INFLUENCE OF ANNEALING ON THE OPTICAL AND

STRUCTURAL PROPERTIES OF SILVER THIN FILMS

Project Report
Submitted to Mahatma Gandhi University in partial fulfillment of
the requirements for the award of the degree of

MASTER OF SCIENCE IN PHYSICS

Submitted By

Jithin H
M.Sc. Physics 2017 – 2019
Reg. No: 170011003214
Under the guidance of
Dr.VINU T VADAKEL
Assistant professor
Department of physics
St.Aloysius College , Edathua

St. Aloysius College , Edathua

1
 CERTIFICATE

This is to certify that this project report entitled ‘INFLUENCE OF ANNEALING

ON THE OPTICAL AND STRUCTURAL PROPERTIES OF SILVER THIN FILMS ’ was
done by Jithin H Reg. No:170011003214 at St. Aloysius, College, Edathua
Mahatma Gandhi University in partial fulfillment of the requirement of the
Master of Science in Physics during the year 2017 – 2019.

Dr. Vinu T Vadakel Prof. Lizymol xavier

[Project Guide] Head of the Department of Physics
Assistant Professor in Physics St. Aloysius College ,Edathua
St. Aloysius College, Edathua

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 DECLARATION

I hereby declare that the project entitled INFLUENCE OF

ANNEALING ON THE OPTICAL AND STRUCTURAL PROPERTIES OF SILVER THIN
FILMS is a bonafide work carried out by me under the guidance of Dr.
Vinu T Vadakel, St. Aloysius’ College, Edathua in partial fulfillment of the
requirement for the award of the degree of Master of Science in Physics
of Mahatma Gandhi University.

Jithin H

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 ACKNOWLEDGEMENT
Every fruitful effort is often backed by the hands of many, whose
aids may or may not be recognized. But at the completion of my project
work, I felt it necessary to thank those who have helped me.

Firstly, I am thanking the omnipotent Almighty whose

divine blessing I felt throughout my work. With great pleasure and
gratitude, I express my sincere thanks to my guide Dr.Vinu T Vadakel,
Department of Physics, St. Aloysius’ College, Edathua under whose
guidance and direct supervision, the present work was carried out.

I would also like to express my heartfelt gratitude to our

former HOD, Dr. Jochan Joseph and to all teachers for their help and
assistance. I thank all of my classmates who supported me in
completion of this project. I also utilize this moment to thank my family
members for their constant prayers and encouragement they have
poured upon me.
Jithin H

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 CONTENTS

Chapter 1
Introduction – Thin Films

Chapter 2
Experimental Techniques

Chapter 3
Results

Chapter 4
Conclusion

Reference

5
Chapter 1
1.1 Introduction-Thin films
The beginning of thin film science can be possibly be traced to the observations of Grove
who noted that metal films were formed by sputtering of cathodes with high energy
positive ions. Since then it has come a long way and today it is no longer a subject of some
casual academic interest but has become a full fledged discipline. The phenomenal rise in
thin film researches is no doubt due to the extensive applications in the diverse fields of
electronics, optics, space science, aircrafts, defense and other industries. These
investigations have led to numerous inventions in the form of active devices and passive
components ,piezoelectric devices, micro mini aturisation of power supply, rectification
and amplification, sensor elements, storage of solar energy and its conversion to other
forms ,super conducting films, reflecting and anti reflection coatings and many others. The
present developmental trend is towards newer types of devices, field effect transistors,
metal oxide semiconductor transistors ,sensors for different applications, switching
devices, high density memory components for computers, etc. Further because of
compactness, better performance and reliability with the low cost of production and low
package weight thin film devices and components are preferred over their bulk
counterparts. Intensive investigations are going not only in the field of basic thin film
physics, but also in material science, thin film circuit designs production engineering
concerning thin films, etc. Film properties are also sensitive not only to their structure but
also to many other parameters including their thickness especially in the thin film regions.

The term thin film has often been loosely used in literatures to imply not only a layer of a
solid material but also of a liquid or a gaseous phase. Further there is neither any well-
defined limit of its thickness to imply the end of the thin film stage nor one to indicate its
transition the thicker film region. All basic researches on thin films are generally confined
to a limited range of a thickness say between a few A0 to about 5000A0 depending on the
properties to be investigated where as , for technological applications where reliability of
performance is the most important criterion the thickness limit at the lower range is
generally higher than 1000 A0 and can be as high as 5-10 micrometer or even more. In
order to cover this wide range of film thickness both for basic researches and applications a
thin film may be arbitrarily defined as a solid layer having a thickness varying from a few
A0 to about 10 micrometer or so. Since the thickness limitation rather arbitrary even
somewhat thicker films may also come within the scope of the above definition .Within the
connotation of the thin film often a further subdivision of thickness is made under the
categories (1)ultra thin(2)thin(or very thin)and (3)comparatively thicker ones the last one
generally being greater than 1000A0.The categories(1)ranking from a few to about 50-100
A0 and (2)from about 100A0-1000A0 or less are all arbitrarily fixed for convenience and the

6
transition region form one category to the next one are not distinct at all. It may be
mentioned here that the above confusion in the nomenclature or definition of film
thickness further complicated by the coinage of a new term ie, thick films which are of
great practical importance. This new term indicated an entirely new case of films rather
composite film layers obtained by the process of screen printing and subsequently firing a
paste composed of a mixture /alloys oxide powder along with or without glass or ceramic
particles suspented in some organic solvent vehicles and these films have thickness of
about 10 micro meter and often more.

Whatever be the film thickness limit , an ideal film can mathematically be defined as a
homogenous solid material contained between two parallel planes and extended infinitely
in two directions (say x & y)but restricted along the third direction (z)which is
perpendicular to the x or y plane. The dimension along z or direction is known as the film
thickness(d<t).Its magnitude may vary from a limit d to 0 to any arbitrary value say to 10
micro meter or more but always remaining much less than those along the other two
directions ie, x and y. A real film however deviates considerably from the ideal case since
its two surfaces are never exactly parallel even when formed in the best experimental
deposition conditions and also the material contained between the two surfaces are rarely
homogenous neither uniformly distributed nor of the same species. It is also a common
experience that film may also contain many imperfections, impurities, dislocations, grain
boundaries and various other defects and may also be discontinuous. Further the top
surface of a film often develops some topographical features and asperities characteristic of
the growth conditions and these features are sometimes so prominent as to be visible even
to naked eyes. Some of these features can no doubt be minimized by appropriate control of
the deposition condition but cannot altogether by avoided .The bottom surface of a film in
contact with a substrate generally takes up the topographical features of the latter.

Some of the factors which determine the physical ,electrical, optical and other properties of
a film are the following ,rate of deposition ,substrate temperature , environmental
conditions, residual gas pressure in the system, purity of the material to be deposited
inclusion of foreign matter in the deposit, inhomogenity of the film ,structural and
compositional variations of the film in localized or wider areas etc. Some of which have
been actually observed .A transition from bulk to the thin films state may even cause a
drastic change in properties as illustrated by the behavior of alkali metals and also noble
metals .Thus highly conduction sodium ,potassium ,rubidium and also gold, platinum etc.
having positive temperature coefficient of resistance(TCR)in the bulk form show negative
TCR when in thin film states thus behaving as semiconduction films. Bulk bismuth and
antimony which are metallic in nature behave as semiconductors in the thin film state.
Buckel and Hilsch observed that thin bismuth films unlike bulk showed superconducting
properties at low temperatures. Highly disordered or amorphous films have electrical or

7
magnetic properties which may differ by several orders from that of the bulk single
crystals.

