CONTENTS

1. Chapter 1
Thin film: An overview
1.1 Introduction
1.1.1 Properties of thin films
1.1.2 Thin film growth process
1.1.3 Epitaxy
1.2 Method used for deposition of thin film
1.2.1 Physical vapor deposition
1.2.2 Chemical vapor deposition
1.2.3 Chemical solution deposition
1.3 ZnO the novel material
2. Chapter 2
Synthesis and experimental Techniques
2.1 Substrate cleaning
2.2 Synthesis
2.2.1 Annealing of samples
2.3 Characterization Techniques
2.3.1 X-Ray diffraction
2.3.2 UV-VIS spectrophotometer
3. Chapter 3
Results and Discussion
3.1 X-Ray analysis
3.2 UV-VIS spectrophotometer analysis
3.3 Conclusion
3.4 Future Scopes
References

Chapte
r -1
Thin Film: An Overview
1.1 Introduction
Thin films are layers of a material whose thickness ranges from fractions of a nanometer
to several micrometers. They are deposited on the substrates to achieve better properties
than that of bulk materials. Electronic semiconductor devices and optical coatings are the
main applications benefiting from this technology. Some work is being done with
ferromagnetic thin films as well for use as computer memory.
Ceramic thin films are also in wide use. Thin films of ceramic materials like BaTiO3,
ZnO etc. has the huge applications in piezoelectric sensors. Coating of ceramic materials
protect against corrosion, oxidation and wear.
The nano-structured thin film enhances the efficiency of solar cells, memory storage
capacity of computers, reduces the costs of devices as well as material losses. However,
thin films have had to be developed using new semiconductor materials, including
amorphous silicon, copper indium diselenide, cadmium telluride, zinc sulphide, zinc
oxide and film crystalline silicon.
The pivotal role of thin film technology in the development of such diverse and
challenging frontiers as microelectronics, optical coatings and integrated optics, thin-film
superconductivity and quantum engineering, surface science, engineering and
technology, micro-magnetism, metallurgical coatings, and amorphous materials now a
part of literature. Deposition of thin films increases the contact area of the cell
components, resulting in a high fraction of reactants. Thin films result in higher current
densities and cell efficiencies because the transport of ions is easier and faster through
thin-film layers than in bulk materials.
Transparent and highly conducting oxide films have attracted many researchers due to
their wide range of applications in industry as well in research; Transparent and
conducting layers of some metallic oxides such as Cadmium Oxide, Tin Oxide, and
Indium Oxide has known for a long time. The electrical property of ZnO thin film
strongly depends on the deposition method, thermal treatment and Oxygen
chemisorption. Doped ZnO also show a dependence of electrical properties on the
substrate temperature and film thickness. ZnO is one of the metal oxides, which has been
widely used as transparent conductor.
Various techniques have been used for the deposition of ZnO thin films on the glass. In
the present work, I have deposited ZnO thin film by chemical bath deposition technique.
Among other techniques, chemical bath deposition method has the following advantages
over the others;
1. Simple
2. Large area of thin film can be deposited without sophisticated instruments.
3. The properties of the material can be varied and controlled by proper optimization of
The chemical baths and deposition conditions.

1.11 Properties of thin films

As we move from bulk to nano-structured thin film, the size affects an important role and
the properties of these film changes drastically. Thin films are quasi-two dimensional,
defect structures different from bulk and strongly influenced by surface and interface
effects. Thin film properties are summarized in the Table-1 with their applications.

Table-1: Characteristics of thin films

Thin-film property category Typical Applications
Optical Reflective/antireflective coatings, Interference filters,
decoration (color, luster), memory disks (CD, DVDs),
Wave guides
Electrical Insulation, Conduction, Semiconductor Devices,
Piezoelectric Drives
Magnetic Memory Disks
Chemical Barriers to diffusion or alloying, Protection against
oxidation or corrosion, Gas/liquid sensors
Mechanical Tribological (wear-resistant) coatings, Hardness,
Adhesion, Micro-mechanics
Thermal Barrier Layers, Heat Sinks
1.1.2 Thin film growth Process
The growth phenomena in thin films take place in following ways;
Adsorption processes
Adsorption is the process that occurs, when gas or liquid solute accumulates on the
adsorbate forming a thin film of atoms or molecules. The adsorption processes are of two
types; a) chemisorptions (b) physisorption
The physisorption and chemisorption are distinguished on the basis of their relative bond
strength and mechanism. Chemisorption is the process in which chemical bond is formed
between the absorbate atom and the substrate. In this case, the adsorption energy Ea ≥
sublimation energy of the substrate (few eV/atom). Physisorption is a type of adsorption
in which adsorption adheres to the surface only through Van-der-Waal interactions.
Physisorption is characterized by low temperature, less than the critical temperature of
adsorbate, low enthalpy, adsorption takes place in multi-layers, low activation energy and
reversible process. Physisorption energies are of order100 MeV/atom.
Condensation
Condensation is the process of accumulation of gaseous particles or atoms by lowering of
their energies on the surface for the adsorption process on the substrate.

