Chapter-2

Thin Film Preparation

Methods for Deposition of SnSe Films
2.1 Introduction

The art and science of the fabrication of thin solid films have an accelerated
growth because of its impact in the electronic devices. The development of number of
thin film devices in which, semiconductor thin films are mainly used, has
revolutionized various fields. The investigations of different parameters governing the
properties of semiconductor thin films lead to manipulation of these properties for the
progress of humankind. The development of thin film technology has led to its
application in diverse fields from microelectronics to optics, space science to aircrafts,
and superconductivity to photovoltaic and to spintronics. Thus, the thin film studies
have directly or indirectly caused the advancement of many new areas of research in
solid-state physics and chemistry and will continue to play increasingly important
roles in the study of a variety of problems of basic and technological importance.

Initially use of thin films was centered on the preparation of anti-reflecting

coating for lenses, multilayer interference filters, automobile headlights and
decorative coatings. Industrialization of thin film technology has been started in the
beginning of the 20th century.

In recent years, thin film science has grown world-wide into a major research
area. The importance of coatings and the synthesis of new materials for industry have
resulted in a tremendous increase of innovative thin film processing technologies.
Currently, this development goes hand-in-hand with the advancements of scientific
and technological breakthroughs in microelectronics, optics and nanotechnology [1,
2]. A second major field comprises process technologies for films with thicknesses
ranging from one to several microns. These films are essential for a multitude of
production areas, such as thermal barrier coatings and wear protections, enhancing
service life of tools and to protect materials against thermal and atmospheric
influences [3, 4]. Presently, rapidly changing needs for thin film materials and devices

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are creating new opportunities for the development of new processes, materials and
technologies. Therefore, basic research activities will be necessary in the future, to
increase knowledge, understanding, and to develop predictive capabilities for relating
fundamental physical and chemical properties to the microstructure and performance
of thin films in various applications. In basic research, special model systems are
needed for quantitative investigations of the relevant and fundamental processes in
thin film materials science. In particular, these model systems enable the investigation
of nucleation and growth processes, solid state reactions, the thermal and mechanical
stability of thin film systems and phase boundaries. Results of combined experimental
and theoretical investigations are a prerequisite for the development of new thin film
systems and the tailoring of their microstructure and performance.

2.2 Brief out Line of Thin Film Preparation Methods

Thin film technology has become extremely important in recent years due to a
dramatic increase in the industrial usage of thin films with its applications in many
diverse areas and the need for new and improved optical and electronic devices. Thus,
in present day technological development, thin films play an important role. Thin film
deposition techniques have a key role in the fabrication of sophisticated solid state
microelectronic devices. A large number of techniques have been successfully utilized
to prepare solid thin films. However, the methods of preparation of thin films may be
divided essentially into four groups, as given bellow.

Physical vapour deposition(PVD)

Sputtering
Chemical vapuor deposition(CVD)
Chemical deposition

2.2.1 Physical vapour deposition

Physical vapour deposition is the most common technique used for deposition
of metal, alloy and many compound films. The primary requirement for the method is
to achieve a vacuum of 10-5 torr or better. In this method the material evaporates or
sublimates in vacuum due to thermal energy (resistive heating) and then the vapor
stream of atoms or molecules condenses on a cooler substrate so as to form a

25
continuous and adherent deposits of desired thickness [5]. Physical vapour deposition
can be achieved by a variety of methods like thermal evaporation, electron beam
evaporation, radio frequency induction heating, laser beam evaporation, electron gun
heating etc. [6-8]. Multi-component alloys or compounds which tend to distill
fractionally may be evaporated by flash evaporation [9-11]. Some of these methods
are discussed bellow.

2.2.1.1 Resistive heating (thermal evaporation)

Different methods are used for evaporation of materials to be deposited. The

most commonly used method is thermal evaporation technique. Thermal evaporation
of the material can be achieved by a variety of physical methods. The oldest process is
evaporation from a boat or a wire helix sources, which consists of a refractory metal
(tungsten, tantalum, or molybdenum) having high melting point and very low vapor
pressure, are heated by an electric current. Vapor sources of different designs are used
for evaporation depending on the evaporant material have described by many authors
[12-14]. Even though new and modified techniques have been developed, electrical
resistive sources are still used extensively to prepare thin films of elements [15-21],
oxides [22-26], dielectrics [27] and semiconductor compounds [28-34].

2.2.1.2 Electron beam evaporation

The electrons emitted from a tungsten cathode are accelerated by high

voltages are focused on the substance to be evaporated which is kept in a water-
cooled crucible. The kinetic energy of the electrons is transformed into thermal
energy, so that the material in the crucible melts and evaporates into the vacuum.
High purity films can be prepared by this method because crucible materials or
reaction products are practically excluded from evaporation. We can evaporate any
material using this method and rate of evaporation is higher than that of resistive
method.