All films prepared by vacuum deposition or by other techniques are invariably associated
with some growth defects or imperfections such as lattice defects ,stacking faults, twinning
disorders in atomic arrangement dislocation grain boundaries foreign atom inclusion etc.
Surface states of a film also play a dominant role in modifying electrical and other
properties .In addition because of a high surface of value ratio in a film a freshly formed
film surface became highly reactive, Further because of the unbalancing of forces near the
surface region new phenomena such as thermionic emission adsorption of gases catalyses
solid state reactions etc. characteristics of a surface are more often observed in thin films
rather than in bulk. It is there for of atmost importance to study thin films not only because
of tremendous technological importance but also of our inadequate knowledge about their
interactions with the electrical magnetic and electromagnetic fields .There is often a
considerably division from that of the bulk behavior and sometimes new phenomena are
observed in the thin film states .Further from these studies it may be possible in certain
cases to predict their interactions with bulk materials.

8
1.2 THIN FILM DEPOSITION METHODS

INTRODUCTION
Any object with one of its physical dimensions (length, breadth and height) less than that of
the other two is called a thin film. A thin film is a layer of material whose thickness varied
from micrometer to nanometer.
Thin films are formed by depositing material on a clean suitable substrate to grown up film
thickness instead of thinning down the bulk material. The mechanical strength of thin films
is better than annealed as well as bulk samples.

THIN FILM DEPOSITION TECHNIQUES

The properties and versatility of the thin films can be obtained by selecting proper
technique of film deposition. Thin film deposition methods can be broadly classified as
either chemical or physical methods. The difference between the chemical and physical
thin film deposition methods depends upon the method of depositing thin film material on
the substrate.
In chemical deposition technique, fluid precursor is used which chemically react with the
substrate. Since the thin film material is conducted through the fluid precursor, chemical
deposition is conformal approaching the substrate without preference to a particular
direction. A conformal is an uneven interface with the body and has a constant thickness on
horizontal and vertical surfaces.
Chemical deposition technique includes the following methods:
Chemical Vapour Deposition (CVD): CVD is a chemical process in which the
gaseous precursors are used. Precursor gases are moved into a chamber
with the substrate. The chemical reaction between the substrate and the
precursor is continued at high temperature till the desired thickness of the
film is obtained.
Plasma Enhanced CVD (PECVD) Method: In PECVD, plasma is formed in a
reaction chamber that transforms the gaseous precursors into reactive
radicals, ions, neutral atoms and molecules. These atomic and molecular
fragments interact with a substrate and this chemical reaction cause to
develop a solid layer on the surface at the substrate. In PECVD, lower
temperatures (300~350 degrees centigrade) are used for thin film
deposition while in CVD high temperatures (600~90 degrees centigrade)
are used to develop thin films
Atomic Layer Deposition (ALD) Method: In Atomic layer deposition, two or
more gaseous precursors are used to react with the substrate sequentially
one at a time. The thin films obtained by this process are conformal. The
process of ALD is divided into two half reactions. These reactions include
deposition of precursor and evacuation of the reaction chamber that run in
sequence and repeated for each precursor. This chemical reaction occurs
on the substrate resulting in the formation of desired film thickness. ALD is
a stepwise procedure; therefore it is slower one but can run even on lower
temperature.
Sol-Gel Method: Sol-Gel is a chemical solution deposition method in which
9
 precursor solutions are highly controlled for the deposition of the films.
Sol-Gel method involves alkoxides where the macromolecular oxide
network is obtained first through the hydrolysis of the alkoxy group after
these polycondensation reactions take place.
In physical deposition technique, mechanical or electromechanical methods are used to
deposit the thin films on the substrate. Materials to be deposited on the substrate depend
upon the temperature, pressure and other physical conditions. In these physical methods,
the thin films formed are directional on nature because particles will follow a straight path
form the target to the substrate.

Physical deposition technique includes the following methods:

Molecular Beam Epitaxy (MBE): MBE combines advantages of both chemical and
physical methods for thin film deposition. Firstly, the target materials to be
deposited are heated directly until they convert from solid to gaseous form.
Then the gaseous elements are allowed to react chemically with the
substrate to grow the thin film. In MBE, target material is deposited in the
form of layers but one layer at a time. MBE is a slow method but the degree
of purity in this method is very high.
Sputtering: Sputtering is a physical thin film deposition method in which the
atoms from a target material are released and come to rest on the
substrate. The target material is kept at low temperature. In this method,
plasma of a noble gas such as argon is used as a target material. Noble gas
does not allow any undesired chemical reactions therefore; it is a fast and
an effective method to achieve the desired level of film thickness.
Pulsed Laser Deposition (PLD): It is an ablation process. High power pulses of
laser light are focused on the surface of the target material in a vacuum
chamber. This results in vaporization of the target material. The atoms
ablated from the target material get deposited on the substrate. Figure
shows pulsed laser deposition technique.

Figure : Pulsed Laser Deposition Technique

Cathodic Arc Deposition: Cathodic arc deposition is also known as arc- PVD. It is
a kind of ion beam deposition where an electrical arc is developed that
blasts the ions from target material to be deposited (known as cathode).
This electric are vaporizes the material from the cathode target. The
vaporized material is condensed on a substrate to form a thin film .
Thermal Evaporation Method: The source material to be deposited is

10
 evaporated in a vacuum by using an electron beam or resistive heating
inside a high vacuum coating chamber. The vacuum allows the vapour
particles to travel directly to the substrate where they condense back to a
solid state to form a thin film.
Electrohydrodynamic Deposition: Electrohydrodynamic deposition is also
known as electrospraying deposition method. In this method, stress is
exerted on the liquid (mixture of nanoparticles to be deposited with the
suitable solvent like methanol) which flow through the capillary nozzle by
applying high electric field while the substrate is kept at ground potential.
This stress results in the deposition of fine droplets of liquid on the
substrate. The substrate is heated for complete evaporation of the solvent.
Electrospray system for thin layer deposition from a suspension is shown
in figure .

Figure : Electrospray System for Thin Layer Deposition from a Suspension


SOL-GEL METHOD

A sol is a dispersion of the solid particles in a liquid where only the Brownian motions
suspend the particles. Suspension of the particles of linear dimension between 1nm and 1um
are called colloids which are formed by hydrolysis and polycondensation reactions of metal
alkoxides such as the oxides of Si and Ti. These oxides of Si and Ti are called precursors. A
precursor is a compound that participates in chemical reaction to produce another
compound. Numerous metal organic precursors including alkoxides, carboxylates,
diketonates and various organic salts are used to form initially metal complexed solutions
but from commercial viewpoint, alkoxides of most metals can be synthesized and are
convenient starting materials with respect to availability and cost.
A gel is a state where both liquid and solid are dispersed in each other which presents a
solid network containing liquid components. A gel is a porous three dimensionally
interconnected semi-solid network that expands in a stable fashion throughout a liquid
medium and is limited by the size of the container. A gel is said to be colloidal if the solid
network is prepared using colloidal sol particles. The liquid is present between the mesh of
the solid network that composes the gel that does not flow out spontaneously and is in
thermodynamic equilibrium with the solid network.

