review _______________________________________________ 9
CHAPTER 3 RESEARCH METHDOLOGY_________________________________ 23
3.1 Introduction to Nanoparticle manufacturing_________________________ 23
3.2 Nanoparticles Manufacturing Approaches __________________________ 23
3.2.1 Top-Down Approach _____________________________________________ 23
3.2.2 Bottom-up Approaches ___________________________________________ 23
3.3 Electrodeposition_______________________________________________ 24
3.4 Chemical Bath Deposition ________________________________________ 25
3.4.1 Advantages of CBD ______________________________________________ 25
3.4.2 Disadvantages of CBD ____________________________________________ 25
 V

3.4.3 Factors Affecting CBD ____________________________________________ 25

3.4.4 Synthesis of ZnO nanorods by CBD __________________________________ 25
3.5 Experimental Procedure _________________________________________ 26
3.5.1 Preparation of the substrate_______________________________________ 26
3.5.2 Substrate cleaning _______________________________________________ 26
3.5.3 3.5.4 Preparation of solution for substrate deposition __________________ 26
3.5.4 ZnO deposition _________________________________________________ 27
3.5.5 ZnO NR growth process ___________________________________________ 28
3.6 Characterization techniques ______________________________________ 29
3.6.1 X-ray Diffraction (XRD) ___________________________________________ 29
3.6.2 Scanning Electron Microscope (SEM) ________________________________ 31
CHAPTER 4 RESULTS AND DISCUSSION _____________________________ 35
4.1 Structural Analysis of ZnO Nanorods _______________________________ 35
4.1.1 Structure parameter ______________________________________________ 35
4.1.2 X-ray diffraction analysis __________________________________________ 37
4.2 Morphology of ZnO Nanorods ____________________________________ 42
4.2.1 SEM Analysis ___________________________________________________ 42
CONCLUSION________________________________________________________ 46
REFERENCES ________________________________________________________ 47
4.2.2 __________________________________________________________________ 51
 VI

LIST OF FIGURES

Figure No. CAPTION PAGE No.

Figure 3.1 A simple electrolytic cell 24

Figure 3.2 CBD apparatus for synthesis of ZnO nanorods 28

Figure 3.3 Flow chart of synthesis and experimental setup 29

Figure 3.4 Bruker D8 Advance X-ray diffraction machine 30

Figure 3.5 X-ray Diffraction in accordance with Bragg’s Law 31

Figure 3.6 Schematic diagram of SEM 32

Figure 3.7 Scanning electron microscope 33

Figure 4.1 XRD pattern of ZnO nanorods for concentration 0.1 to 38

0.4M.

Figure 4.2 SEM image of ZnO nanorods obtained at 0.1 Molar 42

concentration

Figure 4.3 SEM image of ZnO nanorods obtained at 0.2 molar 43

concentration

Figure 4.4 SEM image of ZnO nanorods obtained at 0.3molar 44

concentration

Figure 4.5 SEM image of ZnO nanorods obtained at 0.4 molar 45

concentration.
 VII

LIST OF TABLES

Table No. TITLE PAGE No.

Table 4.1 Measured intensities 39

Table 4.2 Texture coefficient at 0.1M ,0.2M,0. 3M and 0.4M 40

Table 4.3 Standard Lattice parameter 41

 VIII

LIST OF ABBREVIATIONS

ZnO Zinc oxide

HMTA Hexamethylene tetramine

SEM Scanning electron microscope

XRD X-ray diffraction

1-D One dimensional

STM Scanning Tunneling Microscope

HRTEM High Resolution Transmission Microscope

𝐙𝐧(𝐍𝐎𝟑 )𝟐 . 𝟔𝐇𝟐 𝐎 Zinc nitrate hexahydrate

DI De ionized

JCPDS Joint Committee of Powder Diffraction Standards

FWHM Full Width at Half Maximum

SE Secondary Electron

BSE Backscattered Electrons

 1
INTRODUCTION

CHAPTER 1 INTRODUCTION

1.1. Beginning of Nanotechnology

Nanotechnology is a new approach that refers to understanding and properties of matter

at Nano scale: 1 Nano meter is equal to one billionth of matter, is a length of a small
molecule. At this scale matter exhibits numerous properties and the borders between
established scientific and technical disciplines fade. Hence the strong interdisciplinary
character that is associated with nanotechnology. Nanotechnology was firstly
introduced since the Nobel Prize winner Richard Feynman’s talk “there is plenty of
room at the bottom” at Caltech on December 29, 1959. He describes the process by
which the ability to manipulate individual atoms and molecules might be developed,
using one set of precise tools to build and operate and other proportionally smaller set,
so on down to the needed scale. After 20 years later people realized that the importance
of Feynman’s prediction and started the new era of Nano science and Nanotechnology
with the invention of high resolution machines like scanning electron microscope
(SEM), high resolution transmission microscope (HRTEM), which led to the discovery
of allotropes of carbon first identified in 1985, (they have varying numbers of atoms
bonded in structures having 12 pentagonal and 2 or more hexagonal faces)(Kroto,
Heath, O'Brien, Curl, & Smalley, 1985) and carbon Nanotubes (CNT) in another
development the preparation and properties of semiconductor nanomaterials including
quantum dots and nanowires are studied on a large scale and numerous breakthroughs
and achievements in nanoscience have been made (Wang & Song, 2006).A more
generalized description of nanotechnology was subsequently established by the
National Nanotechnology Initiative. Which defines nanotechnology as the
manipulation of matter with at least on-dimension sized from one to 100 nanometers.
This definition reflects the fact that quantum mechanical effects are important at this
quantum realm scale, and so the definition shifted from a particular technological goal
to research category inclusive of all type of research and technologies that deal with the
special properties of matter which occur below the given size threshold. Because of the
variety of potential applications (including industrial and military) the US governments
have invested billions of dollars in nanotechnology research. Until 2012, through its
national nanotechnology initiative, the USA has invested 3.7 billion dollars, the
 2

INTRODUCTION

European union has invested 1.2 billion and Japan 750 million dollars.(Gwilliam,
2012) That NNI is a US government research and development (R&D) initiative
involving the nanotechnology-related of 20 departments and agencies. NNI envisions a
future in which applications of nanotechnology will led to a revolution in technology
and industry that benefits society. Program components areas (PCAs) are the major
subject areas under which the NNI groups related nanotechnology R&D projects and
activities the 2017 federal budget provides more than $1.4 billion for the national
technology initiative (NNI), affirming the important role that nanotechnology continues
to play in the administration’s innovation agenda. A visual over view of national
nanotechnology initiative is given below.

1.2 One-dimensional nanomaterials

One-dimensional (1-D) nanomaterials change their properties dramatically with the

minor change of morphology and structure at Nano-scale than bulk materials. For
example, carbon nanotubes are found to be stiffest materials on earth so for, in terms of
tensile strength and elastic modulus respectively, and both are about 10 times larger
than those of stainless steel (Song, Wang, Riedo, & Wang, 2005) nanomaterials are the
basic building blocks of Micro-Electro-Mechanical systems (MEMS) and future Nano-
Electro-Mechanical systems (NEMS). In order to pave the path for further industrial
and security applications, the need to characterize the physical, chemical, electrical and
optical properties of 1-D nanomaterials becomes essential and important in the current
research (Song, et al., 2005).

1.3 Importance of 1-D ZnO Nanomaterials

One-dimensional (1-D) have novel and unique properties and a wide range of
applications because of this it has attained a lot of attention. ZnO nanomaterials are the
most important nanomaterials due to their special properties that depends on the
morphology and structure of ZnO, like piezoelectric semi conductivity and bio
compatibility in addition to this it exhibits a wide range of morphologies likewise
nanowires, nanobelts, nanoring’s, Nano helixes which are the basic building blocks for
fabricating nanodevices.
 3

INTRODUCTION

1.4 Properties of ZnO

It is the most studied nanomaterial. It has the wurtzite nanostructure with the lattice
parameters of

a=b=(0.3296nm)

c=(0.52065nm)

It is composed of a number of alternating planes with tetrahedrally-coordinated O2- &

Zn+2 ions, stacked alternately along the c-axis. Along the c-axis, the positively charged
Zn-(0001)

Polar surface and negative charged o-(0001) polar surface are the strongest polarity
surfaces. The polar surfaces contribute to the variety of ZnO nanostructures by surface
reconstruction to maintain a stable structure. When a stress force is applied the non-
central symmetric structures will lead to the separation of the central point positive
charges and that of negative charges, resulting in a polarization. This property of ZnO
is called piezoelectricity, and it is more significant property of ZnO. Furthermore, ZnO
is an important semiconductor with a large direct band gap of 3.37 eV. Due to difference
in work function ø between contact metal and ZnO, the ZnO nanowires that based
devices can operate as Ohmic or Schottky devices. The nanowire bases nanogenerators
and force sensors that were discovered in 2006 can be explain by the coupling effect of
piezoelectric and semi conducting properties (Wang & Song, 2006). All these
predominant properties make the ZnO a great potential application material in the
nanoscience and nanotechnology.