Film

Substrate

Figure-1.1: Thin film growth process (condensation)

At certain temperature, there is an equilibrium vapour pressure (sublimation pressure); no

deposit would occur at all unless one has super-saturation. Super-saturation is achieved
just above the substrate surface. Under super-saturation, the density is so high, i.e. the
atomic separation is so short, that condensation occurs due to van der Waals force.
Surface diffusion and nucleation
Surface diffusion
It is the most important factor of thin film structure because it allows the absorbing
species to find each other, find most active sites, or find epitaxial sites. Various methods
have been applied to measuring surface diffusion rates of absorbed molecules, but most
of this work has been done on chemical systems relevant to heterogeneous catalysis
rather than to thin film deposition. The role of surface diffusion in thin films has
mainly been inferred from observations of thin film structure. Under super-saturation the
atoms/molecules are condensed onto the substrate surface. The deposition rate or flux (of
adatom) is directly proportional to the pressure and inversely proportional to squire root
of absolute temperature. After the atoms being absorbed on the surface, they become
adatoms with (positive) adsorption energy Ea, relative to zero in the vapour. The
desorption rate of adatom given by,

Ra ∝ νa exp (-Ea / kT)

Where, νa is the characteristic atomic vibration frequency and is expected to vary
relatively slowly with T.
The adatom can diffuse over the surface, with energy Ed (migration barrier energy) and
14
the corresponding frequency ν d (order of 10 / sec). Since E d << Ea, surface diffusion is
far more than desorption. The probability that during one second the adatom will have
enough thermal energy to pass over the barrier is,
Pa = νa exp (-Ea / kT)
In unit time, adatom makes ν d attempts to pass the barrier, with a probability
of
exp−(Ed / kT) of surmounting the barrier on each try. This is in fact the mean square
displacement of the random walker per unit time, or the tracer diffusion coefficient.
Nucleation and growth of 2D islands
The nucleation is the beginning of phase transformation that is formed from gaseous state
to solid thin film. Nucleation may involve; the assembly of proper kind of atoms by
diffusion, structural change in to one or more intermediate structures, formation of
critical sized particles of new phase known as nuclei. Nucleations are two types;
1. homogeneous or self-nucleation
2. heterogeneous nucleation
In the deposition process, the atoms from the gaseous phase settle down on the surface of
the substrate and the small nuclei will form at some locations on the substrate. When the
density of stable nuclei has increased sufficiently, any further deposition will exclusively
lead to island growth. At this saturation island density, the mean free path of diffusing
adatoms is equal to the mean island separation and adatoms will attach themselves with
much higher probability to existing islands than to create new ones. Approaching
coverage of about half a monolayer, islands eventually coalesce which decreases their
density. The islands formation is shown in Fig.1.2.

Island

Low coverage High coverage

Figure-1.2: Monolayer and Island growth process

If the deposition continues, the nucleation centers become enlarged and formation of 2D
islands occurs. The size of the 2D island increases and the coverage of the substrate
surface gets enlarged. This process may lead to growth phenomena. The growth fallows
the nucleation which determines the final crystallographic structures of the thin films.
The thin film growth phenomena are explained in the Fig.1.3.
 Figure-1.3: Various steps in thin film growth process

Crystallization and film growth

There are mainly three types of structures are obtained in the thin film growth
processes.
Amorphous
Structure obtained in this type has no order in the atoms on the layers or structures of
the thin films.
Polycrystalline
In this category the randomly oriented grains, oriented grains, highly
oriented grains, epitaxy (homo- or hetero-) has been formed.
Single crystal
Single crystal growth process is of two types; homoepitaxy, and hetero-epitaxy. Thin
films grown are amorphous as well as crystalline and well understood as in the
Fig1.4.
 Crystalline Amorphous