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Thin films from sol can be deposited by following methods:
 Dip coating
 Spin Coating
 Spraying

Thin films are prepared by depositing precursor solutions onto various substrates. The
amorphous gel films are pyrolyzed at relatively low temperatures (300oC to 700oC) to form
amorphous or crystalline oxides followed by annealing at relatively high temperature to
allow crystallization.

DIP COATING TECHNIQUE

Dip coating technique is a process where the substrate to be coated is immersed in a
coating sol where a wet layer is formed and then it is withdrawn with a well- defined
withdrawal speed under controlled temperature and atmospheric conditions . The dip
coating technique is shown in figure . The atmosphere controls evaporation of
the solvent and it leads to a gelation process which results in formation of film. The
resulting film has to be densified by thermal treatment and the densification temperature
depends on the composition.

Figure:
Dip Coating
Technique

SPIN COATING TECHNIQUE

In the spin coating process, the substrate spins around an axis which is perpendicular to
the coating area. The spinner is designed to coat thin films of liquids on the wafer surface.
The wafer surface is then dipped with BLT solution. The wafer is then rotated with high

12
speed. The excess BLT sol is driven off because of centrifugal force leaving a thin film of
BLT on the wafer surface. The thickness of wafer is controlled by spin speed, spin time and
viscosity of the solution.
The spin coating process involves the four stages . These stages include deposition, spin up,
spin off and evaporation.
SPRAYING/SPRAY TECHNIQUE
In spray technique, spray solution is spread on hot substrate and other volatile by-
products and excess solvent are removed in the form of vapors . Spraying technique
apparatus involves spray nozzle, motor, liquid level monitors, hot plate, gas regulator value
and air tight fiber chamber and is shown in figure.

Figure : Spraying Technique Apparatus

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1.3 PROPERTIES OF THIN FILMS
The properties of a thin film may be different from those of the bulk
particularly, if the film thickness very small. These anomalous properties are due to
peculiar structure of the film. A thin film may be prepared by a process as simple as
hammering or rolling down a piece of bulk material. More generally ,thin films are
prepared by depositing the film material atom by atom on a substrate.

 OPTICAL PROPERTIES
 ELECTRICAL PROPERTIES
 STRUCTURAL PROPERTIES

OPTICAL PROPERTIES
The phenomenal growth of thin film research contributed lot in the
application of optical films in mirrors and interferometers. The theoretical and
experimental investigations on the optical behavior of thin films deal primarily with
optical constants of films. As a result of these studies complex multilayer optical-device
systems with remarkable reflection, antireflection, interference and polarization properties
were developed. The absorption studies of thin films have led to a variety of interesting
thin film optical phenomena to study the electronic structure of solids.

The optical properties of the thin films show profound sensitivity on the film
microstructure. since various deposition parameters affect the microstructure, the optical
proportion strongly depend on the deposition conditions. Also the optical properties
change due to annealing of the films. In this condition recrystallization as well as surface
and volume oxidation may take place in the film. With increasing film thickness, the effect
of the initial granular structure on the optical properties is decreased but not eliminated
completely. There for thickness dependence is still observed, although the general
behaviour of the optical parameters follows that of the bulk.

The optical constants of metal thin films show a marked thickness dependence .Nearly
dielectric behavior is exhibited by ultra thin discontinuous metal films. A change to metallic
behavior takes place when the film becomes physically continuous and electrically
conducting with increasing thickness.

A typical absorption curve for bulk metals consists of absorption peaks corresponding to
the inter band electronic transitions, superimposed on the absorption by the conduction
electrons. The absorption by conduction electron for thin discontinuous poorly conducting
metal films (t<<)must be small. The absorption by conduction electron for thin
discontinuous absorption maximum appears at a position, which varies with the thickness
of the film or with crystallite size. The absorption in a film can be expressed as

14
Absorption= 4πn0 (1-R-T)/T

n0 =Refractive index of substrate

R= Reflectance of the film at normal incidence

T=transmission of the film at normal incidence

The abnormal optical properties of ultra thin films can be explained by Maxwell Garnett
theory on the basis of structural discontinuities in films. According to this theory the film
consists of a large number of spherical metal particles of diameter small compared with the
wavelength of the light used. The electric field “E” of the electromagnetic wave will polarize
the spherical crystallites then producing an extra field (4/3)*π*p. Where ’p’ is the electric
moment per unit volume of the medium. ”P” is directly proportional to the number of
crystallites per unit volume(N) and inversely proportional to packing factor q.

That is p α N α (1/q)

P=AN=B/q

Where “A” and “B” are two constants

By clausius - mosotti relation,

[(t-1)/(t+2)]=((n2 +2))=(4/3)*π*p=AN=B/q;

“n” is the refractive index of the spheres

The above relation can also be written as

q*((n2 -1/(n2 -1)/(n2 +2))=constant,

Where n* is the effective index of the film .Thus the effective index of the film can be
calculated in terms of n and q.

With suitable deposition techniques it is possible to obtain a material in thin film form
with different crystal structures. Any changes in the electronic structure of the material
would be reflected in its optical behavior such studies have been performed on the
amorphous and crystalline structures of Ge ,Se,etc. When deposited at or near room
temperature the films of these materials are amorphous. Either deposited at elevated
temperature or subsequent annealing of the amorphous film yielded a crystalline structure.

Reflectivity of a surface is depends on the refractive index of the medium. For example the
reflection coefficient is 4% for glass of index 1.5 and 36.9% for Ge of index 4.1.When light is
reflected transmitted ,hence loss increases. The reduction of the reflectance and

15
enhancement of the transmittance may be obtained by the use of suitable surface coatings
called anti reflection coatings. The reflection coefficient R would be obtained at all
wavelengths. This ideal medium cannot be realized in practice. A low index layer on glass
can be produced by removing heavier elements in dense glass by using ion beam
sputtering.

ELECTRICAL PROPERTIES
There are three types of electron materials ;metal, semiconductor and
dielectric .Obviously , the electrical transport nature is different in all type of materials,
therefore it is influence on the electrical properties of materials by the same way. The film
thickness, the lattice dimensions, the purity, the surface roughness , and the imperfect level
of the layer are must significant parameters define the type, mechanism and stability of the
electrical transport.

Electrical conductivity of a granular film in many orders of magnitude smaller than that of
the bulk material and in generally characterized by a negative temperature coefficient of
resistivity (TCR). The conductivity is found to vary exponentially with the inverse of
temperature , suggesting that the conduction mechanism is thermally activated. It is shrill
at low applied fields, but non-linear at high fields.

A large separation (d>>100A0 ). Calculations show that thermionic and schotkky emission
predominate only particles have to d 20 to 50 A0 and with a typical metal work function 4
to 5 eV , tunneling in the dominant mechanism of electron transport unless the
temperature is higher than 300k. Thermionic emission depends exponentially on the
height of the barrier may decrease significantly because of the overlap of the image force
potentials, thus giving rise to higher conductivity . Based on this theory the conductivity

S= (ArT/K)exp((-φBe2 )/d)KT)

A= A constant characterize of each film

T=Temperature

K=Boltzmann constant

E=Electric charge

D=distance between particles

φ= The bulk work function of the metal

The term (Be2 /d) represents the conduction of the image forces. If ‘d’ is sufficiently small,
the effective work function.

16
φeff=(φ-(Be2 /d) represents the contribution of the image forces. If ‘d’ is sufficiently small ,
the effective work function.

φeff=(φ-(Be2/d)=e3/2 E.

Thus, Schotkky emission leads to an exp(-1/T) dependence of the conductivity, an ohmic

behavior at low fields, and an exp independence at high fields.