2.2.1.3 RF heating

Radio frequency can be used to heat the evaporant. By suitable arrangement of

RF coils, levitation and evaporation can be achieved, thereby eliminating the
possibility of contamination of the film by the support crucible.

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2.2.1.4 Laser evaporation

High power, pulsed laser beams can be used for ejecting particles into the
vacuum. The laser source, kept outside the vacuum system, is focused on to the target
material, and the ejected material is deposited on the substrate, placed in front of the
target material inside the vacuum. An advantage of laser evaporation is that because
of its high energy, alloys can be deposited without a change of composition as in flash
evaporation techniques.

2.2.1.5 Flash evaporation

This method is useful in the preparation of multi-component alloys or

compounds that tend to fractionate in the evaporation process. In this method, the
selected material is prepared in powder form with as small a grain size as possible,
and its small quantity is dropped on to a boat that is hot enough to ensure that the
material is evaporated instantaneously. The temperature of boat should be high
enough to evaporate the less volatile material fast. Various methods (ultrasonic,
mechanical, electromagnetic etc.) are used to drop the powder on the boat.

A drawback of this technique is the difficulty in preoutgassing the evaporant

powder. Degassing the powder can be accomplished to some extent by vacuum
storage for 24 - 36 hours prior to deposition.

2.2.2 Sputtering

Sputtering is a process of ejection of atoms from the surface of a material by

bombardment with energetic particles. In this process the substance to be deposited
(target) is kept in the form of an electrode whose surface atoms or molecules are
ejected by momentum transfer from the bombarding ions. The ejected or sputtered
atoms are allowed to condense on a substrate to from a thin film. If the ejection is due
to bombardment by positive ion, the process is known as cathodic sputtering. The ions
required for bombardment is usually obtained by maintaining a glow discharge due to
an applied electric field within the vacuum chamber. Over the years various sputtering
techniques have been developed. The techniques are glow discharge sputtering, triode
sputtering, ion plating, magnetron (direct and reactive) sputtering, ion beam sputtering
reactive sputtering, RF sputtering, etc [35-37].

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2.2.2.1 Glow discharge sputtering

The simplest sputtering arrangement is the glow discharge sputtering system.

In this method an electric field is applied between two electrodes in an inert gas at low
pressure. The plate of the material to be deposited is used as the cathode and the
substrate is mounted on the anode facing the target. When the electric field is applied,
a glow discharge is formed. By the impact of positive gas ions on the target plate, the
atoms of the cathode material will be ejected, which eventually condense on the
substrate as a thin film.

2.2.2.2 Triode sputtering

In this case extra electrons are injected in the discharge by thermionic

emission from an additional hot cathode. The total ionization and the ionization
efficiency are increased by accelerating these electrons. This method is often
combined with a magnetic field.

2.2.2.3 Ion-beam sputtering

In this method ions of the inert gas are produced in a discharge and then
extracted in a separate vacuum chamber and accelerated on to the target. By this
method it is possible to sputter at a pressure even below 10-3 torr, and the
incorporation of the inert gas atoms into the growing film can be reduced.

2.2.2.4 Magnetron sputtering

Magnetron sputtering technology has made significant progress since its

development, for the high rate of the deposition of metal, semiconductor and
dielectric films. In comparison to conventional diode sputtering, magnetron
sputtering, apart from obtaining high deposition rates at lower operating pressures,
makes it possible to obtain high quality films at low substrate temperatures. For a
simple planar magnetic system, a planar cathode is backed by permanent magnets that
provide a toroidal field with field lines forming a closed path over the target surface
(cathode). The secondary electrons generated are trapped in cycloidal on it near the
target and present self-heating of the substrate. The confinement of the plasma and the
resultant intense plasma allow magnetron-sputtering systems to operate at much lower

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pressures and lower target voltages than are possible for r.f. diode sputtering. Here the
deposition rates are higher and cover large deposition areas.

2.2.2.5 RF Sputtering

This can be used to sputter insulator films directly and also possible to
sputter at low pressures. In this case an r.f. potential is applied to the metal
electrode placed behind the dielectric plate target.

2.2.2.6 Reactive sputtering

Films of oxides, nitrides etc. of metals can be prepared by introducing the

reactive gas along with the inert sputtering gas in to the sputtering system. The main
advantage of this method is the variation of the composition from the pure metal to
the highest reaction product caused only by variation of the pressure of reactive gas.

2.2.3 Chemical vapour deposition (CVD)

The deposition of thin film from gaseous phases by thermal decomposition or

chemical reactions on substrates at high temperature is known as the CVD process.
Sometimes a carrier gas is also introduced either to control the rate of reaction or to
prevent undesired reactions at the prevailing elevated temperature.