1.4.1 Mechanical Properties of ZnO (1-D) Nanomaterial

Elastic modulus of 1-D nanomaterials is one of the most important properties that
dictate their applications in nanotechnology. The elastic constants reflect the stress-
strain relation of materials. Strictly speaking, because materials are normally
anisotropic and properties of a material depend on direction, the elastic constant of
material is a 4th rank tensor. For simplicity, the ZnO nanowires can be regarded as a
homogeneous isotropic material, and a scalar constant Young’s modulus (or elastic
 4

INTRODUCTION

modulus) is used to indicate the elasticity of the material. Various methods have been
developed for quantifying the mechanical properties of 1-D nanomaterials. One of the
most popular approaches is based on dynamic resonance of a 1-D nanostructure that is
affixed at one end and free at the other; the mechanical resonance is excited by an
externally applied oscillating electrical field, and the observation is made through
electron microscope. Previous research based on this in-situ TEM resonance method
has measured the Young’s modulus of ZnO nanobelts to be ~52 GPa(Bai, Gao, Wang,
& Wang, 2003). Also, the hardness has been determined to be ~5 GPa from
nanoindentation experiments(Mao, Zhao, & Wang, 2003). This thesis further
investigates the mechanical measurements on 1-D ZnO nanomaterials, and serves as
the first step to electromechanical measurements and applications.

1.4.2 Electrical Properties of ZnO Nanomaterial

Normally, ZnO is an n-type semiconductor, which means electrons are the main carrier
charges. The frequently observed unintentional n-type conductivity has often been
attributed to oxygen vacancies and zinc interstitials. One oxygen vacancy or zinc
interstitial is always accompanied by two electrons in order to keep the charge balance.
OOx ↔ 12 O2 (g) +VO•• + 2e′ and ZnOx ↔ Zni•• + 2e′. Different synthesis methods
for ZnO nanowires will induce different levels of oxygen vacancies and zinc interstitials
so that the conductivity of ZnO nanowires will vary. It is still controversial which kind
of defects dominates in contributing electron carriers since the point defects are hard to
directly observe. One main issue related to electrical transport of ZnO nanowires is the
complicacy in the contact between the ZnO and electrode (Lao, Liu, et al., 2006). The
metal-semiconductor (MS) contact plays a very important role in all solid-state devices.
Two kinds of contacts can be formed at metal-semiconductor junction, one is Ohmic
contact, and the other is Schottky contact. An Ohmic contact is a region on a
semiconductor device that has been prepared so that the current-voltage (I-V) curve of
the device is linear and symmetric. If the I-V characteristic is non-linear and
asymmetric, the contact can instead be termed a Schottky contact. Reliable and
controllable rectifying electric characteristics are essential in solid-state circuits. ZnO
is not only a wide band gap (Eg = 3.37eV) semiconductor, but also room temperature
and high temperature luminance materials with high exciton binding energy as 60 meV.
 5

INTRODUCTION

Due to these two promising properties, people believe ZnO has tremendous applications
in optoelectronics application, and a great amount of effects have been placed on ZnO
nanowires for UV sensors, photodiodes, etc.

1.4.3 Optical Properties of ZnO (1-D) Nanomaterial

About Zinc oxide:

Zinc oxide is an inorganic compound with the formula ZnO. ZnO is a white powder
that is insoluble in water, and it is widely used as an additive in numerous materials and
products including rubbers, plastics, ceramics, glass, cement, lubricants, paints,
ointments, adhesives, sealants, pigments, foods, batteries, ferrites, fire retardants, and
first-aid tapes. Although it occurs naturally as the mineral zincite, most zinc oxide is
produced synthetically. ZnO is a wide-bandgap semiconductor of the II-VI
semiconductor group. The native doping of the semiconductor due to oxygen vacancies
or zinc interstitials is n-type(Özgür et al., 2005). This semiconductor has several
favorable properties, including good transparency, high electron mobility,
wide bandgap, and strong room temperature luminescence. Those properties are
valuable in emerging applications for: transparent electrodes in liquid crystal displays,
energy-saving or heat-protecting windows, and electronics as thin-film transistors
and light-emitting diodes

1.5 Synthesis of ZnO Nano-materials

Since the discovery of nanobelts in 2001 ZnO nanostructures have been commonly
prepared by a high temperature furnace method. By precisely controlling the pressure,
flow rate, temperature and synthesis time, a wide variety of ZnO nanostructures can be
synthesized at the substrates at the downstream of the tube furnaces. Transmission
electron microscopy (TEM) experiment shows that ZnO has three fast growth
directions: <0001>, <01 1 0> and <2 1 1 0>, and two ±(0001) polar-surfaces. A variety
of unusual structure configurations can be synthesized under different growth
conditions such as nanowires (Mai et al., 2008), nanobelts(Pan, Dai, & Wang, 2001),
Nano propellers(Gao & Wang, 2004),and nanocombs (Lao, Gao, et al., 2006). In order
to minimize the total energy, which is composed of elastic energy and electrostatic
 6

INTRODUCTION

energy, Nano bows(Hughes & Wang, 2004), Nano helixes (Kong & Wang, 2003),
nanoring’s (Kong, Ding, Yang, & Wang, 2004) could be the favorable morphology of
ZnO at nanoscale. This research will just focus on the quasi 1-D nanomaterials
including nanowires, nanobelts, and Nano helices. Nanobelts have a rectangular cross-
section, which is a result of the minimization of surface elastic and electric energies.
Though from crystallographic point of view, nanobelts are different with the common
nanowires, which have a circular or hexagonal cross-section and a different growth
direction, they have similar physical and chemical properties, thus sometimes they are
not distinguished in my research. Recently, the research focus has been placed on the
synthesis of vertically aligned nanowire arrays and their application as high density
electronic devices and energy transducers. Currently, the aligned ZnO nanowires have
been achieved by various methods, such as vapor-solid-solid process (Zhao, Willander,
Morjan, Hu, & Campbell, 2003), metal-organic chemical vapor deposition
(MOCVD)(Park, Kim, Yi, Bae, & Lee, 2004), and sol-gel process (Krumeich et al.,
1999).

1.6 Application of ZnO nanomaterials

ZnO has wide direct band gap (3.37 eV or 375 nm at room temperature). Therefore,
its most common potential applications are in laser diodes and light emitting
diodes (LEDs). Some optoelectronic applications of ZnO overlap with that
of GaN(Zheng, Yao, Wang, & Yang, 2015), which has a similar bandgap (~3.4 eV at
room temperature). Compared to GaN, ZnO has a larger exciton binding energy (~60
meV, 2.4 times of the room-temperature thermal energy), which results in bright room-
temperature emission from ZnO. ZnO can be combined with GaN for LED-
applications. For instance as transparent conducting oxide layer and ZnO
nanostructures provide better light outcoupling(Bakin et al., 2007). Other properties
of ZnO favorable for electronic applications include its stability to high-energy
radiation and its possibility to be patterned by wet chemical etching. Radiation
resistance makes ZnO a suitable candidate for space applications. ZnO is the most
promising candidate in the field of random lasers to produce an electronically pumped
UV laser source. The pointed tips of ZnO nanorods result in a strong enhancement of
an electric field. Therefore, they can be used as field emitters(Kucheyev et al., 2003).
 7

INTRODUCTION

Aluminum-doped ZnO layers are used as a transparent electrodes. The constituents of

Zn and Al are much cheaper and less toxic compared to the generally used indium tin
oxide (ITO). One application which has begun to be commercially available is the use
of ZnO as the front contact for solar cells or of liquid crystal displays (Li, Bando, &
Golberg, 2004). Transparent thin-film transistors (TTFT) can be produced with ZnO.
As field-effect transistors, they even may not need a p–n junction, thus avoiding the p-
type doping problem of ZnO. Some of the field-effect transistors even use ZnO
nanorods as conducting channels (Nomura et al., 2003).

1.6.1 ZnO based Sensors

Zinc oxide nanorod sensors are devices detecting changes in electric current passing
through zinc oxide nanowires due to adsorption of gas molecules. Selectivity to
hydrogen gas was achieved by sputtering Pd clusters on the nanorod surface. The
addition of Pd appears to be effective in the catalytic dissociation of hydrogen
molecules into atomic hydrogen, increasing the sensitivity of the sensor device. The
sensor detects hydrogen concentrations down to 10 parts per million at room
temperature, whereas there is no response to oxygen (Heo et al., 2004).

1.6.2 Spintronics

ZnO has also been considered for spintronics applications: if doped with 1–10% of
magnetic ions (MN, Fe, Co, V, etc.), ZnO could become ferromagnetic, even at room
temperature. Such room temperature ferromagnetism in ZnO:Mn has been observed
(Qin, Wang, & Wang, 2008), but it is not clear yet whether it originates from the matrix
itself or from secondary oxide phases

1.6.3 Piezoelectricity

The piezoelectricity in textile fibers coated in ZnO have been shown capable of
fabricating "self-powered Nano systems" with everyday mechanical stress from wind
or body movements (Mofor et al., 2005). In 2008 the Center for Nanostructure
Characterization at the Georgia Institute of Technology reported producing an
electricity generating device (called flexible charge pump generator) delivering
 8

INTRODUCTION

alternating current by stretching and releasing zinc oxide nanowires. This mini-
generator creates an oscillating voltage up to 45 millivolts, converting close to seven
percent of the applied mechanical energy into electricity. Researchers used wires with
lengths of 0.2–0.3 mm and diameters of three to five micrometers, but the device could
be scaled down to smaller size (Qin, et al., 2008).

1.7 Objective of the Thesis

Main objectives of this research work are;

• To deposit ZnO thin films on glass substrates by chemical bath deposition

• To observe the effect of concentration of the reactants on the morphology of the

ZnO nanocrystals.

• To determine the structural properties of the deposited thin films by X-ray

diffraction (XRD) technique.

• To observe the morphology of deposited ZnO thin films at various

concentration of reactants by Scanning Electron Microscopy.

