Chapter#1

THIN FILMS: AN OVERVIEW

1.1 INTRODUCTION
Thin films is a three dimensional condensed matter, deposited on substrate in which
dimension in one direction is much smaller than dimension in the other two perpendicular
directions, Chemical bonds between the atoms composing of thin films give the
nanostructures. Some defects like vacancies, impurities, deformed bond and surface
roughness etc. makes these nanostructures to microstructures. With these defects, voids,
spatial fluctuation of the atomic composition, variation in thickness, granular structure
(grain size, grain boundaries etc.) can effects the structural, electrical, and optical properties
of the thin films. Thickness of thin film is from 10 times of nanometers to micrometers.
Thin film thickness is closely related to the deposition rates deposition technology. Thin
films are synthesized by the deposition of individual atoms or clusters of atoms on the
surface of substrate one by one. These films technology have been used for its various
applications, from more than half century [1]. This film technology is a branch of modern
technology that deals with surface modifications and coatings. In this process the properties
of a substrate surface of a material is changed [2]. Thin film is a general term used for
coatings that are used to modify and increase the functionality of a bulk surface or substrate.
They are used to protect surfaces from wear, improve lubricity, improve corrosion and
chemical resistance, and provide a barrier to gas penetration. In many cases thin films do no
effect the bulk properties of the material. They can, however, totally change the optical,
electrical transport, and thermal properties of a surface or substrate, in addition to providing
an enhanced degree of surface protection. Thin film coating technology is rapidly
advancing. The performance demands on virtually all types of thin film materials are
continuously increasing. To meet these demands, thin film coatings and structures are
becoming more sophisticated with engineered microstructure and properties [3, 4].
A thin film is defined as a low dimensional material created by condensing, one-by-one
atomic molecular or ionic species of matter. The thickness is typically less than several
microns. The basic properties of thin film, such as film composition, crystal phase and
orientation, film thickness, and microstructure and controlled by deposition conditions.
Thin films exhibit unique properties that cannot be observed in bulk materials. Thin film
materials and devices are also available for minimization of toxic materials since the
quantity used is limited only to the surface. Thin film processing also saves on energy
consumption in production and is considered an environmentally benign material
technology for the next century. Thin films are used in number of engineering systems. A
few examples are as follows:
 Great strides in thin film technology have been made in order to advance the rapid
development of miniature, highly integrated electronic circuits. In such devices
confinement of electric charge relies largely on interfaces between materials with
 differing electronic properties. Furthermore, the need for thin materials of
exceptionally high quality, reproducible characteristics and reliability has driven
film growth technology through a rapid succession of significant achievements.
 The use of thin film for protection of structural materials in high temperature
environments is another thin films technology of enormous commercial
significance. In gas turbine engines, for example, thin surface films of materials
chosen for their chemical inertness, stability at elevated temperature and low
thermal conductivity are used to increase engine efficiency and to extend
significantly the useful lifetimes of structural materials that they protect.
 The use of thin films for improving lifetimes of components subjected to friction
and wear. Among the technologies that rely on the use of thin films in this way are
internal combustion engines, artificial hip and knee implants, surgical tools etc.
 Thin films are also used in integral parts of many micro /electro/mechanical
systems.
Surface coating is an effective method to improve the durability of material
used in the aggressive environment. By properly selecting thin film coating method
and coating materials we may prolong the lifetime of materials and increase the
commercial value of the products. Any thin film deposition process involves three
main steps:
 Production of the appropriate atomic, molecular, or ionic species.
 Transport of these species to the substrate through a medium.
 Condensation of the substrate, either directly or via a chemical reaction, to form a
solid deposit.

The basic properties of film, such as film composition, crystal face and
orientation, film thickness, and microstructure, are controlled by the deposition
conditions [5].

