CHAPTER-1

INTRODUCTION

1
1.1. Introduction and Motivation

Nanotechnology describes the practice of science, technology or engineering on a molecular

or atomic scale. It refers to a wide application of uses across many fields of science, such as
organic chemistry, physics and molecular biology, and refers to any manipulation of matter
occurring on a scale of 1 to 100 nanometers. [1]
Nanotechnology was developed in 1980s with the invention of the scanning tunneling
microscope in 1981 and the discovery of fullerenes in 1985. This field was drawn public
awareness in 2000s due to potential implications and the feasibility of the applications. In the
past few years, nanomaterials have attracted tremendous international interest, investment and
effort both in scientific research and in industrial development because of their potential
applications in various fields [2-5].
Thin films
Thin film is the general term for coatings that are used to modify and increase the
functionality of a bulk surface or substrate. Here we need to define substrate and coating.

History of thin film:

The history of thin film technology is briefly discussed below:

1704: Isaac Newton stated in his book, Opticks, that the iridescence in a peacock feather
was due to the fact that the transparent layers in the feather were so thin.[6]

1850: Development of first deposition techniques by M. Faraday, W. Grove, T. A. Edison

and of methods of thickness determination by Arago, Fizeau, Wernicke; Wiener also
commercial introduction of electrochemistry for gold plating of uniform accessories was
invented.

1930: Commercial use of thermal evaporation was started.[7]

1940: Industrial manufacturing of coatings for optical, electronical and mechanical

applications (mostly military)

2
1990: Hard coating for tools and decorative applications had become important new
applications.

1995: Thin film processing allows for the tailoring of microstructures of atomic and
mesoscopic dimensions (Quantum dots by PVD, Cu- technology by electrochemistry applied
to integrated circuits )

2000: Manufacturing of nanocrystaline materials with defined composition and structure for
applications as protective coatings and in tribology. Deposition of highly ordered two and
three dimensional objectives with size in the nm range.

2004: Upscaling of complex reactive coating process for industrial applications.

Combinatorial investigation of ternery and quarternery material systems

2006: Investigation of organic coatings leads to the emergence of organic electronics.[8]

Importance of thin film:

It’s Thin
This is the reason thin film was attractive to begin with. Thin film materials have a property,
called bandgap, which is superior to silicon. Funny as it sounds, silicon just doesn’t like to
absorb light. First of all, it only wants to absorb low wavelength light (red and IR), rather than
most of the light that comes from the sun. It has the wrong bandgap (which wavelength is
absorbed), and it doesn’t even absorb that very well. It takes over 100 microns of material to
absorb the light, where thin film takes only 1 micron. Thin film absorbs the right wavelengths,
and does it with 100x less material. In an industry where materials cost is important, thinner is
much better.
Through the Looking Glass
Thin film uses a less expensive and easier to work with substrate (what the solar cell is built
on). While silicon uses silicon (duh), most thin film uses glass. Silicon is more than 10 times
more expensive, ($36/m2 vs. $3.60/m2). To repeat: materials costs are very important.
Easy as FPD
3
Utilizing glass as a substrate allows for unrivaled scale. The flat panel display (FPD) industry,
which allows us to watch HDTV at a reasonable price, has scaled glass processing tools to an
amazing 50X higher throughput over the last few decades. All that know-how is available to
anyone using glass substrates. A single thin film production line can achieve 300 MW output
per year vs. the 25 MW standard for c-Si. This scaling advantage is huge when it comes to
reducing those non-materials costs such as labor, overhead, and depreciation. [9]

So this thesis work is based on thin film deposition by SOL-GEL technology.

1.2. Literature review:

Nanotechnology ("nanotech") is manipulation of matter on an atomic, molecular, and

supramolecular scale. 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 one dimension sized from 1 to 100 nanometers. It is
therefore common to see the plural form "nanotechnologies" as well as "nanoscale
technologies" to refer to the broad range of research and applications whose common trait is
size. [10]
Thin film technology can be applied to different substrate materials such as metals, ceramics
or polymers. Very common substrate materials are silicon, glass and steel. By properly
choosing the technology and the deposition materials, properties of the substrate material can
be improved, enhanced and tailored to meet the special requirements of a particular
application. In addition, thin film technologies are now available that can be applied to either
flat substrates or objects with very complex geometrical shapes.

Deposition materials for thin film processes can range from metals and pure elements to more
complex compounds, such as oxides, nitrides and polymers. Source materials, in most cases,
require high levels of purity to ensure optimal properties of the thin film coating. It is not
uncommon to use deposition materials with purity exceeding 99.99%.[11]

A very effective method of thin film deposition is SOL-GEL technique. The sol-gel process is
a wet-chemical technique widely used in the fields of materials science and ceramic
4
engineering. Such methods are used primarily for the fabrication of materials (typically metal
oxides) starting from a colloidal solution (sol) that acts as the precursor for an integrated
network (or gel) of either discrete particles or network polymers. Typical precursors are metal
alkoxides and metal salts (such as chlorides, nitrates and acetates), which undergo various
forms of hydrolysis and polycondensationreactions [12].

S.M Attia, Jue Wang, Guangmin WU, Jun Shen and Jianhua “ Review on sol-gel drived
coatings: process, technique and optical applications”, journal of materials science and
technology, vol-18, no-3, 2002 . here conventional sol-gel technique is briefly discussed.

But this technique is not automatic and requires manual control which is not appropriate for
preparing uniform thin films.

Md. Feroz Ali, Utpal Saha and M.F.Hossain* “Design an Automatic Dipping and
Withdrawing System for the Deposition of Thin Films” ICECTE2012. In this paper an
automatic length controlled sol- gel system is designed which can deposit thin film for 2cm,
3cm, 4cm, 5cm,6cm,7cm.
But this system requires the use of ribbon which is very much subjected to vibration and the dipping and
withdrawing speed can not be controlled in this system.

Shuva paul “Optimization of microcontroller based automatic sol-gel method with

respect to optical proparties of ZnO films” B.Sc. Dissertation, EEE, RUET, 2013. in this
paper a digital sol-gel system is proposed.
This system was designed to solve the problem of using ribbon by using mechanical gear but it was not
completely vibration less.

Ayesa Tuz Johra Shilpy “Fabrication of digital SOL-GEL coating system and
characterization of prepared ZnO thin films with respect to optical properties” B.Sc.
Dissertation, EEE, RUET, 2016. In this paper a digital sol-gel system was proposed and Rack
and pinion was replaced by rod and friction wheel.

But the weight of the machine was too small to reduce the vibration of the motor and friction
in the rod and pinion caused non uniform motion of the substrate holder.