1.8 Organization of the thesis

This thesis consists of 4 chapters, chapter one is about the introduction of nanoscience
and nanotechnology and 1 D-nanomaterials, second chapter contains the literature
review and deposition techniques and third is of research methodology which is about
chemical bath deposition and growth of ZnO nanorods. Fourth one is about results and
discussion which explains the analysis of the samples by XRD and SEM.
 9

LITERATURE REVIEW

CHAPTER 2 LITERATURE REVIEW

2.1 Literature Review

In recent years, many efforts have been made for achieving ZnO nanomaterials via
different approaches. However due to lack of information about nanomaterial formation
mechanisms, many researchers have focused on different possible methods to obtain
desired shapes. These methods include: Common thermal evaporation, chemical vapor
deposition, hydrothermal methods, sol gel methods, electrochemical deposition, laser
ablation thermal decomposition and many others. The present section portrays a brief
review of the methods that have been used to synthesize and characterize zinc oxide
nanomaterials:

Odom et al Prepared Well-aligned ZnO nanorod arrays on substrates by hydrothermal

growth under different conditions. The effect of preparing conditions on the deposition
of ZnO nanorods was systematically studied by scanning electron microscopy, X-ray
diffraction and photoluminescence spectroscopy. It is demonstrated that the growth
conditions such as pre-treatment of the substrates, growth temperature, deposition time
and the concentration of the precursors have great influence on the morphology and the
alignment ordering of ZnO nanorod arrays. Pre-treatment of substrates, including
dispersion of ZnO nanoparticles and subsequent annealing, not only plays a main role
in governing the rod diameter, but also greatly improves the rod orientation. Although
the rod diameter and its distribution are mainly determined by pre-coated ZnO
nanoparticles, they can also be monitored to some extent by changing the concentration
of the precursors. The growth temperature has a little influence on the orientation of
nanorods but it has great impact on their aspect ratio and the photo luminescent
property. Kinetic studies show that the growth of ZnO nanorods contains two distinct
steps: a fast step within the first hour, in which the nanorods tend to be short and wide,
and a slow step, in which long rods with high aspect ratio are obtained. This work
provides, for the first time, a systematic study of the hydrothermal growth of ZnO
nanorod arrays on substrates. It has been demonstrated that the preparing Cond itions
such as substrate’s pre-treatment, deposition temperature, growth time and the
 10

LITERATURE REVIEW

concentration of the precursors have a great influence on the microstructure and

ordering of ZnO nanorod arrays (Hu, Odom, & Lieber, 1999).

Diao et al. Studied the pre-coated ZnO nanoparticles with smaller size lead to small
rod diameter, narrow diameter distribution and high growth density. The substrate
annealing’s crucial for the improvement of alignment ordering of ZnO nanorod arrays.
Although growth temperature has little influence on the crystalline structure and the
orientation of the nanorods, it has a great impact on the aspect ratio and the PL of the
nanorods. High growth temperatures result in thick ZnO films composed of well-
aligned nanorods with high aspect ratio. The concentration of precursors can influence
the nanorod size to some extent, although the pre-coated ZnO nanoparticle layer plays
the main role in governing the nanorod diameter. Kinetic studies show that the growth
of ZnO nanorod in radial direction contains two distinct steps: a fast step in the early
stage, in which short but wide rods are formed, and a slow step, in which long rods with
high aspect ratio are obtained. Finally, this work sheds light on the factors that govern
the growth of well-aligned ZnO nanorod arrays, and gains access to the controlled
fabrication of 1D alignments of other materials by hydrothermal deposition (Guo, Diao,
& Cai, 2005).

Karamat et al. have focused on the detailed characterization of

(ZnO)1−x(CuO)x(Al2O3)0.002 bulk samples and their thin films. XRD of bulk samples
showed ZnO peaks without impurity phase which indicates maximum substitution of
copper inside the ZnO lattice. Raman spectra showed a random shift of modes which
might be due to point defects created by copper and aluminum substitution in ZnO.
VSM showed weak ferromagnetic behavior in samples indicating Cu ion substitution
in ZnO. XPS further confirmed the presence of Cu+2 states in the bulk samples. After
detailed characterization of bulk samples, these samples were utilized as targets for
deposition of thin films using PLD technique. Highly crystalline films of doped ZnO
with (002) orientation were grown on (100) Si substrates. Compositional analysis of
thin films done by XPS showed the presence of Cu+2 ions which is the source of
ferromagnetism in the thin film samples. M-H curves showed the ferromagnetic
behavior for the films. Thin films are magnetic and conductive at room temperature
(Karamat, Rawat, Lee, & Tan, 2010).
 11

LITERATURE REVIEW

Hani Khalaf et al. investigated the Chemical bath deposition of ZnO thin films using
six different complexing agents, namely ammonia, hydrazine, ethanolamine,
methylamine, triethanolamine and dimethylamine. As-grown films were mainly ZnO2
with a band gap around 4.3 eV. Films annealed at 400ºC were identified as ZnO with a
band gap around 3.3 eV. X-ray diffraction and micro-Raman spectroscopy revealed that
as-grown films consist mainly of cubic zinc peroxide that was transformed into
hexagonal ZnO after annealing. High-resolution transmission electron micrographs
showed small variations of the order of 10 nm in film thickness which corresponds to
the average grain size. A carrier density as high as 2.24×1019 cm−3 and a resistivity as
low as 6.48 × 10−1 Ωcm were obtained for films annealed at 500ºC in argon ambient
(Khallaf et al., 2009).

Carcia et al. have fabricated high-performance ZnO thin-film transistors on gate

dielectrics of HfO2, HfSiOx, and Al2O3, grown by atomic layer deposition (ALD).
Devices on HfO2 had a mobility of 12.2 cm2/V s with a threshold voltage of 2.6 V and
subthreshold slope of 0.5 V/ decade. Device characteristics for all ALD dielectrics
exhibited negligibly small hysteresis, suggesting a low defect density at the interface of
ZnO with the gate dielectric (Carcia, McLean, & Reilly, 2006).

Fawzy A.Mahmoud et al. have deposited thin films of zinc oxide (ZnO) onto glass
substrates using a simple and inexpensive ultrasonically spray pyrolysis technique.
Aqueous methanolic solution of zinc acetate was used as a spraying solution. The
concentration of the solution was 0.1 M. The films prepared at different substrate
temperature were uniform and well adherent to the substrates. X-ray diffraction (XRD)
studies showed that all the films were polycrystalline in Nano size scale. The SEM
photographs reveal the Nano-size of the constituents. The electrical resistivity of the
films was found to be dependent on the deposition temperature. The room temperature
electrical resistivity was found to be varying in the range 10-5 to 10-6 Ω cm-2. The sample
resistance is measured with the presence of CH4 in AR carrier gas (Mahmoud &
Kiriakidis, 2009).

Kenanakis et al. have grown zinc oxide nanostructured films by the aqueous chemical
growth technique using equimolar aqueous solutions of zinc nitrate and
hexamethylenetetramine as precursors. Silicon (100) and glass substrates were placed
 12

LITERATURE REVIEW

in Pyrex glass bottles with polypropylene autoclavable screw caps containing the
precursors described above, and heated at 95°C for several hours. X-ray diffraction 2θ/θ
scans showed that the only crystallographic phase present was the hexagonal wurtzite
structure. Scanning electron microscopy showed the formation of flowerlike ZnO
nanostructures, consisting of hexagonal nanorods with a diameter of a few hundred
nanometers. The ZnO nanostructures exhibit an ultraviolet emission band centered at
~3.192 eV in the vicinity of the band edge, which is attributed to the well-known
excitonic transition in ZnO (Kenanakis, Androulidaki, Koudoumas, Savvakis, &
Katsarakis, 2007).

Antônio Claret Soares Sabioni et al. determined oxygen diffusion coefficients in pure
and doped ZnO polycrystals by means of the gas-solid isotope exchange method using
the isotope 18O as oxygen tracer. The diffusion experiments were performed from 900
to 1000°C, under an oxygen pressure of 105 Pa. After the diffusion annealing’s, the 18O
diffusion profiles were determined by secondary ion mass spectrometry. The results of
the experiments show that oxygen diffusion in Li-doped ZnO is similar to the oxygen
diffusion in pure ZnO, while in Al-doped ZnO the oxygen diffusion is enhanced in
relation to that observed in pure ZnO, in the same experimental conditions. Based on
these results, they have proposed an interstitial mechanism for oxygen diffusion in ZnO
(Sabioni, Ramos, & Ferraz, 2003).

Mondal et al. have deposited aluminum doped zinc oxide (AZO) thin film on
microscopic glass substrate following a chemical technique called successive ion layer
adsorption and reaction (SILAR). The technique involves multiple dipping of the
substrate in an aqueous solution of sodium zincate kept at room temperature and
deionized water kept near boiling point. Al doping was found to increase the film
growth rate. It was approximately 0.20 μm/mole/dipping for ZnO film and
0.22μm/mole/dipping for AZO film. Structural characterization by X-ray diffraction
(XRD) technique confirmed incorporation of aluminum in ZnO lattice. The c-axis
orientation was significantly enhanced due to Al incorporation which was revealed
from marked increase of (002) peak intensity compared to other peaks of hexagonal
ZnO. The cross sectional view in SEM (Scanning electron micrograph) also reveals
growth of large crystallites perpendicular to the substrate. The resistance of the film
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LITERATURE REVIEW

decreased about one order in magnitude due to Al doping. The activation barrier value
of 0.31 eV for ZnO film was however found to be unaffected due to aluminum
incorporation (Mondal, Kanta, & Mitra, 2008).