Figure-1.4: Crystalline and amorphous structures of thin film

1.1.3 Epitaxy
Epitaxy is the method of depositing a mono-crystalline thin film onto mono-crystalline
substrates. The epitaxy is further classified as in two categories; Homoepitaxy- thin film
deposited on the substrate of same materials as that of thin film, and hetero-epitaxy-
crystalline thin film grown on the crystalline substrate of different materials.
Factors governing epitaxy
Epitaxy depends on the following factors,
1. Substrate: Structural compatibility between substrate and the thin film materials are
most important factor for epitaxial growth of thin films. There should be lattice matching
(crystal structure and lattice constant) between the substrate and the thin film.
2. Chemical compatibility
Chemical compatibility is also required factor for the epitaxial growth of thin films.
3. Temperature
Temperature is also governing factor for epitaxial growth of thin films. The thermal
expansion coefficient should be matched. At the elevated substrate temperature Te good
epitaxy is obtained. Te depends on the deposition rate, particle energy and the surface
contamination. The reason for the need of higher temperature is the reduction surface
contamination by desorption, the enhancement of surface mobility of atoms to reach the
favorable sites, and the enhancement of diffusivity in the deposit thus favoring re-
crystallization and defect annihilation. The influence of substrate temperature with the
film morphology has been shown in the Fig. 1.5.

Figure-1.5: Influence of substrate temperature

The classification of three growth modes was first introduced by Ernst Bauer in 1958.
These are;
1. Layer by-Layer or Frank-Van-der Merwe: growth mode arises because
the atoms of the deposit material are more strongly attracted to the substrate than
they are to themselves.
2. Island (3D), or Volmer-Weber mode: results in which deposited atoms are
more strongly bound to each other than they are to the substrate.
3. Layer-plus-Island, or Stranski-Krastanov growth mode; In this case,
layers form first, but then for some reason or other the system gets tired of
this, and switches to islands.

1.2 Method used for deposition of thin film

Several methods are reported in literature by researchers in order to deposited thin film of
different materials by controlling the important parameters and usage of various
techniques. These methods are mainly divided into three main category a) physical
vapour deposition, b) chemical vapour deposition and c) chemical solution deposition.
Most of the semiconductor devices are grown based on thermal evaporation. We too have
used this technique. Fig. 1.6 shows some commonly used techniques for fabrication of
thin films.

Figure 1.6: Schematic representation of the classification of some of the common

thin film deposition processes.

1.2.1 Physical vapour deposition (PVD)

Physical vapor deposition processes are versatile technique used to deposit almost all
materials. These processes demonstrate high deposition rates, simplicity and it is
relatively easy to use. A wide variety of materials can be deposited, i.e., conductor
materials for electronic circuits and devices, for the application of dielectric and optical
coatings, and for developing technologies, such as high temperature superconductors.
Physical vapour deposition process, involves the formation of thin films on a substrate by
physically depositing the atoms, ions, or molecules of materials. Physical deposition uses
mechanical or thermodynamic means to produce a thin film of solid. The material to be
deposited is placed in an energetic, entropic environment (i.e. at high vacuum), so that
particles escape its surface and then get deposited on the substrate. The whole system is
kept in vacuum deposition chamber, to allow the particles to travel as freely as possible.
Physical vapor deposition can be classified as:
1) Thermal evaporation, has following components as heating source; Filament,
Resistance Boat, Electron Beam and, Arc Source
2) Sputtering,
RF Sputtering,
DC Sputtering,
Cathodic Arc Plasma Sputtering,
Magnetron Sputtering,
Reactive Sputtering
3) Ion Plating-Reactive Ion Plating
4) Molecular Beam Epitaxy (MBE),
5) Laser sputtering,
6) Cluster-Beam.

Thermal evaporation

The thermal evaporation deposition technique consists in resistive heating of materials,

which evaporates in the form of vapor and deposited on to the substrate. A thermal
evaporator uses an electric resistance heater to melt the material and raise its vapour
-6 -5
pressure to useful range. Low pressures are used, about 10 or 10 Torr, to avoid
reaction between the vapor and atmosphere. At these low pressures, the mean free path of
vapor atoms is the same order as the vacuum chamber dimensions, so these particles
travel in straight lines from the evaporation source towards the substrate. Only materials
with a much higher vapor pressure than the heating element can be deposited without
contamination of the film. The equipment available in the laboratory use resistance
heating (Joule effect). The metals used as heating resistance (Boat) are tantalum (Ta),
Molybdenum (Mo) and wolfram (W) etc. A schematic diagram of the deposition
equipment used in the laboratory is showed in the Fig. 3.1. Molecular beam epitaxy is a
particular sophisticated form of thermal evaporation.
Electron beam evaporator

The technique is based on the heat produced by high-energy electron beam bombardment
on the material and material gets melted and goes into vapor state, which is to be
deposited on the substrate. The electron beam is generated by an electron gun, which uses
the thermionic emission of electron produced by an incandescent filament. Emitted
electrons are accelerated towards an anode by a high difference of potential. The crucible
itself or a near perforated disc can act as the anode. A magnetic field is often applied to
bend the electron trajectory, allowing the electron gun to be positioned below the
evaporation line. The Fig. 1.7 shows a diagram of the electron beam gun evaporation
equipment.