1.3. Nanotechnology
One nanometer (nm) is one billionth, or 10-9 of a meter. By comparison, typical carbon-carbon
bond lengths, or the spacing between these atoms in a molecule, are in the range 0.12–0.15
nm, and a DNA double-helix has a diameter around 2 nm. The lower limit is set by the size of

5
atoms (hydrogen has the smallest atoms, which are approximately a quarter of a nm diameter)
since nanotechnology must build its devices from atoms and molecules.[13]

Different types of nonmaterial are shown in figure 1.1

Figure 1.1: different types of nonmaterial

1.3.1. Applications of nanotechnology

The 2000s have seen the beginnings of the applications of nanotechnology in commercial
products, although most applications are limited to the bulk use of passive nanomaterials.
Examples include titanium dioxide and zinc oxide nanoparticles in sunscreen, cosmetics and
some food products; silver nanoparticles in food packaging, clothing, disinfectants and
household appliances such as Silver Nano; carbon nanotubes for stain-resistant textiles; and
cerium oxide as a fuel catalyst. As of March 10, 2011, the Project on Emerging
Nanotechnologies estimated that over 1300 manufacturer-identified nanotech products are
publicly available, with new ones hitting the market at a pace of 3–4 per week. [14]
Applications of nanoparticles in different sectors are shown in figure 1.2

6
 Figure 1.2: Applications of nanoparticles in different sectors

Some recent applications of nanotechnology are briefly discussed below:

Water treatment:

By using nanoparticles the treatment of surface water, groundwater, wastewater, and other
environmental materials contaminated by toxic metal ions, organic and inorganic solutes, and
microorganisms is possible which is shown in figure 1.3. Many nanomaterials are under
research for the treatment of water from contaminations. [15] At present nanotech-based
technologies applied in water treatment consists of reverse osmosis, nanofiltration,
ultrafiltration membranes. Nanotechnology is expected to deal more efficiently with
contaminants which convectional water treatment systems struggle to treat, including bacteria,
viruses and heavy metals. This efficiency generally stems from the very high specific surface
area of nanomaterials which increases dissolution, reactivity and sorption of contaminants.
[16]

7
 Figure 1.3.Water filtration process by using semi permeable membrane

Generation of Hydrogen:
Now-a-days renewable energy has become talk of time. Hydrogen is a promising source of
renewable energy like solar power, nor is it a naturally occurring fuel like methane or coal.
However, the process by which it releases its energy is very efficient, and the only exhaust
gas produced is pure water. Some kinds of nanoparticles (titanium dioxide, which is a
common white pigment in its bulk form) have shown very strong photocatalytic activity.

Figure 1.4.Photocatalytic Hydrogen Productions [17]

8
Solar cell application:

A solar radiation is a source of renewable energy. Solar cell is a device that converts solar
energy directly to electricity. A solar cell is a sandwich of n-type silicon and p-type silicon.
When sunlight shines on the cell, photons (light particles) bombard the upper surface. The
photons carry their energy down through the cell. The photons give up their energy to
electrons in the lower, p-type layer. The electrons use this energy to jump across the barrier
into the upper, n-type layer and escape out into the circuit. Flowing around the circuit, the
electrons make the lamp light up which is clearly seen in figure 1.5

Figure.1.5.Solar cell

1.3.2 Objectives of this thesis

There were some limitations in previously reported automatic sol-gel system.[18] So in this
work first a new sol-gel system has been developed overcoming the limitations of previous
system.

The main objectives of this thesis are given below:

1. Study of different thin films deposition techniques.

2. To develop a digital sol-gel system overcoming the problems of previously reported

automatic sol-gel system.

9
 3. Preparation of ZnO thin films using proposed digital sol-gel dip coating technique
4. Characterization of prepared ZnO thin films with optical properties

1.4. Outline of this thesis

Chapter-1:

This chapter deals with the introduction and motivation to this work. After describing
literature survey objectives of this thesis work has been clarified.

Chapter 2:
In this chapter thin film technology is briefly discussed with property and applications

Chapter 3:
In this chapter methodology of this work has been described. In order to deposit ZnO thin
films sol-gel process have been used in this work.

Chapter 4:
In order to overcome the limitations of previously reported sol-gel system a new digital sol-
gel system has been developed. This chapter deals with the modeling and fabrication of new
digital sol-gel system with necessary figures and circuit diagrams.

Chapter 5:
Experimental procedures for depositing ZnO thin films using sol-gel method have been fully
described in this chapter.

Chapter 6:
This chapter is about the experimental results and discussions that includes optical properties
of prepared ZnO thin films, comparison between previous and proposed sol-gel derived ZnO
thin films .

Chapter 7:
Finally a conclusion of this work has been given in this chapter and future directions related
to the work in this thesis has been also given.

10
 CHAPTER-2
THIN FILM
TECHNOLOGY

11
2.1.Thin films
Thin film is the general term for coatings that are used to modify and increase the
functionality of a bulk surface or substrate. Figure 2.1 shows a typical thin film.

Substrate: This is the base material upon which thin film is deposited. There are various kind
of substrate such as glass, FTO, Si wafer, Ti sheet etc.

Coating: it is a solid body on the substrate which exhibits a significantly lower geometrical
extension in one dimension then in the remaining two spatial dimensions. The properties of
the film or coating have to differ significantly from the bulk.[19]

A thin film is a layer of material ranging from fractions of a nanometer (monolayer) to several
micrometers in thickness. Electronic semiconductor devices and optical coatings are the main
applications benefiting from thin-film construction.

Figure: 2.1.Thin film

12
There is a limit between “thin” film and “thick” film

Thin film: The films which are less than 1µm in thickness and also have high transparency is
known as thin film.

Thick film: the films which don’t have transparency and thickness is greater than 1µm is
known as thick film.[19]

2.2. Properties of thin film

There are many properties of thin film. Some of the properties of thin film is given below:

Electrical property: Conductivity for conductive films, resistivity for resistive films,
dielectric constant, dielectric strength, dielectric loss, stability under bias, polarization,
permittivity, electromigration, radiation hardness.

Thermal property: coefficient of expansion, thermal conductivity, temperature variation

of all properties, stability or drift characteristics, thermal fusion temperature, volatility and
vapor pressure.

Optical property: transmittance, absorption, refractive index, birefringence, spectral

characteristics, dispersion

Morphological property: Crystalline or amorphous, Structural defect density, Step

coverage, Microstructure, Surface topography, Crystallite orientation

Mechanical property: Intrinsic, residual and composite stress, anisotropy, adhesion,

hardness, density, fracture, ductility, elasticity.[20]

2.3. Thin film deposition technique

A wide variety of process technologies are available for the deposition of thin films. The
technologies differ to a large degree in their physical and chemical principles of operation and

13
in the commercially available types of equipment. Each process technology has been pursued
or developed because it has unique advantages over others. However, each process
technology has its limitations. In order to optimize the desired film characteristics, a good
understanding of the advantages and restrictions applicable to each technology is necessary.
Thin film can be deposited by solid particle deposition vapor phase deposition and wet
solution process. Some of the deposition process is briefly discussed below:
2.3.1. Solid particle deposition:
Solid state particle deposition:
Precursor solution (powder or paste) should be made first. A dry and clean glass substrate is
taken. Powder or paste is spread upon the substrate. Then the substrate is calcined at 100 ͦ C-
1000 ͦ C. The procedure is shown in figure 2.2

Figure:2.2. Solid particle deposition technique

Screen Printing:

Screen printing is a printing technique whereby a mesh is used to transfer paste of a solid
material onto a substrate, except in areas made impermeable to the paste by a blocking stencil.
A blade or squeegee is moved across the screen to fill the open mesh apertures with paste, and
a reverse stroke then causes the screen to touch the substrate momentarily along a line of
contact (figure 2.3). This causes the paste to wet the substrate and be pulled out of the mesh
apertures as the screen springs back after the blade has passed.

14
 Figure: 2.3. Screen printing technique

Doctor blade technique:

First the substrate is masked with Tape except desired area. Then paste has to prepare with the
help of required materials. Then the paste is spread on the surface. Then the tape is removed
and the substrate is calcined at 450 ͦ C. Figure 2.4 represents doctor blade technique.