Chen et al. prepared un-doped and doped ZnO powders by the sol–gel method. The
nanoparticles were heated at 700–800 ºC for 1 h in air and then analyzed by X-ray
diffraction (XRD), scanning electron microscopy (SEM), Raman spectra and
photoluminescence (PL). The results of undoped (ZnO) and Al-doped ZnO (AZO)
nanoparticles were also compared to investigate the structural characteristics and
physical properties. XRD patterns of AZO powders were similar to those of ZnO
powders, indicating that micro-Al ions were substituted for Zn atoms and there were no
variations in the structure of the ZnO nanoparticles. From the XRD and SEM data, the
grain size of the AZO nanoparticles increased from 34 to 40 nm when the annealing
temperature was increased. The Raman intensity of the AZO nanoparticles (Al = 5 at
%) increased when the annealing temperature was increased. Increasing the degree of
crystalline not only reduced the residual stress, but also improved the physical
properties of the nanoparticles (Chen et al., 2008).

Shabannia et al. presented vertically aligned undoped and Cu-doped ZnO nanorods
array were successfully grown on flexible substrate by chemical bath deposition method
at a low temperature. The fabricated materials were characterized using X-ray
diffraction (XRD), field-emission scanning electron microscopy (FESEM), energy
dispersive X-ray spectroscopy (EDX) and photoluminescence (PL) spectroscopy. XRD
analysis showed that Cu doping improves the crystallinity of the fabricated ZnO
nanorods. The mean diameter and bending of the ZnO nanorods increase with an
increase of Cu doping, but the density of Cu-doped ZnO nanorods almost unchanged.
Room temperature PL measurement displayed increased intensity in UV peak and
decreased visible peak after Cu doping. Undoped and Cu-doped ZnO nanorods array
were successfully synthesized on flexible PEN substrate using CBD method. The low
compressive strain, and higher intensity of the (002) peak of the Cu-doped ZnO
nanorods indicate better crystal quality compared with undoped ZnO nanorods. The
FESEM images showed that the average diameter of the vertical undoped and Cu doped
ZnO nanorods grown on the PEN substrates were 66 nm and 124 nm, respectively. With
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LITERATURE REVIEW

Cu doping in ZnO nanorods, the relative intensity of the UV emission increased but
that of the green emission decreased. The higher PL intensity ratio ( IUV I DLE ) for
Cu-doped ZnO nanorods reveals an improvement in the crystal band and luminescence
property (Shabannia & Abu-Hassan, 2013).

L.Chow et al. detection of chemicals and biological species is an important issue to

human health and safety. In this paper, we report the hydrothermal synthesis at 95 ◦C
of Cu-doped ZnO low-dimensional rods for room-temperature (RT) sensing
applications and enhanced sensor performances. X-ray diffraction, scanning electron
microscopy, X-ray photoelectron spectroscopy, Raman and photoluminescence are
used to characterize the material properties. To demonstrate the suitability of the Cu-
doped ZnO rods for gas sensor applications and for comparison with pure ZnO, we
fabricated a double rod device using Focused Ion Beam. The responses of pure-ZnO
and Cu-doped ZnO rods studied in exactly the same condition are reported. We found
that Cu-ZnO sensors have enhanced RT sensitivity, faster response time, and good
selectivity. Miniaturized Cu-ZnO rod-based sensors can serve as a good candidate for
effective H2 detectors with low power consumption (Chow et al., 2013).

Lupan et al. study Zinc oxide nanorod arrays were fabricated using a hydrothermal
method on ITO glass substrate. We can find that the dimension of ZnO nanorod will
changes with different growth of time. X-ray diffraction (XRD) patterns show that the
nanorods are high-quality crystals growing along [001] direction with a high consistent
orientation perpendicular to the substrate and it is also revealed that nanorods have
wurtzite crystal structure. The diameter of ZnO nanorods were 100– 300 nm depending
on the time of growth process. The surface morphology of ZnO nanorods were analyses
using Scanning Electron Microscope (SEM).In this study, ZnO nanorods had
successfully synthesized on ITO glass substrate. From the results of XRD and SEM,
the best growth of ZnO nanorods is at 3H at which the average diameter of ZnO
nanorods about 200 nm. These high quality ZnO nanorods can be applied on the
electrode of dyesensitized solar cell to increase the contact area between Zn O and dye,
resulting in the enhancement of efficiency for dye-sensitized solar cell (Lupan et al.,
2010).
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LITERATURE REVIEW

R.K. Shukla et al. performed the experiment of Un doped and Cu doped ZnO film of
two different molarities deposited by spray pyrolysis using zinc nitrate and cupric
chloride as precursors show polycrystalline nature and hexagonal wurtzite structure of
ZnO. Te crystallite size varies between 10 and 21 nm. Doping increases the
transmittance of the flms whereas the optical band gap of ZnO is reduced from 3.28 to
3.18 eV. With increment in doping the surface morphology changes from irregular
shaped grains to netted structure with holes and then to net making needle-like
structures which lends gas sensing characteristics to the film. Undoped ZnO shows
maximum sensitivity at 400∘C for higher concentration of CO2. Te sensitivity of Cu
doped sample is maximum at 200∘C for all CO2 concentrations from 500 to 4000 ppm.
Nanocrystalline Cu doped ZnO film have been successfully deposited on glass
substrates by spray pyrolysis and their structural and optical properties have been
investigated. Te crystallite size decreases with increase in molarity of precursor solution
whereas with doping the crystallite size increases in general. Doping increases the
transmittance of the films whereas optical band gap first decreases and then increases
as the dopant concentration is gradually increased for both molarities in reference. As
the doping increases, the SEM shows formation of irregular shaped grains and then
netted structure with holes followed by net making needle-like structures becoming
dominant over the holes for both molarities. Response of these films for carbon dioxide
has been studied. Undoped ZnO shows maximum sensitivity at 400∘C for higher
concentration of CO 2. Te sensitivity of Cu doped sample is maximum at 200∘C for all
CO 2 concentrations from 500 to 4000 ppm (Shukla, Srivastava, Srivastava, & Dubey,
2006).

V. Kumar et al. reported the development of aluminum boron co-doped ZnO (AZB)
nanostructures deposited by sol–gel method using spin coating technique. The structure
of AZB nanostructure films has been found to exhibit the hexagonal wurtzite structure.
The shape of AZB nanostructures has changed from seed structure to tetra-pods, tetra-
pods to nanorods and finally to nanofibers with increase in aluminum concentration.
The structural, electrical and optical properties of AZB films are tuned with shape and
size of the nanostructures. These AZB nanostructures could be applicable for various
Nano regime devices such as photovoltaic cells, gas sensors and field emission devices.
AZB nanostructures of different shape have been synthesized on glass substrate using
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LITERATURE REVIEW

a low gel process. It was found that the concentration of Al plays a key role in varying
the morphology and other properties of AZB films. A minimum resistivity of 6.8 104
V cm and transmittance of 88% was obtained at 0.6 at.% doping concentration of B and
0.4 at.% doping concentration of Al with a Rs of 24 V/& for NRs in AZB films. This
work shows that the co-doping of ZnO with Al and B significantly improves the
electrical properties of ZnO with no degradation in the optical properties. These AZB
nanostructures can be potentially extended for the application of nanoelectronic devices
(Kumar et al., 2013).

Zhang et al. fabricated a variety of morphologies of ZnO nanostructures successfully

fabricated by chemical bath deposition (CBD) technique at a low temperature. The
structure and morphology of the ZnO products were observed by scanning electron
microscopy. The investigation demonstrated that the ZnO nanostructures showing the
hexagonal wurtzite structure. The aspect ratio of ZnO nanorods decrease with the
equimolar increasing of the reactants. The ZnO nanostructures show different
morphologies with the increasing of the concentration when the reactant concentration
is not equal. The forming mechanism of the ZnO nanostructures was discussed in detail.
one-dimensional ZnO Nano-powder with different morphologies can be fabricated by
a simple chemical bath deposition. A variety of morphologies of ZnO nanostructures
were generated without adding any active agent. The changes of concentration of
Zn(CH3COO)2·2H2O and C6H12N4 have an important influence on the ZnO
morphology. The photographs revealed that the evolution of ZnO nanostructures from
nanorods to dumbbell-shaped and Nano-branches. In addition, the growth mechanism
of multi-structure ZnO was deeply discussed (Zhang, Wang, Fei, Xiu, & Jia, 2015).

Wang et al. studied Uniformly distributed ZnO nanorods with diameter 80 nm-1200
μm and several micrometers long have been successfully grown at low temperatures on
different substrates by using chemical bath deposition. The size of the ZnO nanorods
can be controlled on the different substrates by tuning growth parameters. The
mechanism of the nanorod growth on the different substrates is proposed. The effect of
substrate on the ZnO nanorods morphology was also investigated. the morphology of
the ZnO nanorods changed from rods to wire or pie. By investigation on growth
characteristics of ZnO on the different substrate, these kinds of structure are useful in
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laser and solar cell application uniformly distributed ZnO nanorods with diameter
80nm-1200 μm and several micro meters long have been successfully grown at low
temperatures by using chemical bath deposition. The mechanism of the nanorod growth
on the different substrates is proposed. The effect of substrate on the ZnO nanorods
morphology was also investigated. The morphology of the ZnO nanorods changed from
rods to wire or pie. In addition, the growth mechanism of the ZnO nanorods had also
been discussed. Zn2+ ion concentration play a key role during the process of regulating
the growth rate and forming the ZnO nanorods semiconductor films by CBD (Jia,
Wang, & YAOa, 2010).