Figure 1.7: Electron beam evaporator

Sputtering
Sputtering is the process of ejection of atoms from solid target materials due to
bombardment of high energetic ions. Sputtering was first observed by Grove in 1852 and
Pulkerin 1858 using von Guericke-type oil-sealed piston vacuum pumps. Sputter
deposition of films was first reported by Wright in 1877. It is useful for compounds or
mixtures, where different components would otherwise tend to evaporate at different
rates. The schematic of sputtering process is shown in the Fig.1.8.

Figure 1.8: The schematic representation of the fundamental processes occurring

during sputtering

Magnetron sputter deposition

The prototype of the first magnetron was a mercury electrode lamp, first used by
Kisayevand Pashkovain 1959 and adapted in a flat form by J.S. Chapin in 1974 to deposit
thin films. Magnetron sputtering is one of the most broadly used techniques mainly on
account of the high rate of target sputtering and the reduced range of operating pressures.
The constant magnetic field generated by magnets serves to localize the glow discharge
on the surface of the water-cooled sputtered targets, leading to much higher ionization
efficiency, and denser plasma formed near the cathode at low pressures.
Pulsed laser deposition
Pulsed laser deposition (PLD) system works by an ablation process. Pulses of focused
laser light vaporize the surface of the target material and convert it to plasma; this plasma
usually reverts to a gas before it reaches the substrate.
Cathodic arc deposition
Cathodic arc deposition or Arc-PVD which is a kind of iron beam deposition where an
electrical arc is created that literally blasts ion from the cathode. The arc has an extremely
high power density resulting in a high level ionization (30-100%), multiply charged ions,
neutral particles, clusters and macro-particles (droplets).
Molecular beam epitaxy (MBE)
This process is very slow, more costly and gives high quality thin film. This is a
sophisticated, finely controlled method for growing single-crystal epitaxial films in a high
-11
vacuum of about 10 torr. The films are formed on single-crystal substrate by slowly
evaporating the elemental or molecular constituents of the film from separate Knudsen
effusion source cells onto substrates held at a temperature appropriate for chemical
reaction, epitaxy, and re-evaporation of excess reactants. The furnaces produce atomic or
molecular beams of relatively small diameter, which are directed at the heated substrate,
usually silicon or gallium arsenide. Fast shutters are interposed between the sources and
the substrates. By controlling the shutters, one can grow super lattices with precisely
controlled uniformity, lattice match, composition, dopant concentrations, thicknesses, and
interfaces down to the level of atomic layers.

1.2.2 Chemical vapor deposition (CVD)

Chemical vapour deposition is the process of chemically reacting volatile compounds of a
material to be deposited, with other gases, to produce a non-volatile solid that deposited
atomistically on a suitably placed substrate.
Types of chemical vapor deposition
A number of forms of CVD are in wide use and are frequently referenced in the
literature. Classified by operating conditions are as:
1-Atmospheric pressure CVD -CVD processes at atmospheric pressure.
2-Low pressure CVD (LPCVD) (at 0.2~20 Torr)
Reduced pressure tends to reduce unwanted gas-phase reactions and improve film
uniformity across the wafer. Most modern CVD processes are either LPCVD or
UHVCVD.
 3-Metal Organic CVD (MOCVD)
Metalorganic vapour phase epitaxy (MOVPE) is a chemical vapour deposition method
of epitaxial growth of materials, especially semiconductors from the pyrolysis of
organic compounds containing the required chemical elements.
4-Plasma enhanced CVD (PECVD)
PECVD process is that utilize plasma to enhance chemical reaction rates of the
precursors. PECVD processing allows deposition at lower temperatures, which is often
critical in the manufacture of semiconductors. Plasma is used to force a reaction that
would not possible at low temperature.
The table-2 can summarizes the comparison between different techniques for thin film
deposition.
Table-2: Comparison of thin film deposition parameters by different techniques
Material Uniformity Impurity Grain Film Deposition Substrate Directional Cost
Size Density Rate (A/s) Temperature
Process nm (°C)
Thermal Metals or Poor High 10~100 Poor 10~20 50~100 Yes Very
Evaporation Low Low
melting
point
materials
E-beam Both Poor Low 10~100 Poor 10~100 50~100 Yes High
Evaporation metal and
Dielectrics
Sputtering Both Very Good Low ~10 Good For Metal: ~200 Some High
metal and ~100 Degree
Dielectrics For
Dielectric:
~1-10
PECVD Mainly Good Very 10~100 Good 10~100 200-300 Some Very
Dielectrics Low Degree High
LPCVD Mainly Very Good Very 1~10 Excellent 10~100 600~1200 Some Very
Dielectrics Low Degree High