Figure: 2.4. Doctor blade technique

15
2.3.2. Vapor phase deposition: Vapor phase deposition can be of two types. They are
comical vapor deposition (CVD) and physical vapor deposition (PVD)

Physical vapor deposition (PVD):

Thermal Evaporation:

The thermal evaporation basically follows the vapor-solid (V-S) mechanism. Usually material
powders are placed inside a vacuum chamber, where the vacuum condition is kept in the
range of 10-2 to 10-9 Tor. The powder will be heated up by a heating source to its vapor point
once the appropriate pressure within the vacuum chamber is reached. The vaporized materials
will condense along the cooler surfaces in the vacuum chambers,

Pumpi
ng
unit

Vacuum
chamber
Figure 2.5. Schematic representation of thermal evaporation
as well as on the collection substrate (figure 2.5). By varying the experimental temperature,
pressure in the chamber, atmosphere and facility configuration thin films and various
nanostructures can be produced by this method.
Electron beam, radio frequency (RF) inductive, and resistive heating are the heating
sources typically used in thermal evaporation. Electron beam and RF inductive heating are
used to create localized heating of the source material, which have been limited to produce
highly oriented thin films. Resistive heating is a non-localized heating source and commonly
used for furnace applications. For example, a tube furnace with appropriate design and control
can create a specific temperature gradient along the tube, which is useful for nanostructure
production.

16
Sputtering:
Sputtering is the removal of surface atoms via high energy ions. The modern sputtering
system uses a magnetron sputtering configuration, where a strong magnetic field is applied to
concentrate the plasma near the target to increase the deposition rate. Certain level of vacuum
is required for the sputtering system. During the experiment, after evacuation of foreign gas,
an inert gas normally Ar as the working gas, is introduced into the vacuum chamber where the
source material target and substrate shave been placed in. Then a direct current (DC) or RF
power supply is used to ionize the inert gas so as to produce charged plasma. The ions are
accelerated to the surface of the target, and bombarding the atoms of the source material out
of the target. Resultantly, some of those atoms condense on the substrate to form films.

Figure 2.6. Schematic arrangements of dc sputtering method

A bias voltage sometimes is applied to the substrate to assist the deposition. Figure 2.6 is a
clear representation of sputtering method.

2.3.3. Wet solution process

Sol-Gel Synthesis
ZnO thin films, nanocrystals, nanorods with preferred crystallographic orientation have been
synthesized using the sol-gel method. “Sol” is referred to a colloidal suspension. The
formation of Sol will develop inorganic networks, and as the networks form in a continuous
17
liquid phase, it becomes “gel”. The precursors for synthesizing these colloids consist of a
metal/metalloidsurrounded by various reactive ligands. Metal alkoxides are most popular
because they react readily with water. At the functional group level, three reactions are
involved in the sol-gel process:hydrolysis, alcohol condensation, and water condensation.
However, a number of factors such as PH, temperature and time of reaction, reagent
concentrations, catalyst nature and concentration, aging temperature and time, and drying
have impacts on the characteristics and properties of a particular sol-gel inorganic network by
affecting the rate of hydrolysis and condensation reactions.

Spin coating:

Spin coating is a process used to deposit uniform thin film to a flat substrate. usually a small
amount of coating material is applied on the center of the substrate. The machine used for spin
coating is called spin coater or simply spinner.

Table 2.1.Thin films and nanostructures synthesis methods and their advantages and
limitations [18]
Category Techniques Advantages Limitations
High quality High temperature
Thermal Nanostructures variety Vacuum
evaporation No chemical waste Small scale
Bad adhesion to substrate
PVD Doping High vacuum
(gas SputteringGood adhesion to substrate Nanostructures difficulty
phase) Low temperature capability
High quality High vacuum
Variety of products Expensive equipment
PLD
Precise control of composition Small scale up
Doping profile
Thermal CVD Industrial used technique High temperature
& Nanostructures capable Vacuum
LPCVD
Lower operation temperature Nanostructure difficulty
PECVD
CVD Film deposition Vacuum condition
(gas Precise control of nanostructure Vacuum
LCVD
phase) Dimension and doping Facility requirement
High quality Toxic chemical
Products variety High vacuum
MOCVD
Nanostructures capable High temperature
Expensive facility

18
 Ultra high crystal quality Ultra high vacuum
Nanostructure capable Expensive equipment
MBE
Precise control of doping profile Critical operation requirement
Small scale
Low temperature Product quality
Easy operation Uniformity
Large variety of nanostructures Precise control
CBD
High yield, low cost Environment issues
Scale up capable Doping problem
Bad adhesion to substrate
Low temperature Product quality
Traditional method Uniformity
Nanostructures capable Precise control
SBC ECD
Porous film Environment issues
Low cost
Scale up capable
Low temperature Product quality
Easy operation Uniformity
Large variety of nanostructures Precise control
Sol-gel
High yield Environment issues
Low cost
Scale up capable

2.4. Applications of thin film:

In considering the different applications of deposited thin films,[21][22] the following generic
categories can be identified.
Electronic Components: The fabrication of electronic components, especially solid-state
devices and microelectronic integrated circuits, have undoubtedly found the widest and most
demanding applications for thin film depositions. These films typically consist of
semiconductor materials, dielectric and insulating materials, and metal or refractory metal
silicide conductors.
Electronic Displays: Electronic displays are used for interfacing electronic equipment
with human operators. Different components and device structures are required, such as:
Liquid-crystal displays
Light-emitting diodes (LEDs)
Electroluminescent displays
Plasma and fluorescent displays
Electrochromic displays

19
The fabrication of these displays requires conductive films, transparent and conductive films,
luminescent or fluorescent films as well as dielectric and insulating layers.
Optical Coatings: Optical coatings are applied for antireflection purposes, as interference
filters on solar panels, as plate glass infrared solar reflectors, and for laser optics. In the
fabrication of filter optics, thin films with refractive index gradients are deposited on preforms
from which the optical fibers are drawn. These coatings require dielectric materials with
precisely defined indices of refraction and absorption coefficients. Laser optics require metal
reflective coatings which can withstand high radiation intensities without degradation.
Infrared reflecting coatings are applied to filament lamps to increase the luminous flux
intensity.
Magnetic Films for Data Storage: Thin films of magnetic materials have found wide
commercial applications for data storage in computers and control systems. The substrates can
be metal, glass or plastic polymeric materials. Thin film deposition processes for magnetic
materials and for materials with a high degree of hardness are required.
Optical Data Storage Devices: Thin films are finding increasing commercial use for
optical data storage devices in compact disks and computer memory applications. Processes
for the deposition of organic polymer materials as storage media and as protective overcoats
are required for this technology.
Antistatic Coatings: Thin films of conductive or semiconductive materials are deposited
to provide protection from electrostatic discharges.
Hard Surface Coatings: Thin film coatings of carbides, silicides, nitrides, and borides
are finding increased uses to improve the wear characteristics of metal surfaces for tools,
bearings, and machine parts. Of particularly great current interest are films of diamond-like
carbon because of this material’s heat dissipation properties, electrical insulation, hardness,
and resistance to high-temperature and high-energy radiation.