Behboudnia et al. investigated ZnO thin films which were grown onto glass slides by
CBD (chemical bath deposition) from solutions containing zinc sulfate (ZnSO4),
ethylenediamine (C2H8N2) and Sodium Hydroxide with continuous stirring.
Structural, morphological and optical analysis of the films was studied. Scanning
electron microscopy (SEM) results show compactly aggregated nanorods. The film
showed high transparency about 90% and optical band gap was obtained 3.95ev for the
film. ZnO thin film was fabricated on a clean glass substrate at a low temperature by a
chemical bath deposition method. Under stirring condition aligned ZnO nanorod arrays
were observed. The gravimetric method was performed to indicate the film thickness.
The film growth rate was a very sensitive function of stirring rate of the bath. The ban
gap and transparency of ZnO nanorods was found to be 3.3-3.9 eV and > 90%,
respectively. The growth process proposed in the present work requires no expensive
and precise vacuum equipment, and therefore, permits large-scale fabrication of aligned
ZnO nanorod arrays at a relatively low cost (Rezabeigy, Behboudnia, & Nobari, 2015).

Shaban et al. grown Different zinc oxide (ZnO) nanostructured thin films were grown
on glass substrates at low temperatures by combining successive ionic layer adsorption
and reaction (SILAR) method and chemical bath deposition (CBD). Morphologies and
structures of the samples were investigated by X-ray diffraction (XRD), energy-
dispersive x-ray spectroscopy (EDX) and scanning electron microscopy (SEM). The
reaction mechanism for the growth of ZnO microstructures is analyzed. The results
show that the surface morphology of the ZnO nanostructures films changed from
hexagonal nanorods into hexagonal nanodisc with increasing the growth time of ZnO.
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According to XRD, the growth of a preferred c-axis oriented ZnO nanostructured thin
films in (002) orientation can be easily driven at such low growth temperature. The
present approach demonstrates its potential for large-scale, low-temperature and
controlled structural morphology of ZnO nanostructured films. This work introduced a
facile and low-cost method to fabricate and control the morphology of ZnO
nanostructured thin films via two-step CBD method at low temperature. The surface
morphology of the ZnO nanostructures films changed from hexagonal nanorods into
hexagonal Nano discs by controlling the growth time of ZnO thin film from 2h to 6 h.
The density of the Nano discs is increased as the time increased to 8h. However, the
size of each disc decreased. EDX spectrum showed the high purity of the fabricated
ZnO nanostructured thin films. XRD showed the growth of a preferred c-axis oriented
wurtzite ZnO nanostructured thin films in (002) orientation plane. These nanostructures
are suitable for many applications such as sensing, self-cleaning and photo-catalytic
(Shaban, Zayed, Ahmed, & Hamdy).

Faiz et al. studied the growth of hexagonal ZnO nanorods was demonstrated by low
temperature chemical synthesis approach. X-ray diffraction (XRD) analysis revealed a
wurtzite hexagonal structure of the ZnO nanorods. The optical properties were
measured by UV–vis spectrophotometer at room temperature. X-ray photoelectron
spectroscopy (XPS) confirmed high purity of the ZnO nanorods. The hydrogen sensor
made of the ZnO nanorods showed reversible response. The hydrogen gas tests were
carried out in presence of ambient air and the influence of operation temperature on the
hydrogen gas sensing property of ZnO nanorods was also investigated A low
temperature chemical synthesis method was employed for the fabrication of hexagonal
ZnO nanorods. XRD analysis demonstrated excellent crystal quality for the hexagonal
shaped ZnO nanorods. XPS analysis confirmed high purity of the ZnO nanorods. A
possible growth mechanism for the formation of hexagonal ZnO nanorods has been
suggested. The optical properties were measured by UV–vis spectrophotometer at room
temperature. ZnO nanorods were used for the fabrication of hydrogen sensor working
under ambient air and reversible response. The effect of operating temperature on the
sensing property of ZnO nanorods was also studied (Qurashi, Faiz, Tabet, & Alam,
2011).
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Kim et al. report on the morphology control and electroluminescence of well-aligned

ZnO nanorod/p-GaN heterojunctions prepared by an aqueous solution route at low
temperature (90 °C). They found that the density and size of the grown nanorods and
microrods depended significantly on the ZnO seed density. Synchrotron X-ray
scattering measurements showed an epitaxial relationship between the ZnO nanorods
and the p-GaN thin film. ZnO nanorod/p-GaN heterojunction light-emitting diodes
(LEDs) with an individual chip size of 300 × 300 μm2 were fabricated. Room-
temperature electroluminescence spectra in the visible range were obtained from the
LED at forward bias voltage. This result indicates that such heterojunction LEDs
fabricated from solution are a promising approach for realizing large-area light-emitting
sources that have high external quantum efficiency. They have considered the control
of the morphology and density and the electroluminescence of well-aligned ZnO
nanorod/p-GaN heterojunctions, using a simple aqueous solution method of preparation
at a low temperature of 90 °C. Uniformly distributed ZnO seed nanoparticles of smaller
diameters led to the formation of vertically aligned ZnO nanorods with relatively
uniform diameters during the main growth. More dippings led to a nonuniform
distribution of agglomerated seed nanoparticles with larger diameters, resulting in the
formation of microrods as well as nanorods during the main growth. ZnO nanorods
have a perfect epitaxial relationship to the GaN thin film in the synchrotron X-ray
scattering measurements. Strong EL spectra were obtained in the visible range from a
size 300 × 300 μm2 single chip ZnO nanorod/p-GaN heterojunction LED. They believe
that the results in this work are a significant step toward the realization of nanomaterial-
based novel optical and electrical devices requiring low-temperature processes on a
large scale (Lee, Kim, Yi, Choi, & Kim, 2009).

Galeazzi1b et al. Stated that ZnO nanostructures of rod-like, faceted bar, cup-end bars,
and spindle shaped morphologies could be grown by a low power ultrasonic synthesis
process. pH of the reaction mixture seems to plays an important role for defining the
final morphology of ZnO nanostructures. While the solution pH as low as 7 produces
long, uniform rod-like nanostructures of mixed phase (ZnO and Zn(OH)2), higher pH
of the reaction mixture produces ZnO nanostructures of different morphologies in pure
hexagonal wurtzite phase. pH of the reaction as high as 10 produces bar shaped uniform
nanostructures with lower specific surface area and lower surface and lattice defects,
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LITERATURE REVIEW

reducing the defect emissions of ZnO in the visible region of their photoluminescence
spectra. ZnO nanostructures of different morphologies could be fabricated by ultrasonic
hydrolysis of zinc acetate in aqueous solution by controlling its hydrolysis rate through
pH adjustment. While a solution pH 7 or lower produces impure ZnO nanostructures
mixed with Zn(OH)2 phase, higher pH values of the reaction mixture produce ZnO
nanostructures in pure hexagonal phase. Controlling solution pH in between 7.5 and 10,
phase pure ZnO nanostructures of varied morphology could be produced and the
concentration of their structural and surface defects could be controlled. Utilization of
low power ultrasound for the chemical synthesis of ZnO nanostructures efficiently has
been demonstrated (Morales-Flores1a et al., 2013).

Jia et al. investigated ZnO nanorods that were rapidly synthesized by the simple one-
step room temperature solid-state chemical reaction between zinc salts and alkali in the
presence of a suitable surfactant or organic reagent. The function of surfactant or
organic reagent for the growth of nanomaterials in solid-state chemical reaction was
discussed in detailed. It was found that the morphology of solid-state product can be
controlled by the molecular structure of the added surfactant or organic reagent. The
linear surfactant or organic reagent can act as the inducing agent to control the one-
dimensional directed growth of products and form one-dimensional nanorods. The
sensors based on ZnO nanorods have good hydrogen sulfide gas sensing property at
relatively low working temperature of 190 _C, which makes as-prepared ZnO nanorods
ideal candidates for hydrogen sulfide gas-sensing devices. ZnO nanorods have been
fabricated by one-step room-temperature solid-state chemical reaction via introducing
suitable surfactant or organic reagent into solid-state chemical reaction between zinc
salts and sodium hydroxide. The added suitable long-chain or linear surfactant and
organic reagent can induce the product to grow into 1D nanorods. The method may
provide a path to fabricate special nanostructures of semiconductor oxides with a
convenient and economical solid-state synthetic way. The gas-sensing measurements
show that ZnO nanorods exhibit the excellent responses to hydrogen sulfide. The sensor
signal of ZnO nanorods to 100 ppm hydrogen sulfide can reach 34.8, which is higher
than bulk materials or nanoparticles. The excellent sense property for hydrogen sulfide
makes as-prepared ZnO nanorods ideal candidates for hydrogen sulfide gas-sensing
devices (Cao, Jia, Wang, & Luo, 2013).
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Mostafaei et al. studied Polyaniline (PANI) based nanocomposites filled with ZnO
nanorods were prepared by the chemical oxidative method of the aniline in acid medium
with ammonium peroxydisulphate (APS) as an oxidant. The composition, morphology
and structure of the polymer and the nanocomposites were characterized by Fourier
transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), transmission
electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric
analysis (TGA), UV–vis spectroscopy and electrical conductivity. The characteristic
FTIR peaks of PANI were found to shift to higher or lower wave number in PANI–
ZnO composites due to formation of H-bonding. Different amounts of ZnO nanorods
were used to verify this effect on the characteristics of the synthesized materials. These
observed effects have been attributed to interaction of ZnO nanorods with PANI
molecular chains. XRD results revealed that the crystallinity of PANI was more
pronounced after addition of nanorods, while the intensity of the peaks increased by
addition of ZnO nanorods. Electrical conductivity of the PANI–ZnO nanocomposite
film was found to be smaller than that of the PANI film. The decrease of electrical
conductivity in PANI–ZnO films as compared to PANI was attributed to the interfaces
formed between oxygen of ZnO nanorods and hydrogen of PANI. Also, TGA results
showed that the decomposition of the nanocomposite was less than that of pure
polyaniline which confirms the successful fabrication of products. These conductive
polymers can be used in commercial paints as an additive. A series of ZnO doped
polyaniline nanocomposites have been prepared by in situ chemical oxidative
polymerization at atmospheric pressure and under visible light. The results of
spectroscopic methods such as XRD, FTIR, TEM, SEM, TGA, electrical conductivity
and UV–vis measurements Indi- cate that PANI–ZnO nanocomposite is successfully
prepared in this research. A possible mechanism for the formation of the PANI–ZnO
nanocomposites was proposed. XRD and FTIR results show that interaction between
ZnO and PANI is based on the formation of hydrogen bonding and electrostatic
interaction between camphor sulfonic acid capped ZnO nanorods and poly- aniline
plays a key role in the formation of the PANI–ZnO nanocomposite. Electrical
conductivity measurements demon- strate that the conductivity of nanocomposites is
less than those of PANI and ZnO nanorods and by increasing ZnO nanorods content,
value of electrical conductivity decreased. SEM and TEM micrograph shows that there
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is a uniform distribution of ZnO nanorods in PANI-ZnO nanocomposite. Furthermore,