The influence of substrate on conduction was shown by Hill’s observation that the
conductivity of granular Au films deposited on borosilicate glass could be modified
reversibly by an applied transverse field of 250 1000v/cm. The resistance was found to
followed by a rapid decrease occurred for the position voltage. The maximum charge
decreased with increasing temperature. Fehlner confirmed this effect and further found
evidence for the formation of inter metallic compound of ‘Na’ in the substrate with Au film.
The Na ions present in this particular glass apparently more readily under the influence of
the applied field and thus the film- substrate interface is altered. If traps can be associated
with the inter metallic compound , then the applied field provides a mechanism for altering
the density of the filled and unfilled traps.

Temperature coefficients of resistivity of signs and of variable magnitude have seen if

observed in discontinuous metallic films . The exact behavior of TCR , like that of
conductivity depends on the details of the conduction mechanism. The significant
temperature dependent function in the conductivity expression in exp(-E)/KT, which
yields an expression for the TCR as =(-e2/KT2). The temperature variation of the particle
spacing can also be taken in to account. If the particles are strongly bound to the substrate,
the expansion of the substrate increases the spacing by ∆d =(am-as) r∆T= substrate
expansion coefficient . If the particles are not constrained by the substrate , the separation
is decreased by

∆d =(am-as) r ∆T

∆T=Temperature change

r=Linear dimension of island

(am-as)= Difference of the thermal – expansion coefficients of film material and the
substrate.

ELECTRICAL CONDUCTION IN CONTINUOUS FILMS

Conduction in a material in bulk form is due to the movement of the electrons residing near
the Fermi level region having a mean velocity v and a relaxation time t such that their mean
free path, l = vτ. The mean free path (mfp) is also a function of temperature and affected by
the presence of defects and impurities etc. present in the metal lattice. The higher in the
17
defect concentration the more will be the collision of the electrons per unit time and hence
‘l’ will decrease leading to lower conductivity. If, however the bulk thickness is reduced
gradually to a stage where it is of the order of ‘mfp’ of electrons, then the conduction
electrons will be more frequently scattered by the two surface boundaries, consequently its
conductivity will decrease. This effect due to the reduction of the material size is called ‘size
effect’. Such a thin bulk may be considered as an ideal thin continuous film.

Conductivity of a bulk metal is independent of its dimension. But for the thin
metallic films where thickness (t) is limited and of the order of ‘mfp’ the film
conductivity(σf) will no longer be independent of ‘t’. Thompson treated this from the
consideration of (i) diffuse scattering of conduction electrons by the two film surfaces and
(ii) scattering by lattice materials where mfp of the film lf is equal to lb for some arbitrary
starting point ‘z’ within the film, electrons will be scattered in all directions.

In conclusion we shall deal briefly with the conductivity of films which form a
transition group between films with crystalline structure and continuous ones. Thus, the
conductivity is given by the sum of metallic contribution and that of tunneling thermionic
emission over empty regions.

The surface properties and effects are generally of great importance in the semi
conductors. And they have special influence on their electrical properties. This influence
results from the fact that, the field produced by the surface charge penetrates to the great
depth in the semi conductor and thus affects the electrical transport phenomena.

The term super conductivity denotes the electrical state characterized by negligibly
small values of resistivity, such a state is established in some materials when their
temperature deeps below a critical temperature for a particular material.

STRUCTURAL PROPERTIES
The mechanical properties of the thin films play a major role in every application because
the stability of the thin film system depends on them. An internal stress in the film and the
insufficient adhesion to the substrate may lead to crakes into the film or to its peeling from
the structure. The mechanical properties all, as are all other properties largely determined
by the film structure and that in turn is determined by the method of deposition.

Films may have various crystallographic structures depending on the actual

conditions under which they grow. They are three different groups of films, amorphous,
polycrystalline, and mono crystalline.

Amorphous films are usually formed by elements such as Si, Ge, Se, Te, Some
compounds of Se and Te and by some oxides, if they are prepared with the substrate at
room temperature.

18
 The amorphous state is metastable state and such films easily crystalline with
accompanying liberation of energy the reduction of surface mobility of particle which leads
to the formation of amorphous film may also be achieved in systems which under normal
conditions, form crystalline films. In some films, the stabilization of the amorphous state is
achieved by different impurities.

In some cases when the substrate has a lattice constant approaching that of the film,
pseudomorphism occurs and the film assumes the structure of the substrate until a
thickness of the order 10 is reached. If the difference is greater and the binding between
the substrate and the film is strong, the pseudomorphism occurs for only the earliest
atomic layers.

1.4 APPLICATION OF THIN FILMS

In recent years, thin film science has grown into a major research area. Although the
study of the thin film phenomenon dates back well over a century, it is only over last two
decades that they have been used to a significant level in practical applications. The major
exploitation is still in the field if micro electronics. However there are growing applications
in other areas like thin films for optical and sensor devices. The development of deposition
techniques for the preparation of thin films with controlled, reproducible and defined
properties play an important role in technological applications. Although there is a wide
range of thin film deposition techniques, thermal evaporation technique has many
advantages. Transparent conductor thin films can be used as gas sensors, transparent
electrodes for solar cells, transistors protective coatings and resistors. To study the
properties of these materials Indium oxide, Tin oxide and Indium tin oxide thin films are
prepared for investigating their electrical, optical and structural properties. Properties of
these thin films strongly depend on the method of deposition, the substrate materials, the
substrate temperature, the rate deposition and the background pressure. It is known that
the growth conditions and the nature of the substrate materials affect the structure and the
crystallinity of the films.

Thin films play a vital role in nearly all electronic and optical devices. They are used
as anti refraction coatings on window glasses, video screens, camera lenses and other
optical devices. These are generally films of 100 nm thick made from a transparent
(dielectric) material with a refractive index less than that of the substrate. In solar energy
conversion, similar layers of thin films serving as anti refraction coatings on solar energy
collectors. Semi transparent metal films are used in solar cells, combinations of thin films
are used for photo thermal devices that generate low or high grade heat and thin semi
conductor. Films on metals or glass substrate form a promising type of low cost solar cell.
In integrated circuits also, thin films are very useful.

One of the newest applications of thin films is in circuit based films made in super
conductors. For example, Josephson Junctions, Ferro magnetic thin films play a major role

19
in magnetic recording and storage technology. Cds and Pbs films have photo-conductive
property. They are used in solar cells.

As are result of studies of electronic properties of thin films, thin film of alloys,
compounds and mixtures used as resistors and thin insulated films used in capacitors now
find by spread applications in integrated circuits. The sensitivity of surface conductivity of
thin semi conducting films to transverse electric field has been successfully exploited in the
promising thin film transistor (TFT). Single and multi layer piezoelectric films have been
employed as hypersonic transducers in the giga cycle range. Films having a thickness
comparable with the penetration depth and coherence length or super conductor are ideal
specimens for studying super conducting behavior (magnetization, critical current and
critical magnetization) of type I and type II super conductor in the light of various theories.
Such studies have played a major role in the theoretical understanding of the super
conductivity and have made it possible to determine the superconductivity parameters of
penetration depth, coherence length.