20
 CHAPTER-3
METHODOLOGY

21
3.1. Introduction:
By various deposition techniques such as sol-gel [23-24], molecular beam epitaxy [25], dc
and rf sputtering [26-27], chemical vapor deposition [28], metal-organic chemical vapor
deposition [29], pulsed laser deposition [30], spray pyrolysis [31] etc thin film can be
produced. Among these techniques sol gel dip coating provides simplicity and low cost. We
can get both amorphous and crystalline coating.[32] In materials science, the sol-gel process
is a method for producing solid materials(ceramic , glass) in the form of thin films from small
molecules. This method is used for the fabrication of metal oxides, especially the oxides of Si,
Zn, Ti. The basis for the sol-gel coating process is the hydrolysis of metal alkoxide
compounds in alcoholic solutions The process involves conversion of monomers into a
colloidal solution (sol) that acts as the precursor for an integrated network (or gel) of either
discrete particles or network polymers. Typical precursors are metal alkoxides. [33]

The sol-gel dip coating system [34] is very useful technique for fabricating & characterizing self-assembled
structures & multi-layered thin films. There are many applications of sol–gel technique. Some of
them are protective coating, Thin films and fibers, Nanoscale powders, Optomechanical,
Mechanics of gelation , Structural relaxation.
In this work, as a wet solution processing technique sol-gel route was used to
prepare ZnO thin films. A detail review on sol–gel processes of ZnO film preparation has
been reported by Lamia Znaidi [35]. Depending on the nature of the molecular precursors,
two sol–gel routes are currently used: metal alkoxides in organic solvents or metal salts in
aqueous solutions [36]. The main methods of ZnO preparation are intermediate between the
two sol–gel methods since they use metal salts in alcoholic solutions. ZnO films are obtained
starting from inorganic salts such as nitrates, chlorides, perchlorates or organic salts like
acetates and acetylacetonates, dissolved in alcoholic media. In such media the process
involves two steps. The first one consists of in situ formation of alkoxide or alkoxy-
complexes. In the second step, these complexes undergo transformation through hydrolysis
and polymerization to lead to the oxide.

3.2. ZnO the Novel Material

22
ZnO is a promising material for the fabrication of the nanodevices such as light emitting
diodes, electrochemical sensors, ultra-violet (UV) detectors, nanogenerators and etc.
Currently, zinc oxide is the most studied material among metal oxides due to its
 High energy band gap position (3.37eV)
 Large excitation binding energy (60 meV)
 High photoelectric response
 Anisotropic Property
 Inexpensive and availability
For these reasons, ZnO-based devices can be used in optoelectronics, sensors/transducers and
lasers etc.

Zinc Oxide is an inorganic compound which usually appears as a white powder. There are
few basic physical parameters for the ZnO at the room temperature which is listed in table
2.2. The chemical bonds that form Zinc Oxide are borderline between ionic and covalent
bonds though they lean towards being ionic. ZnO has relatively low solubility in water (1.6 X
10 -6 g/cm3 or 2 X 10 -6 moles/liter) and even less solubility in Ethanol. There is still some
uncertainty in the values of the thermal conductivity due to the presence of some crystal
defects in the material. In addition, a stable and reproducible p-type doping in ZnO is still a
challenge and cannot be achieved. The findings regarding the values related to the mobility of
hole and its effective mass are still arguable. The values of the carrier mobility can surely be
enhanced after achieving good control on the defects in the material.

Table 3.1: Basic physical parameters of ZnO at room temperature [18]

Parameters Values
Lattice constants at 300 K a = 0.32495 nm, c = 0.52069 nm
Density 5.67526 g/cm3
Molecular mass 81.389 g/mol
Melting point 2250 K
Electron effective mass 0.28 m0
Hole effective mass 0.59 m0
Static dielectric constant 8.656
Refractive index 2.008, 2.029
Bandgap energy at 300 K 3.37 eV
Exciton binding energy 60 meV
Thermal conductivity 0.6 – 1.16 W/Km
Specific heat 0.125 cal/g°C
Thermal constant at 573 1200 mV/K

23
 Electron mobility ∼210 cm2/Vs

3.3. Sol-gel process

The sol-gel process is a wet-chemical technique widely used in the fields of materials science
and ceramic engineering. Such methods are used primarily for the fabrication of materials
(typically metal oxides) starting from a colloidal solution (sol) that acts as the precursor for an
integrated network (or gel) of either discrete particles or network polymers. Typical
precursors are metal alkoxides and metal salts (such as chlorides, nitrates and acetates), which
undergo various forms of hydrolysis and polycondensationreactions [37].

3.3.1. Steps of sol-gel process:

Sol-gel process consists of following steps [38]:
i) Preparation of a homogeneous solution either by dissolution of metal organic
precursors in an organic solvent that is miscible with water, or by dissolution of
inorganic salts in water.
ii) conversion of the homogeneous solution into a sol by treatment with a suitable
reagent (generally water with or without any acid/base)
iii) aging;
iv) shaping; and
v) Thermal treatment/ sintering.

In this chemical procedure, the 'sol' (or solution) gradually evolves towards the formation of a
gel-like diphasic system containing both a liquid phase and solid phase whose morphologies
range from discrete particles to continuous polymer networks. Formation of polymer network
involves connecting the metal centers with oxo (M-OM) or hydroxo (M-OH-M) bridges.
M −¿+ H 2 O → M −OH + ROH (3.1)

M −OH + HO− M → M −O−M + H 2 O (3.2)

M −¿+ HO−M → M −O−M + ROH (3.3)

24
 Figure: 3.1.Steps of sol-gel dip coating process

At the first stage a precursor solution is made and then hydrolyzed to have clear solution.
After that a substrate is immersed into and withdrawn from the solution with a well-defined
speed under controlled temperature and atmospheric conditions. Withdrawing the substrate
causes to form wet layer on the substrate and gelation of the layer by solvent evaporation
(figure 3.1). The atmosphere controls the evaporation of the solvent and the subsequent
destabilization of the sols by solvent evaporation leading to a gelation process and the
formation of a transparent film due to the small particle size in the sols (nm range) [38].

3.3.2. Advantages of sol-gel process:

There are various advantages of sol-gel process for the formation of thin film over all other
process. Some of the advantages are given below:

 Low processing temperature

 Low-cost
 High purity and homogeneity
 Good shaping ability and easy fabrication of extremely light and porous materials.
 Can easily shape materials into complex geometries in a gel state.
 Can produce thick coating to provide corrosion protection performance.
 Can produce thin bond-coating to provide excellent adhesion between the metallic
substrate and the top coat

25
3.3.3. Limitations of conventional sol-gel dip coating technique:
Sol- gel is a very simple process. We can produce thin film in conventional process which
includes hand using sol-gel process. But in conventional process there are some limitations
for which we can not get require characteristics of thin film. The limitations of conventional
sol-gel dip coating technique are given below:
 Dipping rate and withdrawing rate can not be fixed in conventional process. For good
film quality dipping rate and withdrawing rate must be in 2-38 mm/s [39]
 At high speed gas bubble can form
 Film thickness is not uniform

3.3.4. Applications of sol gel process:

The applications for sol gel-derived products are numerous.[40-41] For example, scientists
have used it to produce the world’s lightest materials and also some of its toughest ceramics.
One of the largest application areas is thin films, which can be produced on a piece of
substrate by spin coating or dip coating. Protective and decorative coatings, and electro-optic
components can be applied to glass, metal and other types of substrates with these methods.
Cast into a mold, and with further drying and heat-treatment, dense ceramic or glass articles
with novel properties can be formed that cannot be created by any other method. Other
coating methods include spraying, electrophoresis, inkjet printing or roll coating.