TGA and UV–vis results confirm that –NH– group was adsorbed on the surface of ZnO
nanorods as the thermal and optical properties have been changed. Further research on
these nanocomposites in marine paints as an anticorrosive and anti- fouling additives is
in progress (Mostafaei & Zolriasatein, 2012).

Al-Owais investigated that Large-scale uniform aligned ZnO nanorods with a

hexagonal tip were successfully synthesized via a facile process at low temperature of
(_140 _C) without using any additives and substrate. The process is based on a simple
reaction of zinc powder and de-ionized water. The results reveal that the as prepared
ZnO products have an average length of 10 lm and a diameter in the range of 50–260
nm, possessing a single crystal wurtzite structure. The structure and morphology of the
ZnO products are characterized by X-ray diffraction (XRD), field emission scanning
electron microscopy (FESEM) and energy dispersive X-ray spectrometer (EDX). The
possible formation mechanism of nanorods is proposed in brief. aligned ZnO nanorods
with hexagonal tip were prepared by water in a simple reaction of Zn powder and water
at 140 _C without any substrates. This method is found to be a mild, convenient and
efficient route to prepare ZnO nanostructures without the template or crystal seeds. It
may be extended to fabricate other metal oxide nanomaterials. Successfully synthesized
a hexagonal structure of ZnO nanorods in length at relatively low temperature, by a
hydrothermal method which is a very simple, low cost and environmentally friendly.
This convenient synthetic route can be readily extended to other technologically
important metal oxides. The magnetic property was tested with a vibrating sample
magnetometer at room temperature and revealed a high hysteresis loop indicating a
strong ferromagnetic nature of as synthesized ZnO nanorods. The yield producing
nanorods with this method includes ease, flexibility, fast being low cost and ineffective
on environment free.(Al-Owais, 2013)
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CHAPTER 3 RESEARCH METHDOLOGY

3.1 Introduction to Nanoparticle manufacturing

There is a vast role of experimental techniques in the investigation of physical,
chemical, optical, mechanical, magnetic and structural properties of a product. At the
same time morphology enforce properties of the final product. So, there is a need of
deep knowledge of characterization to know the exact properties of the product. This
chapter is about experimental and characterization techniques of ZnO nanorods. To get
grow crystal structure we must have the knowledge of substrate, crystal structure and
morphology. At the same time synthesis techniques and parameters play a vital role in
the synthesis of nanomaterial. If we change any parameter then their will a drastic
change in the morphology of nanomaterials.

3.2 Nanoparticles Manufacturing Approaches

We may use molecular and conventional techniques for the synthesis of ZnO nanorods.
These techniques are known as top down and bottom up approaches.

3.2.1 Top-Down Approach

In this approach material changes its dimensions from bulk to Nano scale. In this
approach, different techniques are applied to get nanostructures. Some of these methods
are given below
• Anodization
• Plasma etching
• Ion beam etching
• E-beam lithography
• Photolithography
All the above methods are used to synthesize nanomaterials. After etching we get the
desired morphology of nanostructures.

3.2.2 Bottom-up Approaches

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RESEARCH METHDOLOGY

Bottom up approaches are opposite to top down approaches. In this procedure atoms
and molecules are assembled to form nanoobjects. In this approach shape and size of
objects is controllable at atomic level. For nanoscale objects Vander wall forces are
very important. These forces are responsible for atomic assemblage. Detail of some
techniques of this approach is given below.

3.3 Electrodeposition
This method is resembled with electroplating in which metal films are deposited on
cathode. The main difference between electroplating and electrodeposition is substrate.
In electrodeposition. we fabricate a thin film on the substrate which is dipped in the
electrolytic solution. Two electrodes are immersed in the electrolytic cell solution
which can conduct electric current, this solution is called electrolytic. At anode anions
are collected and discharge the solution and cations are discharged on cathode. Mostly
anode is made with the element which is required to deposit and the salt of same element
is used as electrolyte. When electrodes are connected with some external source of
voltage then electrons start to flow from anode to cathode. Anions are discharged at
anode releasing their electrons at anode while cations are discharged at cathode after
gaining electrons.
A very simple electrolytic cell is shown in figure.3.1

Figure 3.1: simple electrolytic cell

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RESEARCH METHDOLOGY

3.4 Chemical Bath Deposition

Chemical bath deposition (CBD) is a technique in which thin films of nanostructures are
grown on substrate without electrodes. This is very economical technique which is easy to
handle.

3.4.1 Advantages of CBD

• It is very simple technique.

• Hard and uniform thin films can be fabricated through CBD.
• No vacuum is required in this technique.
• Give homogenous thin films.
• Give stoichiometry reactions.
• We can handle this technique at low temperature.

3.4.2 Disadvantages of CBD

• By products may impure the thin films.

• We must waste the solution after every deposition.
• Dangerous gases can be evolved as by products which are injures to health.

3.4.3 Factors Affecting CBD

The factors which can affect the synthesis of thin films via CBD are given below;
• Concentration of reactants.
• Temperature of reaction.
• PH of solution.
• Reaction time.

3.4.4 Synthesis of ZnO nanorods by CBD

ZnO nanorods were grown on glass substrate by CBD. Substrate surface was cleaned
by immersing in acetone and IPA for 15 minutes in ultrasonic bath. Synthesis was
carried out by first preparing 50 mL solutions of zinc nitrate and HMTA each in DI
water, separately. The concentration of zinc nitrate and HMTA was kept same. Four
solutions with concentrations 0.1, 0.2, 0.3,and 0.4 M were prepared. Zinc nitrate and
 26

RESEARCH METHDOLOGY

HMTA solutions were mixed together and temperature maintained at 90°C for15
minutes under vigorous magnetic stirring. Substrates were then immersed vertically and
temperature of the reaction increased from 0 to 90°C. The reaction mixture was kept at
90°C for a deposition e of 3 hours. A continuous and slow stirring was kept in order to
avoid precipitation in beaker and to produce smooth films on glass substrates. After 3
hours, substrates were removed from CBD beaker; washed with DI water and dried at
room temperature before further characterization.

3.5 Experimental Procedure

3.5.1 Preparation of the substrate

Substrate selection and grooming is a major consideration when working in any

nanotechnology research area. This is especially true when ‘optical growth’ leading to
well aligned ZnO nanorods is desired. Substrate has to be cleaned before any deposition
and, when using the CBD technique, further planning is needed to determine the growth
of ZnO nanorods. ZnO nanorods presented in this thesis were grown on glass substrate.
Substrates were obtained by cutting the glass slides with a diamond tipped scriber into
the required sizes.

3.5.2 Substrate cleaning

Cleaning of substrate and other experimental equipment is really significant to perform

CBD. Modest quantity of impurities can affect the growth dramatically. Before
deposition, the substrates must be properly cleaned using isopropanol and acetone in an
ultrasonic bath.
Reagents
The chemicals used for the ZnO nanorods preparations are listed below:
1: Zinc nitrate hexahydrate, 𝒁𝒏(𝑵𝑶𝟑 )𝟐 . 𝟔𝑯𝟐 𝑶.
2: Hexamethylene tetramine,, (𝑪𝑯𝟐 )𝟔 𝑵𝟒 .
3: Deionized water as a solvent.

3.5.3 3.5.4 Preparation of solution for substrate deposition

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First, take the required zinc nitrate hexahydrate 𝒁𝒏(𝑵𝑶𝟑 )𝟐 . 𝟔𝑯𝟐 𝑶 into 30mL deionized
water. Place a magnetic stirrer into it and start stirring for 30 minutes. After 30 minutes
of stirring, add 10 mL of DI water more into it and start stirring for 10 to 15 minutes
more.
Also take the required hexamethylene tetraamine (𝑪𝑯𝟐 )𝟔 𝑵𝟒 (1.40186grams) into 30
ml of deionized water in a separate beaker. Put a magnetic stirrer into it and start
stirring. After 30 minutes of stirring, add 20 ml of DI water more into it and again start
stirring for 10 to 15 minutes more.
After making of both solutions separately added. Then added 50-ml solution of
𝒁𝒏(𝑵𝑶𝟑 )𝟐 . 𝟔𝑯𝟐 𝑶 in a 100-ml beaker and start stirring of it with the help of magnetic
stirrer. Now add 50ml solution of Hexamethylene tetramine (𝑪𝑯𝟐 )𝟔 𝑵𝟒 into 100 ml
beaker but not abruptly (donot add the whole solution of HMTA into zincnitrate
hexahydrate solution at once, add little volume after short interval for better mixing of
solutions).
Note:”
Before mixing, both solutions were transparent, but after combining and proper stirring
the final result was a little milky in color.