1.2.3 Chemical solution deposition ( CSD)

Chemical root is the bottom up approach; hence this method gives better
control over size and shape of the film. In chemical solution deposition
method, there is no requirement of vacuum and hence this method is cheap
and simple to handle.
Based on literatures CSD are of mainly three
types as follows;
 1- Photo-chemical Deposition (PCD)
2-Chemical Bath Deposition (CBD)
3- Sol-Gel processing--- Spin Coating, dip or immersion coatings.

Photochemical deposition method

A photochemical solution deposition method comprises introducing a starting chemical

solution into a reaction chamber, irradiating the starting chemical solution and substrate
surface with a light energy, and forming a deposition film on a substrate by utilizing a
photochemical reaction, characterized in that the plural starting chemical solutions are
introduced into the reaction chamber and the film is formed on said substrate by causing
chemical reactions by irradiating molecules of these starting solution with individual light
energy having a wavelength region corresponding to an absorption spectrum of each of
said starting solution.

Chemical bath deposition (CBD)

The most used solution technique and also one of the oldest methods for thin film growth
is chemical bath deposition (CBD) or chemical solution deposition (CSD). CBD has been
widely used for the deposition of chalcogenides for various applications. In CBD all the
precursor ions are present at the same time in the reaction vessel. Typically CBD has a
so-called terminal thickness indicating a point where the growth of thin film is stopped
due to depletion of precursors in the solution. The precursor molecules are metastable
releasing slowly ions for the deposition reaction. The product has low solubility, but due
to limited number of free ions a direct homogeneous precipitation in the solution is
prevented.
 Figure-1.9: Thin film deposition steps
For metal sources complexed ions are usually utilized. Generally sulphur and selenium
sources are decomposable molecules, like thiourea or thioacetamide and selenourea,
respectively.
Sol-gel coating
Sol-gel processing is widely used in the synthesis of inorganic and organic-inorganic
hybrid materials and capable of producing nanoparticles, nanorods, thin films, and
monolith. Sol-gel methods for oxide coatings were reviewed by Francis. Prior to sol-gel
transition or gelation, sol is a highly diluted suspension of nanoclusters in a solvent, and
typically sol-gel films are made by coating sols onto substrates. Most commonly used
methods for sol-gel film deposition are spin- and dip-coatings, though spray and
ultrasonically pulverized spray were also used.
In dip coating, a substrate is immersed in a solution and withdrawn at a constant speed.
As the substrate is withdrawn upward, a layer of solution is entrained, and a combination
of viscous drag and gravitational forces determines the film thickness,
Where η is the viscosity, U tthe withdrawal speed, ρ the density of the coating sol, and
o

c 1

is a constant. Fig. 1.10 illustrates various stages of the dip-coating process.

Figure-1.10: Various stages of dip coating process

It should be noted that the equation does not account the evaporation of solvent and
continuous condensation between Nano clusters dispersed in the sol as illustrated in

Fig. 1.11.

Figure-1.11: Sol-gel dip-coating processes

However, the relationship between the thickness and the coating variables is the same
and supported by the experimental results, but the proportionality constant is different.
The thickness of a dip-coated film is commonly in the range of 50-500 nm, though a
thinner film of ~ 8 nm per coating was also reported.

1.3 ZnO the novel material

Most of the literatures reveal that the thin film technologies are also being developed as a
means of substantially reducing the cost of photovoltaic systems, electronic equipments
and enhance the device performance. The nanostructured thin film enhances the
efficiency of solar cells, memory storage capacity of the computers, reduces the costs of
the devices as well as the materials losses. Transparent conducting films continue to
receive considerable attention from both fundamental and application point of view
primarily because of their useful properties.
The thin films of ZnO generated immense interests as a transparent semiconducting
materials, because of coating of this material are relatively inexpensive and have sharp
UV cut-off, that is why they are used as hetero junction solar cells based on CdTe,
CuInSe2 and CuInS. ZnO is also used for piezoelectric devices such as surface
acoustic wave (SAW) devices. Among the transparent conducting oxides, ZnO is
probably the most commonly studied material as it has the following unique merits.
First, ZnO is a wide band gap semiconductor that has huge potential for
electronic, opto-electronic, and optical applications. Second, it is unique in having
semiconducting, piezoelectric, and pyro-electric properties, and is an ideal candidate for
fabricating electromechanical coupled devices. Third, ZnO is a biodegradable and
possibly biocompatible material suitable for medical and biological applications . Various
techniques have been used for deposition of ZnO thin film namely, Pulsed Laser
Deposition , Atomic Layer Deposition, Spray Pyrolysis , Metal Organic Chemical
Vapor Deposition, DC Magnetran Sputtering, Photo Induced MOCVD, Reactive
Molecular Beam Epitaxy, Molecular Beam Epitaxy . The Zinc Oxide film deposited from
the above techniques has both low resistivities and high transparency in the visible
region. There are merits and demerits for each deposition technique, for example
sputtering techniques allow the fabrication of high quality films but the equipment cost
is very high with a low production rate. At the same time spray techniques are very cheap
but the films produced are not consistent. There is a lot of variation in the results reported
by different workers using different techniques.