With rapid technology advances in the preparation of films with controlled

reproducible and well defined structures, thin films are expected to play an important role
in the studies of variety of solid state phenomenon of basic and practical interest.
Properties of a large variety of new and exotic materials obtained by the thin film
techniques will undoubtedly draw considerable attention in the future. A multitude of thin
film optical, magnetic, electronic and superconductive devices have been successfully
operated. With increasing flexibility and diversity of the application oriented industry,
natural courses of growth and selection of the new and promising devices based on
complete and careful utilization of science and technology of thin film will dominate future
development.

20
 Chapter 2
EXPERIMENTAL TECHNIQUES
2.1 Physical Vapour Deposition
Physical Vapour Deposition (PVD) technology consist of the techniques of arc deposition,
ion plating, resistance evaporation, electron beam evaporation, sputtering and many
others. It is used to deposit films and coatings or self-supported shapes such as sheet, foil,
tubing, etc. The thickness of the deposits can vary from angstroms to millimeters. The
application of these techniques ranges over a wide variety of applications from decorative
to utilitarian of two or more of the following – high temperature strength, impact strength,
specific optical, electrical or magnetic properties, wear resistance, fabric ability into
complex shapes, biocompatibility, cost, etc. A single or monolithic material cannot meet
such demand in high technology applications. The resultant solution is therefore a
composite material, i.e., a core material and a coating each having the requisite properties
to fulfill the specifications.
PVD technology is a very versatile, enabling one to deposit virtually every type of inorganic
materials – metals, alloys, compounds and mixtures thereof, as well as some organic
materials. The deposition rates can be varied from 10 to 750 000Å (10Å=1nm) per minute,
the higher rates having come about in the last 25 years with the advent of electron beam
heated sources.
The thickness limits for thin thick films are somewhat arbitrary. A thickness of 10
000Å (1μm) is often accepted as the boundary between thin and thick film. A recent
viewpoint is that a film can be considered thin or thick depending on whether it exhibits
surface-like or bulk-like properties.
The objective of deposition processes is to controllably transfer atoms from a source to a
substrate where film formation and growth proceed atomistically. In evaporation, atoms
are removed from the source by thermal means. Two methods of PVD are used in our
laboratory:
 resistance (thermal) evaporation
 electron beam evaporation
.

The physical vapour deposition processes take place in vacuum. The vacuum environment
is a complex one and is neither a void nor inert. To be successful, thin film deposition must
be done with awareness of the effect of the environment upon the vapour flux and growing
film. The three most important aspects of the vacuum environment to thin film deposition
are: the pressure, expressed as the mean free path, the partial pressure of reactive gasses
and in inert working gasses and the film vapour arrival to reactive gas impingement rate
ratio. In our laboratory system shown in Fig. 1. is employed for vacuum evaporation of
metals. The basic pumping system consists of oil-diffusion pump backed by rotary
mechanical pump. The upper chamber must be vented to air in order to load substrates. A
dual vacuum-pumping circuit consisting of three valves, in addition to vent valve, is
required to accomplish these ends.

21
 Resistance evaporator
Deposition of thin films from resistance heated evaporation sources was the first practical
thin film deposition technique. The resistance refractory metal source is the heart of the
evaporation system (Fig.1). Selection of a suitable source (Fig.2) is the critical decision in
designing a resistance evaporation process. A source is selected to meet the following
process requirements: evaporant compatibility (many important evaporants dissolve all
refractory metals to some extend), capacity and power availability. In general, sources are
made of refractory metal (Mo, Ta, W) of three design classes: coils, boats and special
purpose designs.
Electron beam gun
The electron beam heated evaporation source is a thermal evaporator as is a resistance
heated source. It differs from resistance heated source in two ways: the heating energy is
supplied to the top of the evaporant by the kinetic energy of a high current electron beam,
and the evaporant is contained in a water cooled cavity or hearth. Heating by electron
beam allows attainment of temperatures limited only by radiation and conduction to the
hearth. Evaporants contained in a water cooled hearth do not significantly react with the
hearth, thus providing a nearly universal evaporant container.
The electron beam heated source is made up of a power supply and evaporation source.
Power supply (Fig.3) consist of three interconnected but independent power supplies, high
voltage, filament and magnet. Evaporation source (Fig.4), as used for high technology thin
films fabrications has 3 basic sections: the electron gun, the beam deflection magnetic lens
and the evaporant-containing hearth. The beam is formed in the gun, passes through the
magnetic lens and is focused upon the evaporant.

Fig 1

22
Fig.2

23
 Fig.3

Fig.4

24
 To perform the evaporation one should:
1. Switch on the cooling water – taps are behind vacuum plant, next to the wall
2. Switch on vacuum plant
3. Open the chamber (button UP) and place wafer in Al holder above evaporator No2 or No3
and close the chamber (button DOWN)
4. Pump high vacuum:
a) Switch on rotary pump, open valve P(3) and pump prevacuum in chamber – 10-2hPa
b) Close P(3), open P(2) and pump prevacuum in diffusion pump
c) Open P(1), switch on diffusion pump and pump high vacuum in the chamber - more
than 10-3hPa (it takes 30 minutes)
5. Evaporating:
a) Select proper evaporator and switch it on
b) Increase power slowly
c) After melting Al maintain power till the end of evaporating Al
d) Decrease power to zero and switch it off
6. Wait 7 minutes, close P(1) and vent chamber – valve P(4)
7. Open the chamber, take wafer out and close the chamber
8. Pump prevacuum in the chamber
9. Close P(3), open P(2) and switch diffusion pump off
10. After 15 minutes close P(2) and switch rotary pump off

2.2 PREPARATION OF THIN FILMS

Thin films are evaporated on to clean glass substrate using thermal evaporation method.
Thermal evaporation is a simple method in which the material is created in a vapour form
by means of resistive heating. On heating a material in vacuum, sublimation takes place and
the atoms are transported and get deposited on to pre cleaned substrate held at suitable
distance at desired temperatures. The material for deposition is supported on source which
is heated to produce desired vapour pressure. The requirement for the source are that it
should have a low vapour pressure at the deposition temperature and should not react
with the evaporant. The shape of the source is designed and fabricated in such a way to
hold the evaporant 45 material. The semiconductor is evaporated using Molybdenum or
tungston boat. The unit is operated at 10V/100A ratings of the step down transformer.

SUBSTRATE CLEANING

25
A wide variety of cleaning procedures are available to develop good quality thin films,
highly polished and thoroughly cleaned glass substrates are used here for deposition of
films. First, the substrates are cleaned using liquid detergent and then cleaned using
running water. And then it is kept in dilute hydro chloric acid for sometime. After this, the
substrates are cleaned using distilled water. Then the substrates are agitated in acetone.
Finally the substrates are dried in hot air.

VACUUM COATING UNIT

The type of vacuum equipment depends on the desired purity of the films. Detailed reviews
on various types of vacuum systems and their ultimate pressure are given by Holland,
Carewell, Dushaman and Roth. The vacuum system employed to deposit and the
characterize thin film contains an assortment of pumps, tubes, valves and gauges to
establish and measure the required reduced pressure as shown as in figure. Basically the
vacuum system “Hind Hivac” vacuum coating unit model No. 12A4D consists of 0.4m
diffusion pump backed up by oil sealed rotary pump. Ultimate pressure obtained in a 0.3m
diameter steel bell jar is of the order of 8×10-6 mbar. It has set ups of electron beam
evaporation and flash evaporation. Most of the evaporation is carried out at a pressure of
(1-2)× 10-5 torr. The pressure measurement in the system is done by means of Pirani and
Penning gauges with the system. The Pirani gauge model Hind Hivac- A 6 STM is used to
measure vacuum in this range 0.5 ×10-3 torr. The penning gauge model STM4 is used to
measure vacuum in the range 10-2 to 10-6 torr in two ranges with instant range –charger
provided by a toggle switch.