3.5.4 ZnO deposition

Precursor solution were added in the jacketed beaker circulating hot water with the
help of water bath. The water can distribute through the cap (this procedure is served
by holding the temperature constants or at uniform temperature). Two sets of glass
slides holed by Teflon holder so that the film may deposit only on single side of each
slide. The holder is constructed up of ‘Teflon’ (a plastic with high thermal resistivity).
Adjust the temperature of water bath at 90C for 3 hours and deposit the Zinc Oxide for
0.1, 0.2, 0.3 and 0.4M respectively for getting different samples.
 28

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Figure 3.2: CBD apparatus for synthesis of ZnO nanorods

3.5.5 ZnO NR growth process

The chemical bath was prepared by mixing equimolar aqueous solution of Zinc nitrate
hexahydrate 𝑍𝑛(𝑁𝑂3 )2 . 6𝐻2 𝑂 and hexamethylene tetraamine (HMTA) (𝐶6 𝐻12 𝑁4 ). To
grow ZnO NRs, substrates were placed vertically inside the chemical bath at optimized
pH of 6 and deposition time 3 hours for 0.1, 0.2, 0.3 and 0.4M concentration
respectively. The detailed chemical reactions involved in the growth of ZnO nanorods
are as follows
𝑪𝟔 𝑯𝟏𝟐 𝑵𝟒 + 𝟔𝑯𝟐 𝑶 ←→ 𝟔𝑪𝑯𝟐 𝑶 + 𝟒𝑵𝑯𝟑 ………………………………………...3.1

𝑪𝟔 𝑯𝟏𝟐 𝑵𝟒 + 𝒁𝒏+𝟐 → [𝒁𝒏(𝑪𝟔 𝑯𝟏𝟐 𝑵𝟒 )]+𝟐……………………………………….…3.2

𝑵𝑯𝟑 + 𝑯𝟐 𝑶 ←→ 𝑵𝑯+ −
𝟒 + 𝑶𝑯 …………………………………………………....3.3

𝒁𝒏+𝟐 + 𝟒𝑵𝑯𝟑 → 𝒁𝒏(𝑵𝑯𝟑 )+𝟐

𝟒 …………………………………………………….3.4

𝒁𝒏+𝟐 + 𝟒𝑶𝑯− → 𝒁𝒏(𝑶𝑯)−𝟐

𝟒 ………………………………………………….….3.5

𝒁𝒏(𝑵𝑯𝟑 )+𝟐 −
𝟒 + 𝟐𝑶𝑯 → 𝒁𝒏𝑶 + 𝟒𝑵𝑯𝟑 + 𝑯𝟐 𝑶………………………………….3.6

𝐙𝐧(𝑶𝑯)−𝟐 −
𝟒 → 𝒁𝒏𝑶 + 𝑯𝟐 𝟎 + 𝟐𝑶𝑯 ……………………………………………...3.7
 29

RESEARCH METHDOLOGY

[𝒁𝒏(𝑪𝟔 𝑯𝟏𝟐 𝑵𝟒 )]+𝟐 + 𝟐𝑶𝑯− → 𝒁𝒏𝑶 + 𝑯𝟐 𝑶 + 𝑪𝟔 𝑯𝟏𝟐 𝑵𝟒 ......….……………….3.8

Figure 3.3: Flow chart of synthesis and experimental setup

3.6 Characterization techniques

In order to get exact information about the crystal structure, surface morphology,
particle size etc. the following characterization techniques were used.
• X-ray Diffraction (XRD)
• Scanning Electron Microscope (SEM)

3.6.1 X-ray Diffraction (XRD)

Up to 1895 the study of matter at the atomic level was a difficult task but the discovery
of electromagnetic radiation with 1 Å (10-10 m) wavelength, appearing at the region
between gamma-rays and ultraviolet, makes it possible.
 30

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Figure 3.4: Bruker D8 Advance X-ray diffraction machine

As the atomic distance in matter is comparable with the wavelength of X-ray, the
phenomenon of diffraction find its way through it and gives many promisable results
related to the crystalline structure. The unit cell and lattices which are distributed in a
regular three-dimensional way in space forms the base for diffraction pattern to occur.
These lattices form a series of parallel planes with its own specific d-spacing and with
different orientations exist. The reflection of incident monochromatic X-ray from
successive planes of crystal lattices when the difference between the planes is of
complete number n of wavelengths leads to famous Bragg’s law: nλ=2dsinƟ
 31

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Figure 3.5: X-ray Diffraction in accordance with Bragg’s Law

Where n is an integer 1, 2, 3….. (Usually equal 1), λ is wavelength in angstroms (1.54

Å for copper), d is interatomic spacing in angstroms, and θ is the diffraction angle in
degrees. Plotting the angular positions and intensities of the resultant diffracted peaks
of radiation produces a pattern, which is characteristic of the sample. The fingerprint
characterization of crystalline materials and the determination of their structure are the
two fields where XRD has been mostly used. Unique characteristic X-ray diffraction
pattern of each crystalline solid gives the designation of “fingerprint technique” to XRD
for its identification. XRD may be used to determine its structure, i.e. how the atoms
pack together in the crystalline state and what the interatomic distance and angle are
etc. From these points it can be concluded that X-ray diffraction has become a very
important and powerful tool for the structural characterization in solid state physics and
materials science.

3.6.2 Scanning Electron Microscope (SEM)

The scanning electron microscope (SEM) uses a focused beam of high-energy electrons
to generate a variety of signals at the surface of solid specimens. The signals that derive
from electron reveal information about the sample including external
morphology (texture), chemical composition, and crystalline structure and
 32

RESEARCH METHDOLOGY

orientation of materials making up the sample. In most applications, data are collected
over a selected area of the surface of the sample, and a 2-dimensional image is generated
that displays spatial variations in these properties. Areas ranging from approximately 1
cm to 5 microns in width can be imaged in a scanning mode using conventional SEM
techniques (magnification ranging from 20X to approximately 30,000X, spatial
resolution of 50 to 100 nm). The SEM is also capable of performing analyses of selected
point locations on the sample. The design and function of the SEM is very similar to
the EPMA and considerable overlap in capabilities exists between the two instruments.

Figure3.6: Schematic Diagram of SEM

Accelerated electrons in an SEM carry significant amounts of kinetic energy, and this
energy is dissipated as a variety of signals produced by electron sample interactions
when the incident electrons are decelerated in the solid sample. These signals include
secondary electrons (that produce SEM images), backscattered electrons (BSE),
diffracted backscattered electrons (EBSD that are used to determine crystal structures
and orientations of minerals), photons (characteristic X-rays that are used for elemental
analysis and continuum X-rays), visible light (cathodoluminescence--CL), and heat.
 33

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Figure 3.7: Scanning electron microscope

Secondary electrons and backscattered electrons are commonly used for imaging
samples: secondary electrons are most valuable for showing morphology and
topography on samples and backscattered electrons are most valuable for illustrating
contrasts in composition in multiphase samples (i.e. for rapid phase discrimination
SEM analysis is considered to be "non-destructive"; that is, x-rays generated by electron
interactions do not lead to volume loss of the sample, so it is possible to analyze the
same materials repeatedly. The SEM is routinely used to generate high-resolution
images of shapes of objects (SEI) and to show spatial variations in chemical
compositions: 1) acquiring elemental maps or spot chemical analyses using EDS,
2)discrimination of phases based on mean atomic number (commonly related to relative
density) using BSE, and 3) compositional maps based on differences in trace element
"activators" (typically transition metal and Rare Earth elements) using CL. The SEM is
also widely used to identify phases based on qualitative chemical analysis and/or
 34

RESEARCH METHDOLOGY

crystalline structure. Precise measurement of very small features and objects down to
50 nm in size is also accomplished using the SEM.
 35

RESULTS AND DISCUSSION

CHAPTER 4 RESULTS AND DISCUSSION

4.1 Structural Analysis of ZnO Nanorods

4.1.1 Structure parameter

• Texture coefficient

The degree of preferred orientation of the different crystalline planes can be determined
from the Harris’s analysis, by calculating the texture coefficient as shown in Equation
4.1;

I(hkl) 1 I(hkl)
P(hkl) = I (hkl)
⁄ N ∑ I (hkl) ..…………………………. (4.1)
0 0

Where P(hkl) is the texture coefficient of the plane specified by Miller Indices (hkl);
I(hkl) and I0(hkl) are the measured and standard intensities of ZnO nanorods
respectively, and n is the number of diffraction peaks.