Thin films and fibers:

With the viscosity of a sol adjusted into a proper range, both optical and refractory ceramic
fibers can be drawn which are used for fiber optic sensors and thermal insulation,
respectively. Thus, many ceramic materials, both glassy and crystalline, have found use in
various forms from bulk solid-state components to high surface area forms such as thin films,
coatings and fibers. [42] The sol-gel method can also be used to make indium tin oxide thin
films (a transparent conducting oxide) for low-cost solar photovoltaic applications.[43]

Nanoscale powders:

26
Ultra-fine and uniform ceramic powders can be formed by precipitation. These powders of
single and multiple component compositions can be produced on a nanoscale particle size for
dental and biomedical applications. Composite powders have been patented for use as
agrochemicals and herbicides. Powder abrasives, used in a variety of finishing operations, are
made using a sol-gel type process. One of the more important applications of sol-gel
processing is to carry out zeolite synthesis. Other elements (metals, metal oxides) can be
easily incorporated into the final product and the silicate sol formed by this method is very
stable.

Another application in research is to entrap biomolecules for sensory (biosensors) or catalytic

purposes, by physically or chemically preventing them from leaching out and, in the case of
protein or chemically-linked small molecules, by shielding them from the external
environment yet allowing small molecules to be monitored. The major disadvantages are that
the change in local environment may alter the functionality of the protein or small molecule
entrapped and that the synthesis step may damage the protein. To circumvent this, various
strategies have been explored, such as monomers with protein friendly leaving groups (e.g.
glycerol) and the inclusion of polymers which stabilize protein (e.g. PEG).[44]

Other products fabricated with this process include various ceramic membranes for
microfiltration, ultrafiltration, nanofiltration, pervaporation and reverse osmosis. If the liquid
in a wet gel is removed under a supercritical condition, a highly porous and extremely low
density material called aerogel is obtained. Drying the gel by means of low temperature
treatments (25-100 °C), it is possible to obtain porous solid matrices called xerogels. In
addition, a sol-gel process was developed in the 1950s for the production of radioactive
powders of UO2 and ThO2 for nuclear fuels, without generation of large quantities of dust.

Opto-mechanical:

27
Macroscopic optical elements and active optical components as well as large area hot mirrors,
cold mirrors, lenses and beam splitters all with optimal geometry can be made quickly and at
low cost via the sol-gel route. In the processing of high performance ceramic nanomaterials
with superior opto-mechanical properties under adverse conditions, the size of the crystalline
grains is determined largely by the size of the crystalline particles present in the raw material
during the synthesis or formation of the object. Thus a reduction of the original particle size
well below the wavelength of visible light (~500 nm) eliminates much of the light scattering,
resulting in a translucent or even transparent material.

Furthermore, results indicate that microscopic pores in sintered ceramic nanomaterials,

mainly trapped at the junctions of microcrystalline grains, cause light to scatter and prevented
true transparency. it has been observed that the total volume fraction of these nanoscale pores
(both intergranular and intragranular porosity) must be less than 1% for high-quality optical
transmission. I.E. The density has to be 99.99% of the theoretical crystalline density.[45]

Medicine:

Unique properties of the sol-gel provide the possibility of their use for a variety of medical
applications[46-47] A sol–gel processed alumina can be used as a carrier for the sustained
delivery of drugs and as an established wound healer. A marked decrease in scar size was
observed because of the wound healing composite including sol–gel processed alumina. A
novel approach to thrombolysis treatment is possible by developing a new family of injectable
composites: plasminogen activator entrapped within alumina.

28
 CHAPTER - 4
DEVELOPMENT OF
DIGITAL
SOL-GEL SYSTEM

29
4.1. Introduction:
To overcome the problems of conventional sol-gel method automatic sol-gel system has been
introduced which is referred to [48]. But there are some limitations in this system. Some of
the limitations are overcome by Ayesha Tuz Johra Shilpy [18]. But still there are some
limitations in the system referred to [18]. So, in this work a digital sol-gel system has been
developed by overcoming the limitations of previous systems. In this chapter designing and
operating principle of newly developed system is described.

4.2. Problems and proposed improvements of existing digital sol-gel system.

The existing digital sol-gel system has some major limitations. The limitations of existing
digital sol-gel system are given below:

 The substrate dipping and withdrawing is not completely free form vibration due to
rod and friction wheel.
 The weight of previous machine is so low. So when the motor starts it also causes
vibration.
 There are some programming defects of the microcontroller so the machine does not
operate accurately.
 The lowest speed of the machine we can have is not up to the desired level.

In the proposed automatic sol-gel system these limitations are overcome. The proposed
system designed to minimize the vibration of the system so that we can get improved
characteristics. In proposed system

 Dc gear motor with encoder is used.

 rod and friction wheel is replaced by belt pulley mechanism.
 Steel steet is used to cover the entire machine which increases the weight of the
machine.
 To achieve a robust structure of the machine aluminium sheet is used to build the
structure.
 There is no need to adjust the beaker base. Just some initial inputs are given and the
machine operates on its own.

30
4.3. Block diagram representation of digital sol-gel system

Fig.4.1 shows the basic block diagram representation of proposed digital sol-gel system. The main parts of the
digital sol-gel system are dc power supply unit, 3*3matrix keypad, 16*2 LCD unit, motor driver, pulley, belt,
lead screw, motion filter, substrate holder and a microcontroller unit which is the heart of the automatic
arrangement. DC power supply unit rectifies 220V ac supply into 5V dc which is supplied to various
components of the system.

Figure 4.1.Block diagram representation of digital sol-gel system

The dc gear motor used in this work is of 12V dc bipolar motor. A motor driver a 16 pin IC named L293D has
been used. Pulley belt and lead screw mechanism has been used to convert the circular motion of DC gear motor
into linear motion and a crocodile clip is connected with the rod which is used to hold the substrate. As a input
device a 3*3 matrix keypad and as a display unit a 16*2 LCD character display has been used. After giving input
value through matrix keypad microcontroller sends out control signal to the motor driver to drive the DC gear
motor. According to the control signal, the DC gear motor starts rotation either in clockwise or anticlockwise
direction.

4.4. Complete setup of automatic sol-gel system

Fig. 4.2 shows the homemade automatic sol-gel system. The total body is covered by steel
sheet. The structure of the machine is made with aluminium sheet to increase the stability of
the machine. The lower portion consists of the electronics part that is microcontroller, DC
power supply unit, motor driver, LCD, matrix keypad, pulley 1, pulley 2, belt etc. Figure 4.3
shows the internal view of the machine. Pulley 1 is attached with the motor shaft and Pulley 2 is connected with
pulley 1 by a belt. Then pulley 2 is connected to a lead screw which is placed vertically from lower portion to the
upper portion of the machine. A rod (to which the substrate holder is attached) with a screw is attached to the
lead screw. So when the lead screw rotates the rod moves upward or downward according to the rotation of the
lead screw. Thus the circular motion of the motor shaft is converted to linear motion.

31
 Figure: 4.2. Complete setup of proposed automatic sol-gel system

A motion filter is used to reduce the mechanical vibration when the motor rotates to have an
uniform speed of the substrate.