1.1.1 Stages of Fabrication:

The production of useful and commercially attractive “engineered surfaces” using thin
film deposition process involves a number of stages which are independent. The stages
are [3].
 Choice of the substrate.
 Defining and specifying critical properties of the substrate surface.
 Development of an appropriate surface preparation process which includes
cleaning and may involve changing the surface morphology or surface
modification.
 Selection of the film material and film structure to produce the film adhesion and
film properties required.
  Choice of the fabrication process to provide reproducible film properties and long
term stability.
 Development of the fabrication equipment, process parameters, parameters limit.
 Development of production equipment that will the necessary product throughout.
 Development of appropriate characterization techniques to determine the
properties and stability of the product.

1.2 Factors That Affect Film Properties

Thin Film coatings are used to modify the functional properties, including
physical, chemical, electrical, magnetic, mechanical, wear-resistant, corrosion resistant
properties and morphology of a surface or substrate, which makes them a broad subset of
surface engineering. The properties of a film of a specific material formed by any atomistic
deposition process depend on following factors, namely [4].
1. Substrate
2. Substrate temperature
3. Source
4. Contamination
5. Evaporation rate and film thickness
6. Adhesion of thin films

1.2.1 Substrate
The substrate is used to support the thin films mechanically. Nature of the substrate is
very important in thin film application because it effects directly on the structural
properties of the thin films. It acts as an insulator in electronic type applications of the
thin films. Nature of substrate has also its importance for long term stability of thin film
because chemical reactions between source material and substrate strongly affect
properties of the film. During the section of substrate, it is great requirement that
substrate is providing the required forces between evaporated materials and substrate
effect on the thin film growth mechanism. An increase in binding forces between
substrate and source results in decrease of mobility of evaporated atoms. Due to increase
in the mobility, there is increase in the number of initial nuclei and hence in the increase
of adhesion between substrate and source. Difference of coefficients of expansion
between substrate and the evaporated film produce some stresses in the thin film which
effects on its structural properties. To reproduce the electrical properties of thin film,
substrate should be smooth. Selection of substrate is made on the requirement of different
properties of thin films. For poly crystalline films, mostly glass, fused silica or some
Al2O3 based ceramics are used. For a single crystal epitaxial growth silicon, germanium,
mica, sapphire or mostly alkali halides are used. Contents of alkali especially sodium is
very important in glass substrate. Sometimes higher contents of alkali in the glass
substrate causes non stable electrical properties of thin films. Contents of alkali halides
 Na2O up to 4% is practically suitable. But at higher concentrations, when temperature
and electric field are higher, there is less adhesion due to fast travelling of atoms. Higher
contents of these halides cause electrolytic corrosion of the film because of the presence
of moisture. Ceramic substrates have higher thermal resistance and thermal conductivity
as compared to glass substrate but lower quality due to having less smoothness. For solar
cell applications glass substrate are used due to their higher transparency and smoothness.
Mostly coming 7059 glass substrates are used.

1.2.2 Substrate Temperature

Substrate temperature has its own effect on the thin film properties. Heating of the
substrates causes the absorption of contaminates. Less amount of contamination results in
the higher adhesion of thin films and their accurate properties. Due to increase in
temperature of the substrate, surface mobility of the condensed atom increased which
may change the crystalline structure of the film. Temperature of substrate also effects on
inner diffusion between adjacent layers. Higher the temperature, higher will be the inter
diffusion that result in more homogeneous thin film. Probability of the deposition of
evaporated atoms can also increase with increasing substrate temperature.

1.2.3 Source Temperature

This factor is important for the evaporation of the source material. Value of source
temperature at which evaporation is occurred also depends on the level of the vacuum.
Value of emissivity ranges from 0 to 1 and depends on the nature of the material. When
temperature is increased, emission rate will also increases. Splattering of the source
material and heater burnout must be kept in mind before the source temperature
optimization.

1.2.4 Contamination
Consideration of contamination in the growth of thin film gives better understanding of
thin film properties. Contamination has strong influence on the structure of thin films.
The main sources of contamination in evaporated films are contaminants present in the
deposition system, heater material and the gases which released from the evaporation.
Main disadvantage of the contamination for thin film growth is the adhesion of evaporate
on the substrate.
Contamination in the deposition system and on substrate can be removed from many
mechanisms. In the deposition systems contaminations are removed by creating the
vacuum. For substrate, it is great requirement that it should be cleaned with some suitable
method. But even cleaning some contaminants still remain on the surface of the substrate.
These contaminants may be removed by heating the substrate in the vacuum. By heating
the substrate, there is desorption of contaminants which then can be removed by vacuum.
It has been observed when a clean substrate is exposed to air, it get some contamination
 which produce larger number of initial nuclei in film growth. Even a little amount of
contamination may also influence on nucleation in film growth Process, ant its structure.
But it is difficult to understand what types of interactions are being occurred due to non-
identification of contamination and its small amount.