26
 Vacuum coating unit

Figure: Schematic diagram of a vacuum coating unit with

1. Bell jar
2. Diffusion pump
3. Rotary pump
4. Control Panel
5. L T Control
6. Pirani gauge
7. Penning gauge

Vacuum coater model 12A4-D is a versatile laboratory model coating unit for thin film
applications with facilities for evaporation, glow discharge cleaning etc. This unit offered
with optical accessories like Substrate Heating, Rotary Drive, Flash Evaporation, EB Gun
evaporation etc. It is an ideal coating in Research, Educational institutions, semiconductor,
optics and material development institutions. The vacuum coating unit & chamber
categories are manufactured using high vacuum compatible materials.

27
SYNTHESIS OF SILVER THIN FILMS
The silver thin films of uniform thickness were deposited on a clean glass substrate using
thermal evaporation method under high vacuum atmosphere of about 2x10-6mbar.
Electrical, optical and structural properties of these thin films have been studied after
thermal annealing at different temperatures of 50,100,150and 2000C for one hour .The
thickness of the thin film is measured by using an air wedge apparatus. The structural and
morphological characterization was done using XRD and UV analysis respectively.

Applications
The following are the application areas of silver:

 In photography
 In dentistry
 As cutlery and mirrors
 As a catalyst in oxidation reactions
 In high-capacity zinc long-life batteries
 As a precious metal to make coins and jewelry
 In electrical and electronic industries for items such as printed circuits and
computer keyboards

Metallic thin films, such as silver, gold etc. exhibit high optical reflection over a wide optical
radiation spectra that make them suitable for the use as optical mirrors. For this purpose
the thin film should be continuous what can be achieved when a coating is at least 50 nm
thick. Another requirement is very flat and smooth surface in order to achieve a high
directional reflection. However, application of non-continuous thin films can benefit from
their unique properties: the films may exhibit semi-transparency, while still preserve their
ability to light reflection. For example, such films have already found application in the
construction of so-called low emissivity coatings applied in architectural glass windows.
The high thermal stability of the Ag thin film was developed and it could application on
electron devices. Recently, there has been an increase in the number of applications of
silver (Ag) thin film, due to their unique optical, electrical and mechanical properties. These
properties have led them to play an irreplaceable and increasing role in many areas of
today’s very demanding and rapidly developing technology, especially in the
microelectronic device applications and optical industries .The advantages of the Ag thin
film application on microelectronic devices are as follows:(1) Low specific resistivity, (2)
Good thermal stability, (3) High uniformity across the flat substrate, (4) Low particle
contamination, (5) Good adherence to substrate, (6) Low manufacturing cost ,; Silver
nanoparticles have potential applications in fields of nanosicence and technology.

28
2.3 XRD – Structural Analysis
X-ray diffraction (XRD) methods are the most widely-used methods for determining the
crystal structure of materials which identify respective chemical compounds and product
quality rather than their compositions of chemical elements .X-ray diffractometry is a
spectroscopic type of diffraction method that depends on phenomenon of wave
interferences. According to Bragg’s Law, electromagnetic waves of X-ray beams incident on
a crystallite solid will be diffracted by the crystallographic planes as illustrated in Figure

Two in-phase incident waves, beam 1 and beam2, are deflected by two crystal planes (A
and B). The deflected waves will not be in-phase except when the following relationship is
satisfied.

nλ= 2d sin θ 1

where:

n = order of reflection

λ = wavelength of the x-rays

d = characteristic interplanar spacing

θ = angle between the incident beam and the normal to the reflecting lattice plane

Equation (1) is the basic law of diffraction called Bragg’s Law and it can be simply acquired
by calculating the path differences between the two beams in Figure . The path difference
depends on the incident angle (θ) and the spacing between the parallel crystal planes (d).
In order to keep these beams in-phase, their path difference (SQ + QT = 2d sin θ) has to
equal one or multiple X-ray wavelengths(nλ).

The annealing temperatures of the Ag thin films were 323K,373K,423K,473K respectively.

The crystalline structures were determined by X-ray diffraction(XRD) using the CuKα
radiation (Kα = 1.5418 Å).Some process can change the residual stress of thin films and
improve the structural and mechanical properties of thin films. Annealing thin films at the
high temperature is one of these methods. Heating treatment supplies energy to
rearrangement of grains.

29
Fig. Bragg Diffraction by Crystal Planes

According to Bragg’s Law, when constructive interference is detected at a given incident

angle and a wavelength of the incident beam, information on the spacing between atomic
planes of a crystal can be obtained. Knowing the spacings of crystallographic planes by
diffraction methods, crystal structure of materials can be determined .

The XRD of dried powder were characterized by using an X-ray diffractometer X’PERT PRO
PW3040 (Cu Kα radiationand wavelength, λ = 0.1541 nm) for product quality. Typical
geometric arrangement of Xray diffractometer is illustrated in Figure.

Fig. Geometric
Arrangement of X-
ray Diffractometer

30
 Applications of XRD
• XRD is a nondestructive technique

• To identify crystalline phases and orientation

• To determine structural properties:

Lattice parameters (10-4Å), strain, grain size, epitaxy, phase composition, preferred
orientation (Laue) order-disorder transformation, thermal expansion

• To measure thickness of thin films and multi-layers*

• To determine atomic arrangement

• Detection limits: ~3% in a two phase mixture; can be

~0.1% with synchrotron radiation

Spatial resolution: normally no

2.4 THIN FILM THICKNESS AIR WEDGE METHOD

The air wedge consists of a wedge shaped air film formed between two thin rectangular
optically plane glass plate, one of the plate is placed over the other

Slight inclination by keeping a thin straight wire near one edge parallel to edge . The plates
are simply held together.

The thin film is placed between two optically plane glass plate and tightly tied together, to
form air wedge. Light from sodium lamp is resolved parallel by a convex lens. This light is
then made to reflect from a glass plate placed inclined at 45 horizontal. So that is incident
at normally at the air wedge. A vernier microscope is arranged vertically above glass plate.
The microscope is properly focused. Then a number of equidistant alternate bright and
dark interference bands are observed. The point of intersection of crosswire is made to
coinside with any dark band and the microscope reading is taken. Similarly readings are
taken from m+5,m+10,… The band width β is then calculated.

The interference fringes formed in an air wedge and those based on the theory of two –
beam interference such as the pluta microscope and M Michelson interferometer are
utilized for estimating the thickness and / or refractive index of transparent poly propylene
thin films. The theories of the methods are presented and their applications to
measurement of film thickness and refractive index are given. The accuracy of the
measured film thickness and refractive index is calculated. The three interference methods

31
provide that they could be transformed in to valuably technological tools. The study
established that, estimation of the thickness of thin films by the air wedge interference
method is more simple and more accurate than the others. Films not more than 50
micrometer thickness are recommended in the pluta interference microscope. Thickness of
thin film can be calculated using the formula

t=λl/2β

β=bandwidth

l=length of glass plate

λ=wavelength of light used

t =thickness

2.5 UV- VISIBLE SPECTROSCOPY

Ultraviolet- visible or UV -VIS spectroscopy has been used for a long time and was really
one of the first spectroscopic techniques developed. In the electromagnetic spectrum you
find that radio frequencies, microwaves and infrared radiation all have longer wavelength
than visible light. Ultraviolet light and X-rays are found at the other end of the
electromagnetic spectrum and have even shorter wavelengths. The visible range spans
from 800nm (this is red) to 400nm (which is blue or more precisely, violet). The UV region
extends from 400nm down to 200nm. If you wish to record a UV- VIS spectrum, you will
need special UV cuvette. The UV – VIS spectrophotometer scans the visible and the UV
region. It then produces a plot of absorbance against wavelength, which we call a UV – VIS
spectrum. The visible region is of interest only if our sample is colored to the eye. If the
sample is not and appears as “colorless”, then will be content with recording a UV spectrum
between 400nm and 200nm, will obtain UV spectrum with a single absorption peak. The
information we get from the UV spectrum is the wavelength at which the compound shows
maximum absorbance, also called lambda max (𝛌max). Some compounds can have several
such maxima.