32
 Figure: 4.3. Internal view of the machine

The width of pulley1 = 1 inch

The width of pulley2 = 3.5 inch
This means that to rotate pulley 2 for one time, pulley 1 has to rotate for three and half times. Now the lead
screw has 13 threads per inch. That means when the screw rotates for one time its vertical distance is 1/13 inch.
So to have a vertical distance of one inch the lead screw has to rotate 13 times, pulley 2 has to rotate for 13
times, pulley 1 has to rotate for 45.5 (13*3.5)times. Thus we can have a very lower speed of the linear motion.
The lowest speed that we could achieve is 1mm/sec.

33
4.5. Operating principle of digital sol-gel system
The operating principle of digital sol-gel system is shown is Fig. 4.4. At first prepared precursor solution is kept
on the beaker base and a clean substrate is hanged on the substrate holder. Then the machine plug is connected to
the Ac line. After making the primary setup, power switch is turned on and a message “Welcome to Nano Lab
Of Ruet….Automatic sol-gel machine” comes out on display. After 2 sec a message “press ‘*’ to Start, A or B
to adjust” comes to display and we can adjust the position of the substrate holder. Then a massage “Input Initial
Position” comes out on display and we have to input the initial position of the substrate holder. Then a massage
“Input Solution Level” comes out on display and we have to input the solution level. After that a massage “Input
DIP Speed” comes out on display and we have to input the required dipping speed of the substrate. Then a
massage “Input Waiting Time” comes out on display and we have to input the desired waiting time before
withdrawing the substrate. There must not to be made hurry while pressing two keys one after another. Because
intentionally there have been made a delay of 0.5s between two keys pressing for programming purpose.
After correctly giving all of the input values from keyboard the motor starts to rotate in anticlockwise direction
to move the substrate in downward direction at a rate of given rpm. And a message “dipping process running”
comes on display. After completing the dipping

34
 Figure: 4.4 operating principle of proposed system

length the substrate wait in the solution for a given waiting time. Then it starts to withdraw at a given rpm and
when it reaches to a predetermined position it closes an alarm switch and alarm sound is heard and a message
“Thank you” comes on display and the current operation breaks down. Then the digital sol-gel system goes to
the start position and is prepared for another operation.

4.6. Internal circuitry arrangements of the digital system

35
 Figure 4.5.Complete circuit diagram of proposed digital system showing in (a) dc power supply unit,
and (b) interconnection of microcontroller with dc gear motor, keypad and LCD display.

Since all the ICs and the dc gear motor used in this work need dc power, hence a rectifier
circuit is implemented as shown in Fig. 4.5(a). At first, the conventional 220V ac supply has
been stepped down to 12V ac, using a stepped down transformer, which has been further
rectified using a bridge rectifier. The output of the rectifier has been found to be of pulsating
dc and hence has been filtered using 1000μF capacitor to get pure 12V dc. After that, this dc

36
voltage has been fed to LM7805 voltage regulator to have regulated 5V dc. The voltage
regulator has inherent advantages that dc output voltage remains unaffected with the change
of load current. Microcontroller and LCD display, keypad, motor driver L293D requires 5V
dc.
Fig. 4.5(b) shows the electrical interconnection of microcontroller ATmega8 with dc gear
motor, through motor driver circuit, matrix keypad and LCD display. The program was
written using BASCOM-AVR software. ATmega8 is a 28 pin IC. It has 3 port, port B, port C,
port D. Port B, port D have 8 pin and port C has 7 pin. LCD is connected to port B, keypad is
connected to port D, motor driver is connected to port B and power supply unit is connected
to pin no 7.
LCD display used in this work is of 16*2 character type. Among eight data pins of LCD only
D4 to D7 has been connected to the PB2 to PB5 of microcontroller respectively.
In this work 3*3 matrix keypad has been interfaced with the microcontroller. Actually this
type of matrix keypad is nothing but a combination of four rows and four columns and in
between each overlapping row and column line there is a key.

4.7. Smart beaker carrier

Now suppose we want to have layers of different solution on a substrate or layer of different solution on different
substrates. So we will have beakers of different solutions. We can’t place several beakers on the beaker base and
every time we have to change the beaker manually to have layers of different kind of solutions on the substrate.
To remove this problem an additional feature I have made which is the smart beaker carrier. We can see it in
figure 4.6. It contains four sections to place four beakers on it. And with a press on the button associated for the
beaker this beaker carrier can rotate clockwise. It rotates 90 degree at a time and consequently we can place our
required beaker underneath the substrate holder among the four beakers. A stepper motor is used to have the
circular motion of the beaker carrier.

37
 Figure: 4.6. Smart beaker carrier

The stepper motor of the beaker carrier takes power from the switch placed in front of sol-gel
machine. Now if we wish we can use the beaker carrier or we can do the dipping process
without it.
There are four bearings under the base of the beaker to support the four beakers placed on it
which is shown in figure 4.7. The base is mounted with the shaft of the stepper motor. When
the motor rotates the beaker carrier rotates clockwise for 90 degree at a time when we press
the button.

Figure 4.7: Bearings and motor of the beaker carrier

38
Figure 4.8: Complete setup of the automatic sol-gel machine with smart beaker carrier

39
 CHAPTER-5
EXPERIMENTAL
SECTION

40
5.1.Introduction:
The optical and structural properties of ZnO thin films prepared by sol-gel process depends on
several parameters such as pre heating and annealing temperature, concentration of solution,
presence of polyethylene glycol (PEG) content, film thickness and so on [49-50]. Among
these factors film thickness is directly related to the resistivity, crystallites size and orientation
of ZnO films [51]. It has been reported that film thickness of sol-gel derived ZnO film is
greatly dependent on the withdrawing rate and for uniform thickness of the films withdrawing
rate must be constant [52]. But in conventional sol-gel process [53-55] dipping and
withdrawing process is done manually, hence maintaining constant and smooth dipping or
withdrawing rate is quite difficult. As a result the interference fringes will not remain constant
and films thickness will be non-uniform. But automatic sol-gel process can be employed to
overcome the drawbacks associated with the conventional sol-gel technique. In this work,
ZnO thin films were deposited on different lengths of glass substrate by using proposed
digital sol-gel system. Zinc acetate di-hydrate was used as a precursor and diethanolamine
was used as stabilizer. After annealing the as-deposited films at 500℃for 2 h they
characterized with optical properties using UV/Visible spectrometer at room temperature
within the wavelength range of 300-900 nm.

5.2. preparation of ZnO thin film:

ZnO thin film can be prepared by using four steps, substrate cleaning, precursor solution
preparation, substrate dipping and withdrawing, and heat treatment. The whole process is
shown in fig.5.1

Figure: 5.1. Different steps of sol-gel process

41
5.2.1 Substrate cleaning
A variety of substrates including glass microslides,FTO (Florin Doped Tin Oxide) glass
substrate, special ITO (Indium Doped Tin Oxide) substrate, quartz, sapphire,and silicon can
be used to deposit ZnO thin films. Substrates such as sapphire that have a somewhat better
crystal match toZinc Oxide Wurtzite tended to show better film crystal orientation.Similarly,
putting a seed layer on the substrate would result in better crystal orientation [56].
In this work, glass microslides of 7 cm length were used for ZnO thin films and shown in the
following Fig. 5.2.