The variation is due to the difference in the deposition parameters and the purity of the
elements. Literatures show that variation in the process parameters give the many more
nano-structures and different morphology by the thermal evaporation technique and we
can control these parameters easily. The thermal evaporation system method is less costly
than other methods for depositing the ZnO nano-structured thin films. Semiconductor
nano-wires are a promising candidate for fabrication of basic nano-devices and
complicated nano-circuits Zinc Oxide is a versatile functional semiconductor with wide
applications, such as the gas sensor and the transparent conducting film in the flat
display screen. The outstanding features of zinc oxide with a wide band gap (3.37eV)
and a large excitonic binding energy (60 meV) lead to the existence, extremely stability,
of exciton at room temperature, and enable ultraviolet luminescence (UV) lasing in ZnO
crystals. The ultraviolet luminescence from nanophase ZnO crystals in the form of thin
film or particles has been widely studied in recent years. By optimizing the process
parameters in the thermal evaporation system we can make ZnO nano-dots, nano-rods,
nano-springs and nano-belts. Literatures show that Nano-rods and nano-belts of ZnO
have tremendous applications in the sensors and memory applications at nano scales. By
the review of lots of literature survey, our attention goes towards the development of
ZnO nano-structures by the CBD technique.
 Chapte
r -2
Synthesis and Experimental Techniques
2.1 Substrate cleaning
A thoroughly cleaned substrate is essential for the preparation of films having good
adhesion and reproducible properties. The choice of cleaning procedure depends on the
nature of substrate, the type of the contaminants and the degree of cleanliness required.
Here we have taken glass as the substrate material for depositing thin film of zinc oxide
and other chemical reagents like soap solution, chromic acid and acetone for cleaning the
substrate. The glass substrates were previously degreased in chromic acid for 48 hrs,
cleaned in cold water with detergent, cleaned with acetone, ultrasonically cleaned with double
distilled water and drip dried in air.
2.2 Synthesis
A chemical bath deposition method was employed in preparing zinc oxide films on glass
substrates. The synthesis of the films was carried out using concentrated ammonia and
triethanolamine (TEA). This was done from controlled chemical reaction using TEA and a
stable zinc complex, Zn(NH3)3SO4, which slowly releases the zinc ions. The reaction bath
for the deposition of ZnO contained 1M1ml ZnSO4, 1ml 100%NH3, 1ml 100% TEA and
made to 50ml with distilled water and allowed to stay for 24 hours. The reaction baths were
tested for pH - value and it was found to be in a purely alkaline medium before the slides
were introduced into the chemical baths.

But it is occurring at room temperature with TEA and NH 3 acting as complexing agent in
alkaline medium. The reaction baths were observed to be clear solutions for about 4 hrs
When the substrates were withdrawn after 24 hours, rinsed with distilled water and drip
dried in air, white thin films were deposited on the glass substrates.
 2.2.1 Annealing of samples

As deposited thin film has stresses and less crystalline and could not be used for
device purpose because stresses reduce the desired properties of the film. A method
to reduce the stresses and improves the crystallinity was needed. The first obvious
approach was to anneal the sample to try to relax the ZnO film. Adhesion property also
improves on annealing the sample. Now we have annealing the sample at different
temperatures

Table 3: ZnO thin film on glass substrate (as grown) annealed at

different temperatures in air environment

SAMPLE ANNEALING TIME (IN ANNEALING

MINUTES) TEMPERATURE K
A 60 300
B 60 420
C 60 450

2.3 Characterization techniques

2.3.1 X-ray
diffraction
A powerful technique used to uniquely identify the crystalline phases present in materials
and to measure the structural properties (strain state, grain size, epitaxy, phase
composition, preferred orientation, and defect structure) of these phases; also used to
determine the thickness of thin films and multi-layers, and atomic arrangements in
amorphous materials (including polymers) and at interfaces. Bragg’s Law gives condition
for constructive interference from planes with spacing dhkl,

λ = 2dhkl x Sinθhkl
The X-ray diffraction patterns of various samples of ZnO thin films has been recorded
using X-ray diffractometer (at STIC, CUSAT) with CuKα radiation of wavelength 1.5418
 0
A obtained from the copper target using an in built Ni filter to ascertain crystalinity,
and the phases present. For zinc oxide thin film, the film coated on the glass slides was
0
directly taken held in the mounting on the diffractometer. The X-ray scanning rate was 3
per minute.