An increase from the unity in the texture coefficient indicates a higher degree of
preferred orientation along a particular plane and vice versa. The deviation in the
texture coefficient from unity for a particular Miller plane also corresponds to change
in atomic densities corresponding to that plane as X-ray intensities are function of
atomic structure factors. Thus higher value of the texture coefficient corresponds to
increase in planar density along a particular crystal plane as compared to ideal values.
Crystalline size

Lattice constants can be determined using X-ray diffraction. The lattice constant,
or lattice parameter, refers to the physical dimension of unit cells in a crystal lattice.
Lattices in three dimensions generally have three lattice constants, referred to as a, b,
and c. However, in the special case of hexagonal crystal structures,
‘a’ and ‘b’ constants are equal, and we only refer to the ‘a’ and ‘c’ constants. Lattice
parameter ‘a’ can be calculates as;

(√(1⁄3) λ)
a= ....................................................................... (4.2)
sinθ
 36

RESULTS AND DISCUSSION

And the Lattice parameter ‘c’ can be calculated as;

λ
c= ................................................................................ (4.3)
sinθ

• Crystalline size

From X-ray diffraction patterns, the crystallite size or particle size (D) can be found
using the Scherrer’s formula as;

Kλ
D= ........................................................................... (4.4)
βCOSθ

Where ‘k’ is a constant determined by the geometry of the crystallites and it is

approximately 0.9 for spherical particles, β is the full width at half maximum (FWHM)
intensity of the observed diffraction peak. The broadening considered in Scherrer
equation is due to particle size alone. The angular width at a point where the intensity
has fallen to half of its maximum value (Full width at half maximum intensity or
FWHM) is a measure of broadening of x-ray peak.

• Dislocation density

The dislocation density is a measure of the number of dislocations in a unit volume of

a crystalline material. Two methods are used to measure this parameter. In the first, the
total length of dislocation line in a unit volume is measured and divided by the volume
to give: D = (L / 13) m-2. In the second method the number of dislocation lines crossing
unit area in the sample is counted to give:  D = (n/12) m-2. This second method is
frequently easier to apply with the dislocations being revealed by chemical etching. A
count of the number of etch pits per unit area on the etched surface gives the dislocation
density. For crystalline structural measurements dislocation density can be calculated
as;

1
δ= ………………………………….…………………… (4.5)
D2
 37

RESULTS AND DISCUSSION

• Lattice strain

Polycrystalline materials deform when subjected to external stimulus. As long as the

stress is small the deformation is reversible and leads to elastic strain. When a material
is deformed, the lattice plane spacing in the grains change from their stress-free value
to a new value corresponding to the magnitude of applied stress and this new spacing
is (nearly) uniform from one grain to another for any particular sets of planes with
similar orientations.

βcosθ
ε= .......................................................................... (4.6)
4

4.1.2 X-ray diffraction analysis

Figures 4.1 depict that the X-Ray Diffraction (XRD) patterns nanocrystalline ZnO
nanorods deposited on glass substrate at 90℃ for deposition time of 3 hours at 0.1,
0.2, 0.3 and 0.4 Molar concentration of the reactants((ZnNO3).6H2O and HMTA)).
From the XRD pattern, it is clearly shown that the (0 0 2) peak is the most intense,
which confirms the preferred growth along c-axis direction
 38

RESULTS AND DISCUSSION

Figure 4.1: XRD Pattern of ZnO Nanorods for concentration of 0.1,0.2,0.3 and 0.4
respectively
 39

RESULTS AND DISCUSSION

Measured intensity

Table 4.1 Measured intensity

(h k l) 100 002 101 102 110 103

0.1M 22.89156 100 18.07229 9.638552 8.43373 10.84337

0.2M 23.77049 100 27.04918 8.19672 6.967212 7.786884

0.3M 72.443 100 45.85 13.755 15.589 12.838

0.4M 28.26096 100 24.4566 8.42394 6.52176 6.7935

Texture coefficient

1 𝐼
𝑇𝐶 = (𝐼/𝐼0 ) ⁄ ∑
𝑁 𝐼0

Where I (h k l) is the measured relative intensity of the plane (h k l), Io (h k l) is

the standard intensity of the plane (h k l) taken from the standard data, and n is the
number of peak for which data is going to be calculated. Any deviation of the calculated
TC value from unity implies preferred growth. The texture coefficient values of ZnO
films calculated for the diffraction peak (1 0 0) and (0 0 2) are compiled in table It can
be seen from the table that, the value of TC (0 0 1) initially decreases with value 0.54
nm and then it increases linearly with increase with 2theta. Whereas TC (0 0 2) is the
highest peak in the graph and has the highest texture coefficient values which tell us
the deviation in the peaks of the xrd patterns is more at that plane i.e. (002). Where the
TC value is 5.66 nm which is highest of all as can be seen from graph of XRD.
 40

RESULTS AND DISCUSSION

Table 4.2: Texture coefficients of 0.1M,0.2M,0. 3M and 0.4M

Planes ( 0.1M 0.2M 0.3M 0.4M

(h k l)
TC

Average 2.53218 0.28022 1.44002 0.40798

TC

The values obtained for the Miller indices ‘h’, ‘k’ and ‘l’ are in a good agreement with those
reported in the Ref. pattern Zin cite, 00-001-1136.

For HKL(100):

The Lattice constant ”a”, lattice constant “c”, crystallite size D, dislocation density “𝛿”, and
strain “𝜀” of the as-grown films were calculated for (100) reflection using Eq. (1), Eq. (2),
Eq. (3), Eq. (4)and Eq. (5) respectively:

(√(1⁄3) 𝜆)
𝑎= ……………………………….…………4.1
𝑠𝑖𝑛𝜃

𝜆
𝑐= ………………………………………………….4.2
𝑠𝑖𝑛𝜃

𝐾𝜆
𝐷= ………………………….……4.3
𝛽𝐶𝑂𝑆𝜃

1
𝛿= …………………………….…….4.4
𝐷2

𝛽𝑐𝑜𝑠𝜃
𝜀= …………………………….….4.5
4
 41

RESULTS AND DISCUSSION

Where k is a constant to be taken 0.9 and λ, β and 𝜃 are the XRD wavelength (1.5406Å),
full width at half maximum (FWHM) and bragg’s angle respectively. The calculated
structural parameter of the thin film are presented in table given below

Table 4.3: Structure parameter

Sample A c FWHM D (nm) strain δ×10−4

(°) (nm)−2
−3
ε×10

0.1M 2.7738 5.0926 0.4 21.7531 1.663 21.13

0.2M 2.7913 5.1248 0.15 57.9715 0.624 2.98

0.3M 2.7895 5.1213 0.2 57.9715 0.829 2.98

0.4M 2.7895 5.1214 0.2 43.4832 3.3290 5.29

The values obtained for the Lattice constant ‘a’ has range from 3.1912 to 3.1786 Å
and Lattice constant ‘c’ has range from 5.5256 to 5.5039 Å , which are in a good
agreement with those reported in the Ref. pattern Zin cite, 00-001-1136.

The values obtained for the Lattice constant ‘a’ has range from 3.1912 to 3.1786 Å and
Lattice constant ‘c’ has range from 5.5256 to 5.5039 Å , which are in a good agreement
with those reported in the Ref. pattern Zin cite, 00-001-1136.

It can be noted that the sample prepared at 0.2M showed the maximum (002) intensity,
minimum FWHM and large crystallite size. Which means this concentration is the
optimum deposition concentration to get high quality ZnO nanorods using low cost
CBD.
 42

RESULTS AND DISCUSSION

4.2 Morphology of ZnO Nanorods

4.2.1 SEM Analysis

Figure 4.2 shows the SEM image of ZnO nanorods deposited on glass substrate for
0.1M concentration and deposition time of 3 haours at 90℃ with continuous stirring.
The SEM image shows ZnO nanorods are hexagonal in shape with smooth surface and
the diameter of the nanorods ranges from 334.7 to 421.64 nm. The length of the
nanorods was observed to be in the range from 144.9 to 492.66nm.

Figure 4.2: SEM image of ZnO nanorods obtained at 0.1 Molar concentration

In 2nd experiment, ZnO nanorods were deposited on glass substrate with a deposition
time of 3 hours at 90℃. The SEM image as shown in Figure 4.3 reveals that deposited
ZnO nanorods are hexagonal in shape with diameter ranging from 133.33 to 466.62 nm.
 43

RESULTS AND DISCUSSION

The average length of ZnO nanorods is found to be in the range from 1133 to1466.52
nm.

Figure 4.3: SEM image of ZnO nanorods obtained at 0.2 molar concentration
 44

RESULTS AND DISCUSSION

Figure 4.4: SEM image of ZnO nanorods obtained at 0.3 molar concentration

In 4rth experiment, ZnO nanorods were deposited on glass substrate with a deposition
time of 3 hours at 90℃ with 0.4M concentration of reactants The SEM image as shown
in Figure 4.5 reveals that deposited ZnO nanorods are hexagonal in shape with diameter
ranging from 980nm to 1537 nm. The average length of ZnO nanorods is found to be
in the range from 753 to1311 nm.
 45

RESULTS AND DISCUSSION

Figure 4.5: SEM image of ZnO nanorods obtained at 0.4 molar concentration
 46

CONCLUSION

In conclusion, we explored the effect of precursors zinc nitrate hexahydrate and HMTA
concentration impact on the structural, morphological and properties of the chemical
bath synthesized ZnO nanorods. Morphological studies have revealed the formation of
nanorods. The XRD results revealed that the slight changes in the lattice parameters
have occurred and the formation of defect complexes. X-ray Diffraction studies have
revealed that changing concentration (HMTA(Hexamethylenetetramine) and Zinc
nitrate hexahydrate) into the ZnO have great impact on crystalline size. From the SEM
studies, Zinc nitrate hexahydrate and HMTA was found to be an effective precursor for
the formation of ZnO nanorods with large diameter. Conversely, ZnO nanorods with a
small diameter obtained at 0.1M of HMTL and zinc nitrate hexahydrate. By choosing
a suitable precursor (HMTL and zinc nitrate hexahydrate) and concentration, we can
control the diameter of ZnO nanorods, which is important for the fabrication of Nano-
optoelectronic devices.
 47

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