1.2.5 Evaporation Rate and Film Thickness

Evaporation rate is rate of bombardment of evaporate on the substrate. It is function of
temperature and pressure. It has strong effect on the thin film thickness. Variations in the
temperature and pressure may change the film thickness with same deposition time. For
thin films grain size is affected by the thickness but in thicker films grain size is mostly
independent of thickness. The intrinsic stresses which are arises during growth process
depends on the film thickness and sometimes at the deposition rate.

1.2.6 Adhesion of the Film

Adhesion of the thin film on some substrate is a significant factor that effect on the film
properties and film growth. Adhesion depends on the strength of interacting forces or
bonding between the source materials and the top surface of the substrate. There are
mainly two type of adhesion. One is chemical and other is dispersive adhesion. In
chemical adhesion, mostly there are ionic, covalent or hydrogen bonding. But in
dispersive adhesion of films, Van Dar Wall Forces is active force between molecules.
Bonding in adhesion with glass substrate is probably physical adsorption bonding. This
bond strength is influenced by activated chemisorption, diffusion and chemical reaction
related processes.

1.3 Thin Film Applications

Thin films technology has a large number of applications in the field of electronics,
computer, optics, optoelectronics etc. these applications are divided into following generic
categories

ELECTRONIC DEVICES:
Minimization in dimension and weight of electronic components in terrestrial electronics
has core importance in terrestrial electronics. Due to fabrication of these electronic
components, especially solid state devices and microelectronic ICs have demanded the wide
application of the film technology. Thin films, which are used in these components, are
made of semiconductor, insulator dielectric and refractory metal conductors.

ELECTRONIC DISPLAYS:
There are many thin film based electronic displays, which are used in interfacing electronic
equipment that support the human operators. These displays are:
  Liquid-crystal displays
 Light-emitting diodes (LEDs)
 Electroluminescent displays
 Plasma and florescent displays
 Electro chromic displays

Conductive, transparent, luminescent and fluorescent thin films are used for these displays.
Dielectric and insulating layers are used in these components

OPTICS:

Optical coatings have great demand in solar based applications. Optical coatings are made for
anti-reflection purposes. These coatings are used as interference filters and as infrared solar
reflectors on solar panels. Thin films having gradient of refractive index are used for these
coatings. Due to the selective reflectance and transmission, thin films of gold are used for
reflection of heat radiations.

SOLAR CELL TECHNOLOGY:

Solar cells are widely used as a source of energy in last few years. As much cost is involved in
the energy generation with other process so world is taking deep interest in research of solar
cells. Solar cells are also called photovoltaic (PV) devices. These are PN junctions which convert
incident light energy into electrical energy using photovoltaic effect phenomenon. These PV
devices have been used for many applications like space applications, consumer products,
calculators, clocks, toys. They are also used power generation at large scale like as part of a
building. Thin films based solar cells are developed in laboratory and industry. Solar cell of
CdTe/CdS gives efficiency of more than 15%. As efficiency of single junction solar cell is
limited so research is in progress to get the efficiencies more than 20-30% with tandem solar cell
[11].
Chapter#2

METHODS AND TECHNIQUES

2.1 FILM DEPOSITION

The action by which thin film is applied on the surface is called thin film deposition. Large
number of different deposition techniques is used in order to deposit a thin film of any
material on a substrate or to any previously other deposited layers. There are two broad
categories of deposition techniques, depending on nature of the process wither it is primarily
chemical or physical [32]. The deposition of thin film involves the three basic steps:
 Creation of Vapor phase Species:
A target material can be evaporated to produce the appropriate atomic, molecular, or
ionic species.