Figure 2.1: X-ray reflection pattern

2.3.2 UV-VIS spectrophotometer

Optical transmittance (T) of ZnO thin film was measured in the wavelength range of
250nm to 500nm with the UV-Visible spectrophotometer (UV 2450 Spectrophotometer).
For this, samples were placed in the path of one of the two light beams while a clean
substrate (i.e. bare glass slide) in the other of reference.
Measurements essentially involve sequential recording of the intensities of two
transmitted beams (through the sample and the reference) and displaying of the
difference, as the transmittance (T) of the sample. The measurements were made at
nominal incidence only.
Semiconductor devices composed of a thin film of ZnO on various substrates like glasses,
Al2O3, Silicon dioxide on silicon and on silicon. Since certain electrical properties are
dependent on film thickness, it is necessary to have a rapid, accurate and non-destructive
means of measuring the film thickness. A convenient method has been described by Carl
and Wimpfheimer.
 B R1 R2
Air θ

SiO2/ZnO Film Thickness (t)

Si/Glass Substrate

Figure 2.2: Ray diagram for optical reflection

Theory
The method used for measuring film thickness is called the interference fringe technique.
It has been applied to both infrared and ultraviolet-visible spectroscopy.
In theory the phenomenon is quite simple. A beam of incident light (B) strikes the zinc
oxide film layer at an angle α (see in the fig.). A portion of the beam is reflected (R1) by
the film layer surface. The remainder of the beam is refracted by the film, reflected at the
interface of the film and the substrate and emerges as beam (R2). The combined intensity of
the net resultant ray at a given wavelength is a function of the phase difference
between the two beams at the given wavelength.
When the wavelength of light striking a ZnO layer, having uniform thickness, is
continuously varied using a scanning double-beam spectrophotometer, the resulting
spectrum is a continuous series of waves (maxima and minima). These maxima and
minima are caused by the alternate reinforcement, at certain wavelength produces the
maxima and minima, while destructive interference, or cancellation, causes the minima.
The resulting spectrum is a series of interference fringes. It can be shown that the film
thickness (t) is a function of:
λ1= a convenient maximum wavelength

λm= a convenient minimum wavelength

n= the index of refraction
N= the number of fringes between λm and λ1

α= the angle of incidence

The relationship used to express film thickness is expressed:

2 2 1/2
t= [N (λ1λm) C] / [2(λ1-λm) (N -sin α) ]

0
Where a factor C has been introduced to yield a film thickness in Angstroms (A ),
assuming wavelength is expressed in nanometers.

C =10 A0/nm (conversion factor)

The band-gap of the of the thin film can be calculated by the following formula;

Eg=hc/λ

Where λ is the absorption edge of the transmission spectra.

Limitation of the method

The primary limitations of the method are;

0
1. A lower thickness limit of 1000A (or 0.1µm);

2. Purity of film and surface condition; and

3. Variation of refractive index with wavelength.

Advantages of the method

This method offers a rapid, accurate, and non-destructive method for the determination of
the thickness of the thin films. Carl and Wimpfheirmer demonstrate the excellent
correlation between the UV-VIS interference method, the weighing method, and the double
beam interferometer method. Only the UV-VIS interference method is non- destructive.
 Chapter
-3
Results and Discussion
3.1 X-ray analysis

The crystal structure and orientation of synthesized thin film were investigated by X-ray
Difractrometer. The X-ray diffraction patterns of various samples of ZnO thin films has
been recorded using X-ray diffract meter (at Sophisticated Test and Instrumentation centre,
Cochin University of Science and Technology)

Before annealing the XRD diagram is presented in Fig.3.1. Such diagram corresponds to
zinc hydroxide Zn(OH)2 [JCPDS 89-0138].The Zn(OH)2 is converted into ZnO by air
annealing one hour at 450 K (Fig3.2).
 Figure 3.1 XRD diagram of a CBD film after deposition, the diffraction lines correspond
to Zn(OH)2 films

Figure 3.2 XRD diagram of a CBD film after annealing one hour at 450 K, the
diffraction lines correspond to ZnO films

The annealed films are crystallized in the hexagonal structure. The lattice parameters have
been calculated from:

The mean values are a = 3.255 Å, c = 5.209 Å.