It is an important and popular technique for the preparation of thin films of a

wide variety of materials, on various substrates. Films of high purity and quality, with
required composition and doping levels, can be prepared by this method. In this
method, solid films are formed on the substrate, maintained at a suitable temperature,
by the reaction of the constituents in their vapor phase. The chemical reaction itself is
an important characteristic of all CVD processes. Several types of chemical reactions,
such as chemical transfer, thermal decomposition (pyrolysis), reduction, oxidation,
nitride and carbide formation etc. are available to carry out the CVD processes.

2.2.3.1 Photochemical vapour deposition

Photo CVD is a recently developed, low temperature deposition technique for

the preparation of high quality films for many technological applications. In this
process, the photochemical deposition takes place when high energy photons

29
selectively excite states in the surface-absorbed or gas phase molecules leading to
bond rupture and the production of free chemical species to form the films or to react
to form compound films on the adjacent substrate. Ultra violet lamps or lasers are the
sources used for the photochemical deposition.

2.2.3.2 Plasma-enhanced chemical vapour deposition

It is a versatile technique for depositing a wide variety of film materials for

microelectronic, photovoltaic, and many other applications. In this process, the
plasma produced by r.f., dc or microwave fields are used to promote the chemical
reactions.

2.2.4 Chemical methods

In chemical deposition method, thin films are deposited on the substrate from
aqueous solution either by passing a current or by chemical reaction under appropriate
conditions. Large or small and even or uneven surfaces of all types conducting or
insulating can be coated with relative ease by this cost effective method. The electro-
deposition, spray pyrolysis, closed space sublimation (CSS), anodization, solution
growth, etc. are different chemical deposition techniques normally used for the
deposition of thin films [38-40]. These methods used simpler equipments and are
more economical than physical methods. Chemical methods of thin film deposition
include the following.

2.2.4.1 Electrolytic deposition

This is an electrochemical process in which the anode and cathode are mersed
in a suitable electrolyte and the passage of electric current serves to deposit the
material on the cathode. By this method, it is possible to deposit only on metallic
substrates and the film may be contaminated by the electrolyte.

2.2.4.2 Electroless deposition

Electroless deposition is simple, and is possible for large-area deposition from

a solution, in which no electrode potential is applied, unlike electrodeposition. The
rate of deposition depends on the temperature of the bath and the chemical reduction
in some cases needs to be stimulated by a catalyst.

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2.2.4.3 Anodization

This is another electrochemical process, used to deposit oxide films over

certain metals. Here when the electric current is passed, the anode reacts with
negative ions from the electrolyte and forms an oxide coating.

2.3 Choice of Deposition Process

The deposition technique can be chosen depending upon the type of material
and its intended use for various applications which is actually decided by various
parameters characterizing the material. The ideal deposition process of thin film
should meet following functional criteria:

capability of deposition of any material, metal, alloy, simple or complex

chemical compounds,
ability to form crystalline or amorphous deposits,
retention of the stoichiometry in compounds,
good growing power,
proper adhesion to different substrates,
low residual stress and concentration of defects (line, point, area or volume)
ability to deposit over a wide range of deposition parameters,
ability to control the structural parameters like residual stress, dislocation
density, and
ability to control deposition parameters such as deposition temperature,
deposition rate, thickness etc.
All the deposition methods have their inherent advantages and limitations.
Hence the choice of certain deposition technique for is to be made very carefully.
Vacuum evaporation is one of the oldest techniques for thin film deposition.
However, it is still widely used both in laboratory and in industry. This technique
possesses three basic stages-
Generation of vapor from the condensed phase, solid or liquid.

Transfer of the vapor from the source to the substrate in presence of low
pressures.

Condensation of the vapor molecules on the surface of the substrate.

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 Generally, 10-5 torr pressure is used for normal evaporation. When
evaporation is made in vacuum, the evaporation temperature is considerably lowered
and the incorporation of oxides and other impurities is reduced strongly. Among
vacuum evaporation techniques, the most of the above criteria can be met in the
method of thermal evaporation technique. The simplicity and versatility of vacuum
evaporation to obtain materials of desired qualities particularly for the fabrication of
devices on insulating substrates are some advantageous attributes of thermal
evaporation method. The thermal evaporation technique has been most extensively
used for the preparation of thin layers of photoconductors.

It is well known that the structural and optical parameters of the deposited thin
films are very much dependent on method of deposition. Thermal evaporation method
is the most common method in producing thin films because of its suitability,
reproducibility and high deposition rate. Various deposition parameters are easier to
maintain and control in case of thermal evaporation technique in comparison with
other techniques. This simplicity makes this technique more common and attractive
for thin film deposition.