Ultraviolet visible(UV – VIS) spectrophotometry refers to absorption spectroscopy or

reflectance spectroscopy in the ultraviolet- visible spectral region. This means it uses light
in the visible and adjacent (near- UV and near- infrared [NIR]) ranges. The absorption or
reflectance in the visible range directly affects the perceived color of the chemical involved.
In this region of electromagnetic spectrum, molecules undergo electronic transitions.

The instrument in ultraviolet- visible spectroscopy is called UV/Vis

spectrophotometer. It measures the intensity of light passing through a sample (I) and

32
compares it to the intensity of light before it passes through the sample (I0). The ratio(I/I0)
is called the transmittance, and is usually expressed as a percentage (%T). The absorbance
A is based on the transmittance:
A=- log(%T/100%)
The UV -visible spectrophotometer can also be configured to measure reflectance. In this
case, the spectrophotometer measures the intensity of light reflected from a sample (I) and
compares to the intensity of light reflected from the reference material (I0). The ratio (I/I0)
is called the reflectance and usually expressed as a percentage (%R).
The instrument used in ultraviolet–visible spectroscopy is called a
UV/Vis spectrophotometer. It measures the intensity of light passing through a sample
and compares it to the intensity of light before it passes through the sample.The ratio is
called the transmittance, and is usually expressed as a percentage (%T). The absorbance, is
based on the transmittance:

Schematic diagram of UV-visible spectrophotometer.

The UV–visible spectrophotometer can also be configured to measure reflectance. In

this case, the spectrophotometer measures the intensity of light reflected from a
sample and compares it to the intensity of light reflected from a reference material
(such as a white tile). The ratio is called the reflectance, and is usually expressed as
a percentage (%R).
A complete spectrum of the absorption at all wavelengths of interest can often be
produced directly by a more sophisticated spectrophotometer. In simpler instruments
the absorption is determined one wavelength at a time and then compiled into a

33
 spectrum by the operator. By removing the concentration dependence, the extinction
coefficient (ε) can be determined as a function of wavelength
In the process of absorption and reflectance, the visible range directly affects the percieved
colour of the chemicals involved. In this region of the electromagnetic spectrum, atoms and
molecules undergo electronic transitions. Absorption spectroscopy is complementary to
flourescence spectroscopy, in that flourescence deals with transition from the excited state
to the ground state, while absorption measures transitions from the ground state to the
excited state.

34
Chapter 3: OPTICAL AND STRUCTURAL STUDIES OF Ag THIN
FILMS
3.1.XRD STUDIES
X ray diffraction pattern of Ag thin films of thickness 12.904 μm, as deposited and annealed
in air at 2000c for one hour are shown in figure

Ag as deposited

Ag thin film annealed at 2000C

35
For the as deposited film a sharp peak is identified. which shows the crystalline
nature of the thin film. The as deposited film shows a peak with 2θ =33.1630 and
corresponding d spacing is 2.69923 A. The corresponding hkl vaue is (110). For the
annealed sample some peaks are identified, which shows the polycrystalline nature
of the thin film. The Ag thin film annealed at 2000 c shows peaks with 2θ =
33.157,39.074,45.260,65.299,78.203 and the corresponding d spacings are
2.69967,2.30343,2.00191,1.42780,1.22135 A0 respectively. .. The corresponding (h
k l) values are (110), (111), (200), (220) and (311). It is also clear from the Figure
that only silver peaks are present throughout the coated surface indicating the
purity of the coated films.In this case the observed maximum values of 2θ
=33.168,39.074,45.255,65.301,78.1970 and corresponding values of FWHM are
0.263,0.290,0.325,0.324,0.4200 respectively. . In XRD patterns, the samples showed
the characteristic peaks of Ag and only the face-centered cubic structure was found.
The presence of diffraction peaks at 2θ values 33.163°and 33.157°corresponds to
(110) plane of silver, for as deposited and annealed at2000 c respectively. No other
peaks of impurity or second phases have been detected. The XRD patterns showed
the characteristic peaks of Ag (JCPDS no. 40783), and only the face-centered cubic
structure was found. The intensity of the diffraction peaks of Ag thin films increased
when it is annealed at 2000 c, suggesting that better crystalline quality was obtained.
Since glass was used as an amorphous substrate, no extra peak detected. The XRD
pattern of thin film annealed at 200C temperature shows that, Ag film has several
grains related to (111), (200), (220),and (311) planes. The (111) peak are relatively
sharp. When temperature increased Ag peaks were heightened. A little shift in the
place of Ag peaks occurred, which related to the uniform strain due to applying high
temperature. High intensity of Ag(111) implies the high compact of Ag grains along
the (111) direction. High compact of (111) grains shows that thermal treatment
empowered Ag (111) grains and allowed Ag thin film to have the (111) direction as
its preferred orientation. The results show that the crystallization of the films
increases after annealing and The polycrystalline Ag films can be observed after
annealing at 200 C and the peaks namely the (111), (200), (220) and (311) visible in
Fig. are due to the cubic Ag phase. The (111) Ag peak intensity was larger than that
of the other peaks because the (111) direction in Ag film has the lowest surface
energy For the annealed films, . The XRD results have shown that the crystalline Ag
films with preferred orientation along (111) direction cannot be observed before

36
 annealing .The silver oxide phase and improvement of crystallinity was observed
after annealing at temperature of 200 ◦C .

CALCULATION OF CRYSTALLINE SIZE

The grain size was calculated using scherre formula

D=Kλ/βCos(θ)

D = The average crystalline size

K = Constant(~0.94)

λ = Wavelength of xray source(1.5406 A0)

β = Fall width half maximum (FWHM) of peaks

θ = The diffraction angle

Peak position Theta Cos(θ) FWHM(β) FWHM (β) D=Kλ/βCos(θ)

2theta (degree) (radian) (in degree) (in radian) (nm)

33.168 0.29022 0.958180943 0.263 0.0046025 32.8379789

39.074 0.3418975 0.942120177 0.29 0.005075 30.288334671
45.255 0.39598125 0.922618527 0.325 0.0056875 27.59778098
65.301 0.57138375 0.841153454 0.324 0.00567 30.3640329
78.197 0.68422375 0.774909926 0.420 0.00735 25.4260666