Figure: 5.2. Glass micro slides for thin films deposition

Before depositing ZnO thin films, the glass substrate must be cleaned properly so that no dust
particles remain on the substrate. If there are dust particle on some portion of the substrate,
then no thin film will be grown on that portion. In order to clean substrates ultrasonic cleaner
was employed in this work.
An ultrasonic cleaner is a cleaning device that uses ultrasound (usually from 20–
400kHz) and an appropriate cleaning solvent (sometimes ordinary tap water) to clean delicate
items. Cleaning normally lasts between three to several minutes.Ultrasonic cleaning uses high
frequency sound waves to agitate in a liquid. Cavitations bubbles induced by the agitation act
on contaminants adhering to substrates like metals, plastics, glass, rubber, and ceramics. This
action also penetrates blind holes, cracks, and recesses. The intention is to thoroughly remove
all traces of contamination tightly adhering or embedded onto solid surfaces. Objects must not
be allowed to rest on the bottom of the device during the cleaning process, because that will
prevent cavitations from taking place on the part of the object not in contact with water. The
ultrasonic cleaner employed in this work is shown in the following Fig. 5.3.

42
 Figure 5.3.Electronic Ultrasonic cleaner used for cleaning substrate

The cleaning procedures employed in the present work are given below:
1. Choosing the appropriate length of substrate.
2. Keeping the substrate in a culture dish with Ethanol (C 2H5OH) such that
substrates are fully immersed.
3. Keeping the dish on Ultrasonic cleaner base and cleaner must be filled with
distilled water but level of water to be less than dish height.
4. Turning the Ultrasonic cleaner on and setting the cleaning time (Say 5 min or
10 min)
5. Drying the substrate with air compressor to remove ethanol.
6. Repeating the steps 2 to 5 keeping the substrate in dish with distilled water.

5.2.2 Preparation of precursor solution

Chemical reagents

ZnO precursor solution was prepared using absolute ethanol (M=46.07, CH3CH2OH, EtOH) as
solvent, zinc acetate di-hydrate (M=219.50, Zn(CH3COO)2.2H2O, ZAD) as precursor, diethanolamine
(M=105.14, [CH2(OH)CH2]2.NH, DEA) as chelating agent and de-ionized water.

43
Precursor solution preparation procedures

ZnO precursor solution was prepared in the following way. At first, specific amount of zinc
acetate was dissolved into specific amount of absolute ethanol to yield specific concentrated
solution and then was magnetically stirred for 20 min. The magnetic stirrer employed in this
work is shown in Fig. 5.4.

Figure: 5.4. Magnetic stirrer used for stirring solution

A milky solution was obtained where a specific amount of DEA with a molar ratio of
DEA/ZAD as 1:1 and with a molar ratio of de-ionized water/ZAD as 2:1 specific amount de-
ionized water was added into the emulsion. The solution was again stirred and a clear solution
was obtained after about 15 min. Meanwhile, a homogeneous mixer of absolute ethanol and
de-ionized water was prepared with a volumetric ratio of 8:2. Finally, the precursor solution
was hydrolyzed with drop by drop addition of prepared mixer of ethanol and de- ionized
water keeping the solution under continuous stirring. After about 2 hrs when the clear solution
just turned into little whitish in color then hydrolyzing was stopped and the solution and the
solution was ready for deposition of ZnO thin films. [18]

In this work, ZnO films were deposited for zinc acetate concentration of 1mol/L. ZnO
preparation procedure is shown in fig.5.5. At first 10.98g zinc acetate was dissolved in 50ml
absolute ethanol to yield 1mol/L concentration. Then it was magnetically stirred for 30 min A
milky solution was obtained. After that a specific amount of DEA (4.82ml) and specific
amount of de-ionized water (1.8ml) was added into the solution. The solution was again
stirred and a clear solution was obtained after about 15 min.

44
 Figure: 5.5. ZnO precursor solution preparation procedure

5.2.3.Substrate dipping and withdrawing

In this work, substrate dipping and withdrawing was done by using previously reported digital
sol-gel system [18] and proposed sol-gel system.

5.2.4. Heat treatment

After completing one dipping and withdrawing iteration the coated films were dried at room
temperature for 24 h and then heated at 450 0C in air for 2 h to decompose the precursor film
to ZnO. After that another deposition cycle was carried out. After completing the required
deposition cycles, the films were again annealed at 4500C for 2 h.

5.3. Characterization of prepared ZnO films

Prepared ZnO thin film by new method were characterized basis on three property

 Optical property
 Surface Morphology
 Crystallite
Every characterization need different machine. We can get optical property like band gap,
absorbance, and transmittance from UV spectra photometer. Nano structure and uniformity is

45
seen by SEM (Scanning Electron Microscopy). Crystallite is observed by XRD (X-ray
Diffraction).

Optical property:
The optical behaviors of a semiconductor are investigated in terms of the three phenomena
namely transmittance, reflectance and absorbance by using UV visible spectrometer shown in
figure 5.6(a). Therefore, it is necessary to study the ultraviolet (UV), visible and infrared (IR)
characteristics of the material. The optical behavior of a material is generally utilized to
determine its optical constants, n and ko. The absorption of radiation by any medium occurs
through the excitation of electrons and photons and the photon-electron interactions. Then
intensity of radiation is generally attenuated in an exponential form of the type exp(-αt),
where α is the absorption coefficient and related to the imaginary part of k o of the refractive
index by
4 π ko
α=
λ
(5.1)
The absorption coefficient of thin film can be measured by passing monochromatic light
through the film under study and measuring the incident and transmitted beam intensity by a
photosensitive detector. When a ray of monochromatic light incident perpendicularly to a flat
section of the film, a portion of the incident light will be reflected and the reminder part will
be transmitted into the film. The transmitted light can be absorbed by the film material.
In the fundamental absorption region the transmission T is given by

T = A exp ( −4 πλ k t )
o

(5.2)
Where, ko is the extinction coefficient. From the equation (5.2), t is the film thickness and 𝛌 is
the wavelength of incident light. If ko<<n then the principle variation of T occurs in the
exponential term and the pre-exponential term A which accounts for reflecting effect is close
to unity. Therefore,
T = exp (-αt) (5.3)
Then from equation (5.1), we can write for the absorption coefficient,

46
 Absorption coefficient, α = 2.303 log ( 100T ) (5.4)

Hence, knowing the value of transmittance T the value of absorption coefficient α can be
determined.
hc 1240
Again, from the equation of photo energy, E = hυ = = (ev)
λ λ
(5.5)
Therefore, from the equation (5.2), the value of wavelength and from equation (5.5) the
value of band gap can be determined.
In this work, Optical spectra was measured in wavelength ranges 300 <λ< 900 nm using a
Halo SB-10 UV-visible spectrophotometer, as shown in Fig 4.8(a), forall the prepared
ZnOfilms. Before placing a ZnO films in the slot of spectrometer base was corrected using a
reference glass substrate. Optical transmittance of the films for normal incidence was
obtained. Obtained transmittance (%T) values were plotted against wavelength to find the
transmission spectra.
Using Beer–Lambert equation (Equation 5.1) optical absorption was found for each
wavelength from corresponding transmittance (%T) data.
Absorption = 2-Log(Transmittance) (5.6)
The direct and indirect allowed optical transitions between valance and conduction bands can
be evaluated by fitting a straight line in strong absorption spectral region using the Tauc
relationship as shown in Fig 5.6 (b). According to Tauc law dependence of absorption co-
efficient (α) on photon energy (hν) can be given by

(αhν )= A(hν −Eg)r (4.7)

Where α is the absorption co-efficient, A is the edge width parameter, and hν is the photon
energy, and r is a constant, for direct allowed transition r equals ½ and for indirect allowed
transition equals 2. [18]

47
 Figure 5.6. Characterization of optical properties (a) UV/Visible Spectrometer, and (b) example of
Tauc plot for band gap calculation.
Surface morphology (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-sample interactions reveal information about the sample including external
morphology (texture), chemical composition, and crystalline structure and 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. Figure 5.7 shows an SEM machine

48
 Fig 5.7: SEM machine (Atomic Energy Center , Dhaka)

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. Secondary electrons and backscattered
electrons are commonly used for imaging samples: X-ray generation is produced by inelastic
collisions of the incident electrons with electrons in discrete ortitals (shells) of atoms in the
sample. As the excited electrons return to lower energy states, they yield X-rays that are of a
fixed wavelength (that is related to the difference in energy levels of electrons in different
shells for a given element). Thus, characteristic X-rays are produced for each element in a
mineral that is "excited" by the electron beam. 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.