Table 1. X-ray diffraction comparison between the reference data (JCPDS 86-1397) and the
experimental result obtained with CBD ZnO annealed in air for one hour at 450K
In order to evaluate the mean crystallite size of the films, the Debye-Scherer formula is
adopted.

0.9λ
D=
β cosθ

Where λ is the X-ray wavelength , β is the line broadening at half the

maximum intensity (FWHM), after subtracting the instrumental line broadening

in radians. This quantity is also sometimes denoted as Δ(2θ).

The mean crystallite size of the films are 36 nm, 41 nm and 32 nm for the (100), (002)

and (101) direction respectively, along the c axis direction.

 3.2 UV-VIS Spectrophotometer Analysis.

Figure 3.3 Absorbance A as a function of wavelength(λ) for ZnO thin films under various
thermal treatments.
 Figure 3.4 Transmittance(T) and reflectance(R) as a function of wavelength(λ) for ZnO

thin films under various thermal treatments.

The spectral absorbance of the film is shown in Fig.3.3 while the spectral transmittance

and reflectance of the films are shown in Fig.3 . 4 . The film observed absorption peaks at

368nm, 449nm and 566nm. The annealing of film to 420K initially did not show any clear

difference as they overlapped with the film deposited at 300K up till 476nm from where the

absorbance started showing a marked difference. Although absorbance spectra decreased

with increasing wavelength it is observed that the film annealed to 420K and 450K

showed lower absorbance than deposited film at 300K The reduction in the absorbance of
the film due to annealing could be attributed to the changing of Zn(OH)2 to ZnO.

Transmittance of the film improved with its annealing. The reflectance of film decreased

from the UV region towards the NIR region on average of 12 to 17% which is moderately

high. The moderately high transmittance and reflectance of the film throughout the UV-

VIS-NIR regions makes it a good material for applications as antireflection thermal control

coating material.

3.3 Conclusions
The chemical bath deposition technique allows to grow columnar ZnO films with
good structural properties for use in solar cells. Zinc oxide films have been successfully
deposited on glass substrates at room temperature and annealed at various temperatures.
The XRD pattern also explains that the existence of ZnO single phase with a hexagonal
structure. XRD analysis of the annealed thin films shows that, the crystallinity got with
increase in annealing temperature and film was highly crystalline at 450K.The
moderately high transmittance and reflectance of the film throughout the Solar spectrum
regions make ZnO thin films good material for applications as antireflection thermal
control coating material.
3.4 Future Scopes
Followings are the future scopes;
1) Since ZnO shows piezoelectric behavior, so it can be used as cantilever of AFM
tip and for sensor applications.
2) ZnO is high band gap material, and hence it may be used in LED’s.
3) The ZnO shows ferroelectricity at room temperature; hence it can be used in
spintronic for memory applications.
4) Adhesion measurement of ZnO thin films can be done on the different substrate
like SiO2/Si, quartz, sapphire and Si.
References

1. A. KATHALINGAM, N. AMBIKA Chemical bath deposition and characterization of

nanocrystalline ZnO thin films- Materials Science-Poland, Vol. 28, No. 2, 2010

2. Hani Khallaf, Guangyu Chai- Investigation of chemical bath deposition of ZnO thin

films using six different complexing agents- J. Phys. D: Appl. Phys. 42 (2009) 135304

(8pp)

3. S M Huang, Z Q Bian, J B Chu, Z A Wang- One-step growth of structured ZnO thin

films by chemical bath deposition in aqueous ammonia solution- J. Phys. D: Appl. Phys. 42

(2009) 055412 (6pp)

4. Properties of ZnO thin films deposited by chemical bath deposition and post annealed-

2006 J. Phys. D: Appl. Phys. 39 1954

5. Growth and Electrical properties of ZnO Films prepared by Chemical Bath Depostion

Method- Dewei Chu- Physics Status Solidi A 206

6. Chemical Solution deposition of ZnO thin films with controlled crystallite orientation

and intense ultraviolet emission-Mingsong Wang, Sung Hong Hahn-Thin Solid Films

516(2008) 8599-8603

7. Thin Film Fundamentals - A. Goswami

8. Thin Film Solar Cells- K.L. Chopra, S.R. Das

9. Thin film phenomena - K L Chopra

10. Materials Science - G. K. Narula, K. S. Narula, V. K. Gupta

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