The average crystalline size D = 29.30283 nm

37
3.2 THIN FILM THICKNESS AIR WEDGE METHOD

Least count=0.001 cm

Order Microscopic Reading Fringe width

m MSR(cm) VSR(cm) Total(cm) B (cm)

m 5.3 26 5.326 0.079

m+1 5.2 47 5.247 0.067

m+2 5.1 80 5.180 0.065

m+3 5.1 15 5.115 0.067

m+4 5 48 5.048 0.066

m+5 4.9 82 4.982 0.067

m+6 4.9 15 4.915

CALCULATIONS
Mean fringe width β = 0.0685 cm =0.0685x10-2 m

Wavelength of sodium light λ =589.3x10-9 m

Distance of film from the line of contact of the glass plate l =3 cm= 3x10-2 m

Thickness of the film t =λl/2β = (589.3x10-9 x 3x10-2)/(2 x 0.0685x10-2)

=12.904 micro meter

38
3.3 UV-VIS ANALYSIS
BAND GAP

In solid state physics, a band gap also called an energy gap or bad gap, is an energy range
in a solid where no electron state can exist. In graphs of the electronic band structure of
solids, the band gap generally refers to the energy difference (in electron volts) between
the top of the valence band the bottom of the conduction band is insulators and
semiconductors. This is equivalent to the energy required to free an outer shell electron
from its orbit about the nucleus to become a mobile charge carrier, able to move freely with
the solid material. So the band gap is a major factor determining the electrical conductivity
of a solid substance with large band gaps are generally insulator, those with smaller band
gap are semi conductors, while conductors either has very small band gap or none, because
the valence and conduction bands overlap. The conductivity of intrinsic semiconductors is
strongly dependent on band gap. The only available barriers for conduction are the
electrons, which have enough thermal energy to be excited across the band gap, the band
gap energy of a semiconductor tends to decrease with increasing temperature. When
temperature increases, the amplitude of atomic vibrations increase, leading to large
interatomic spacing.

THEORY

Strong absorption band arising from electron excitation produces essentially a UV cut off ,
causing most glasses to appear opaque in the UV. These electrons excitations are generally
are of two types ,

Intense excitation , where electrons are excited from the valence band to unoccupied states
, in the excitation all the conduction band levels .

Transfer of an electron between the shells of one ion and the shells of a neighbouring ion.

Optical absorption studies of the thin film are made by using UV – VIS NIR(ultra violet –
visible-near infrared.)spectrometer varian carries 5000. From the absorption spectra
optical parameters like absorption co-efficient(α), optical band gap(Eg) have been
evaluated. The absorption co-efficient(α) was calculated from the equation.

α=2.303 (A/t)

Where t is the thickness and it is measured by using air wedge arrangement. A is

absorbance of the silver film. The direct optical band gap (Eg) was determined by fitting
absorption data to the equation.

39
αhv=B(hv-Eg)1/2 For absorption coefficient α ≥10^4 cm.

The exponent n can take the value 2.3, ½,3/2 for indirect allowed, indirect forbidden ,
direct allowed and direct forbidden transition respectively. Glass is an indirect band gap
amorphous material , there for the value of n is 2. Then ,

αhv=B(hv-Eopt)2

(αhv)1/2=A(hv-Eopt)

Where A is another constant.

hv is the photon energy, B is the constant related to the material. E g is found by extra
polating the straight line in the (αhv)1/2 versus hv graph.

The UV-Visible absorption spectra of Ag thin films of thickness 12.904μm annealed

at different temperatures are given below.

Ag as deposited

Ag thin film annealed at 500 c

40
 Ag thin film annealed at 1000c

Ag thin film annealed at 1500c

Ag thin film annealed at 2000c

41
Transmittance spectra of Ag thin films of thickness 12.904μm annealed at different
temperatures are given below

Ag as deposited Ag annealed at 500C

Ag annealed at 1500C

Ag annealed at 1000C

Ag annealed at 2000C

42
Reflectance spectra of Ag thin films of thickness 12.904μm annealed at different
temperatures are given below

Ag as deposited Ag annealed at 500 C

Ag annealed at 1000C Ag annealed at 1500C

Ag annealed at 2000C

43
The study of optical absorption is a useful method for investigating the induced
transition and providing information about the band structure in the materials. The
basic principle behind the optical study is that the electron will excite from the
ground state by absorbing a photon with energy greater than band gap. The optical
absorption spectra of pure silver thin film and that annealed at 50, 100, 150, 2000 C
over a wavelength range of 200nm – 1000nm is shown above.

All the spectra are nearly identical and that a very little effect is observed .All the
samples possess a B band near 310 nm. The intensity of the absorption peaks for the
thin films changes with annealing temperature.

DETERMINATION OF THE ENERGY GAP(Eg)

To obtain information about the direct and indirect inter band transitions, the
fundamental absorption edge data could be analyzed within the frame work of one –
electron theory of Bardeen.

The variation in absorption coefficient (α ) with photon energy for band to band
transition is obtained as

α = α 0[(hv-Eg)]n

Where Eg the energy gap and n determines the type of transition. α 0 is a constant. n
has discrete values ½,3/2,2,3 or more depending on whether the transition is direct
or indirect and allowed or forbidden. In the direct and allowed cases n=1/2 where
as for the direct but forbidden cases it is 3/2. But for the indirect and allowed cases ,
n=2 and for the indirect forbidden cases it will be three or more. The magnitude of n
can also be estimated from the slope of the log α vs log hv and hence can suggest the
type of transition by extrapolating the linear portion of the graph to α=0. Also if the
absorption coefficient α<<104, cm-1 represents allowed indirect transitions and α
>>104, cm-1 represents allowed direct transitions.

The dependence of (hvα ) on photon energy (hv) was plotted for different values of
n. The most linear fit was obtained for n=2 , showing the existence of indirect band
gap . Figure shows the functional dependence of (hvα)1/2 on hv for the silver
deposited and annealed films, and extrapolating to zero absorption , the band gap is
obtained.

44
45
46
The value of energy gap are listed below.

Annealing temperature(0C) Fundamental energy gap(eV)

Ag deposited 3.3056
50 3.5908
100 3.6048
150 3.6243
200 3.6361

The variation in energy gap with the annealing temperature is due to the excitation
of electrons across the gap from valence band to conduction band which may be
attributed to phase transitions. The variation of band gap is attributed to the
deposition of oxygen during annealing. This causes an increase in donor levels at the
bottom of the conduction band and results a variation in band gap.

47
 Chapter 4
CONCLUSION
The silver thin films of uniform thickness were deposited on a clean glass substrate using
thermal evaporation method under high vacuum atmosphere. Electrical, optical and
structural properties of these thin films have been studied after thermal annealing at
different temperatures of 50,100,150and 2000C for one hour .The thickness of the thin film
is measured by using an air wedge apparatus. The structural and morphological
characterization was done using XRD and UV analysis respectively.

The thickness of the thin film is calculated by using air wedge apparatus and is found to be
equal to12.904 μm. For the deposited film a sharp peak is identified., which shows
the crystalline nature of the thin film. The XRD patterns showed the characteristic
peaks of Ag (JCPDS no. 40783), and only the face-centered cubic structure was
found. The intensity of the diffraction peaks of Ag thin films increased when it is
annealed at 2000 c, suggesting that better crystalline quality was obtained. The grain
size was calculated using scherre formula. The average crystalline size D = 29.30283
nm. All the absorption spectra are nearly identical and that a very little effect is
observed .All the samples possess a B band near 310 nm. The intensity of the
absorption peaks for the thin films changes with annealing temperature

The dependence of (hvα ) on photon energy (hv) was plotted for different values of
n. The most linear fit was obtained for n=2 showing the existence of indirect band
gap.

48
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