Fig 5.8: schematic diagram of SEM [57]

49
Crystallite (XRD):
X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of a crystalline material and can provide information on unit cell dimensions.
The analyzed material is finely ground, homogenized, and average bulk composition is
determined. Figure 5.9 shows a XRD machine.

Fig 5.9: XRD machine (BCSRI, science lab, dhaka)

Bruker's X-ray Diffraction D8-Discover instrument:

X-rays are generated in a cathode ray tube by heating a filament to produce electrons,
accelerating the electrons toward a target by applying a voltage, and bombarding the target
material with electrons. When electrons have sufficient energy to dislodge inner shell

50
electrons of the target material, characteristic X-ray spectra are produced. These spectra
consist of several components, the most common being Kα and Kβ. Kα consists, in part, of
Kα1 and Kα2. Kα1 has a slightly shorter wavelength and twice the intensity as Kα2. The
specific wavelengths are characteristic of the target material (Cu, Fe, Mo, Cr). Filtering, by
foils or crystal monochrometers, is required to produce monochromatic X-rays needed for
diffraction. Kα1and Kα2 are sufficiently close in wavelength such that a weighted average of
the two is used. Copper is the most common target material for single-crystal diffraction, with
CuKα radiation = 1.5418Å. These X-rays are collimated and directed onto the sample. As the
sample and detector are rotated, the intensity of the reflected X-rays is recorded. When the
geometry of the incident X-rays impinging the sample satisfies the Bragg Equation,
constructive interference occurs and a peak in intensity occurs. A detector records and
processes this X-ray signal and converts the signal to a count rate which is then output to a
device such as a printer or computer monitor The geometry of an X-ray diffract meter is such
that the sample rotates in the path of the collimated X-ray beam at an angle θ while the X-ray
detector is mounted on an arm to collect the diffracted X-rays and rotates at an angle of 2θ.
The instrument used to maintain the angle and rotate the sample is termed a goniometer. For
typical powder patterns, data is collected at 2θ from ~5° to 70°, angles that are preset in the
X-ray scan.

Fig 5.10: schematic diagram of XRD [58]

51
I could only find the optical properties of the prepared films because we only have the UV
visible spectrometer in our nanotechnology laboratory which is only capable of finding the
optical properties of thin film.

CHAPTER - 6
RESULTS AND
DISCUSSION

52
6.1. Introduction:
In this chapter experimental results of prepared ZnO thin film is discussed. At the starting of this chapter images
of different lengths of substrates covered by ZnO thin films that have been deposited by proposed digital sol-gel
process is shown. All the prepared films have been characterized by optical properties with UV Visible
spectrometer in the wavelength range of 300-900 nm. Comparison between previous digital sol-gel
[13] derived and proposed digital sol-gel ZnO films have been figured out. The direct band
gap has also been found with satisfactory value.

6.2.Deposition of ZnO film by length variation:

Figure 6.1 shows the images of ZnO films prepared by length variation by proposed digital
sol-gel process. It can be easily figured out that the proposed digital sol-gel system is
successful in depositing ZnO thin films on the required length of substrate without any
problem. It is also clearly shown that the surface of prepared films has been grown uniformly.

53
 Figure: 6.1.ZnO thin film by length variation

Figure 6.2 shows the optical transmittance spectra of the prepared film of length 2.5cm. The film have a very
sharp cut-off at around 375 nm wavelength and reaches to peak at around 400 nm.

Figure: 6.2. Transmittance spectra of ZnO thin film (2.5cm)

54
The direct and indirect allowed optical transitions between valance and conduction bands can
be evaluated by fitting a straight line in strong absorption spectral region using Tuac
relationship According to Tauc law dependence of absorption co-efficient (α) on photon
energy (hν) can be
αhν = A(hν − Eg)m (1)
where m is equal to 1/2and 2 for direct and indirect transitions respectively , α is absorption
coefficient , A is the edge width parameter and hν is the photon energy. For ZnO thin films
we can only find the band gap energy by direct transition only.

figure 6.3 shows The curves of [αhν]2 versus photon energy hν for direct band gap transitions
of ZnO thin film. It is seen in figure 6.3 that the band gap energy of the prepared ZnO thin
film is near about 3.3ev which is almost equal to the ideal band gap of ZnO.

Figure: 6.3. The curve of [αhν]2 versus photon energy hν for ZnO thin film of length 2.5cm

6.3. Comparison between previous and proposed digital sol-gel derived

ZnO films:
Figure 6.4 shows the images of ZnO thin films prepared by both previous [13] and proposed
sol-gel method. It can be clearly understood that proposed digital sol-gel derived ZnO films
are visually more transparent than previous derived ZnO films.

55
 Figure: 6.4. Images of ZnO thin films (a) previous and (b) proposed sol-gel derived.
Figure 6.5 shows the optical transmittance spectra of the prepared films. Both the films have a
very sharp cut-off at around 380 nm wavelength and reaches to peak at around 400 nm.

100

80
Transm ittance (% T)

present system
60 previous system

40

20

0
300 400 500 600 700 800 900
W avelength (nm )

Figure: 6.5. Transmittance spectra of ZnO thin films (a) previous and (b) proposed sol-gel derived.

The films are highly transparent in the visible range and have low transmittance at the UV
region. It is to be noted that the average transparency of proposed sol-gel derived ZnO films
(94.79%) is higher than the previous digital sol-gel derived ZnO films (81.28%) in the visible
range.

56
 CHAPTER - 7
CONCLUSION &
FUTURE WORK
57
7.1. Conclusion
The work reported in this thesis is mainly focused on development of a new user friendly
automatic sol- gel system and after that preparation of ZnO thin film and characterization of
prepared film with respect to optical property.

Starting with aim of the work, first the limitations of existing digital sol-gel system were
identified. In spite of the higher cost the new system overcomes the limitations of existing
system to a great extent. Also a comparison between previous and proposed system is shown.

Lastly ZnO thin film was prepared successfully by length variation. And prepared films were
characterized with respect to optical property (transmittance, absorbance, direct bandgap) by using UV
visible spectrophotometer for 300-900nm.

7.2. Future work

This thesis represents the modeling of a new automatic sol-gel system. The prepared ZnO can
be used for various applications like transparent conductive oxide, UV detector, optical
window, DSSC solar cells, waste water purification, air purification etc. Future directions
related to the work in this thesis are presented below:
1. By improving the modeling of substrate holder more substrate can be deposited at a
time.
2. To achieve more lower speed of the substrate up to 1cm/min.
3. Characterization of the prepared films with electrical properties

58
 4. Characterization of the prepared films with structural properties (GIXRD,AFM, SEM)

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