 Transportation of material from source to substrate:

Vapor species are transported from source to substrate through medium.

 Growth of film on substrate:

The condensation of the vapor species and formation of film by nucleation and
growth procedure onto the surface of the substrate directly or chemically and/or by
electrochemical reaction, to form a solid deposit.

Deposition of thin film depends on different parameters such as, deposition rate, substrate
material, substrate temperature, and deposition atmosphere.

2.2 Classification of Deposition Process

There are number of deposition technologies for material formation. The classification of
thin film deposition methods are used for forming layers of thickness ranging from a few
nanometers to about ten micrometers, the classification of technologies is made simpler by
limiting the number of processes to be considered. The deposition processes are shown in
figure 2.1.
Thin film deposition techniques are simply physical or entirely chemical. Some processes
combine both chemical and physical methods, such as glow discharges and reactive
sputtering combine both physical and chemical reactions; these kinds of processes can be
categorized as physical chemical methods [10, 33].
Generally, vapor deposition method is of two types, physical vapor deposition (PVD) and
chemical vapor deposition (CVD). The PVD method of material vapor is created by
evaporation or sputtering and the condensation of vapor in the surface of a substrate to form
a film. In CVD processes, generally a deposition of solid materials is made from a vapor
phase on the heated surface of substrate as a result of chemical reaction [9]. Both the
processes have one superior advantage over the other as, CVD process has the advantages of
 good thrown power, while PVD method has a higher deposition rates than those in CVD
processes at a lower deposition temperature [34].

Physical Vapor Deposition (PVD)

Thermal evaporation Sputtering

Electron beam evaporation

Chemical Vapor Deposition (CVD)

PE-CVD ALD Spray Ink jet

Figure 2.1: Thin film deposition process [32]

2.3 CHEMICAL PROCESS

In chemical method the film is formed by the chemical reaction takes on the surface of
substrate. These deposition processes be likely to be conformal, rather than directional. The
deposition is further categorized as:
 Chemical Vapor Deposition (CVD)
 Chemical Solution Deposition (CSD)
 Plating

2.3. Chemical Vapor Deposition:

In CVD process when a compound to be deposited on a substrate is first vaporized. These
vapors are thermally decayed into molecular or atoms, and reacted with any other gases,
vapors, or liquids on a substrate to give up nonvolatile reactions on the surface of the
 substrate; such a process is known as thermal chemical vapor deposition (CVD). The
CVD processes require comparatively high temperature (nearly 1000℃). The basic rule
of this procedure is that a chemical reaction takes place within the vacuum chamber
involving the source gases. As a result the product of a reaction is solid material which
condenses the surface there in the reactor, as shown in figure 2.2

Figure 2.2: Chemical Vapor Deposition (CVD) procedures.

2.4 PHYSICAL PROCESS

In PVD process a film is formed by the transportation of atoms from sources to the
substrate directly through gas phase. Generally PVD techniques have primarily two
categories:

 Thermal evaporation process

 Sputtering

PVD techniques have extensive range of applications starting from decorative, too

high a temperature superconducting thin films. It has deposition rates very high; by the use of
electron beam a heated sources of 25µm/sec have been achieved. A PVD technology is capable
to use for deposition of various inorganic materials also a number of organic materials can be
deposit. Evaporation and sputtering have the terminology that refers to mechanism where the
condensed species is transferred to a vapor phase [32].
 Several factors that differentiate PVD from CVD process are

 Physical mechanism (that is evaporated or coalitional impact) by which source atoms are
enters to gas phase.
 Reduced pressure environment during which the gaseous species can transport.
 Absence of a chemical reaction in a gas phase and on the substrate surface except
reactive PVD process.
 Physical vapor deposition (PVD), that included both sputtering and evaporation process.

The substrate used in PVD techniques can range from very small to very large
size and the substrate have any shape from flat to any multifaceted geometry. PVD have
typically a deposition rate ranging from 100Å per second [3].

Physical Vapor deposition

Thermal process
Sputtering

Vacuum Laser
Evaporation
MBE Ion plating AVD
ablation

Figure 2.3: Different common physical vapor deposition methods