In this work it was decided to study different properties of SnSe thin films and
their use in Schottky barrier devices. Many thin film preparation techniques have been
reported for the deposition of SnSe thin films by early researchers such as electro-
deposition [41], chemical bath deposition [42], laser ablation [43], hot wall deposition
[44] etc.. N. Kumar et al [45] and R. Indirajith et al [46] have reported thermal
evaporation technique for the deposition of SnSe thin films. Hence, in present
investigations, efforts have been made to deposit thin films of SnSe using thermal
evaporation technique.

2.4 Processes of Formation of Thin Film

The important processes involved in the formation of thin film are

condensation, nucleation and growth on the substrate. Transformation of a substance
from its vapour phase to the liquid or solid phase is called condensation, which in this
case is initiated by the formation of small clusters or nuclei through combination of
several incident atoms adsorbed on the substrate to form finally a coherent film is
termed as growth.

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2.4.1 Condensation

The partial vapour pressure in the gaseous phase should be equal to or greater
than its vapour pressure in the condensed phase at the same temperature for
condensation to occur on a substrate. If the substrate material is different from the
vapour material, the impinging vapour atoms are first adsorbed on the surface of the
substrate and condensation is initiated by the formation of small clusters of the
adsorbed atoms. These small clusters then act as the initial centers of condensation.

In this process the impinging vapour atoms on approaching the substrate

surface within a few atomic diameters come under the influence of the field of force
of the surface atoms of the substrate and may follow several interactions like:

an impinging atom may be reflected almost instantly retaining most of its

kinetic energy.

there may be physical adsorption of vapour atoms under influence of Van der
Waals force of the substrate atoms.

there may be chemical adsorption due to force of the type forming chemical
bond between a vapour atom and a substrate atom.

impinging atom may form immediate association with other atom or atoms
already adsorbed after finite stay time, or it may strike to the surface of the
substrate and then migrate literally to join a cluster of adsorbed atoms.

If the kinetic energy of an incident atom is less than the energy of desorption,
the thermal accommodation takes place by giving up its excess kinetic energy through
lattice vibration of the substrate and the atom is adsorbed. Under appropriate
conditions, when the rate of adsorption becomes greater than the rate of desorption,
the small clusters (consisting of monomers) begin to enlarge, leading to stable
nucleation and growth. Several workers [47-49] have studied condensation
phenomena experimentally.

2.4.2 Nucleation and Growth

In the process of depositing thin film on a substrate the first stage is the
formation of adsorbed monomers of one or more atoms which in the second phase,
under the action force similar to surface tension, or capillarity combine to form small
clusters. These clusters like the monomers are not stable and likely to be desorbed

33
unless they attain a certain critical size. On reaching a critical size, they continue to
grow forming stable condensates. Several theories are proposed to explain the
formation of critical clusters leading to the growth of stable condensates. Out of all
these, the two principal theories are the capillarity model and the atomistic model
[50].
Capillarity model [51] predicts that the free energy of a cluster passes through
a maximum as it increases in size, and this maximum of free energy corresponds to
the critical size of the cluster, which becomes stable above this critical size, but may
re-evaporate below this critical size. This is similar to the process of formation of
liquid droplets from vapours as explained by classical capillarity theory.

Figure 2.1 A Schematic diagram of growth process from vapour phase by different steps.
In the latter process, rate at which the critical nuclei grow is given by the
initial number of nuclei per unit area of the substrate and the rate at which the
adsorbed monomers diffuse to join them. Capillarity model of the theories of
nucleation enables one to evaluate free energy of formation of cluster of critical size
and shows as to how the critical size and nucleation rate depend on the substrate
temperature, impingement flux and the nature of the substrate. The atomistic or small
cluster model of the theories of nucleation [52] is most identical with the capillarity
model. The important prediction to be noted in this theory is that if the size of the

34
critical nucleus changes by even one atom with super saturation, a discontinuity will
occur in the nucleation rate versus temperature curve, and this may be verified
experimentally. Lewis [53], comparing the results of nucleation process derived from
capillarity and small cluster models, shows that the fundamental concepts underlying
the two models are identical. The essential difference between them is that the small
cluster model uses discrete arrangement of atoms where as the capillarity model uses
simple geometrical shapes of the clusters. Experimental tests as to the validity of the
nucleation theories have been made by several workers [54] by different techniques.
The best among them were the direct observations of the cluster formation and their
growth in the electron microscope [55, 56]. The prediction of the nucleation theories,
in general have been found to be true even through relatively crude experimentations.

However, the observations have revealed distinct four stages of film growth
leading to a continuous film as given bellow.

Nucleation and island formation

Coalescence of islands
Channel formation and
Formation of continuous film.

The existence of barriers for nucleation as predicted by nucleation theories

favours the formation of islands in the initial stage of film growth. When the
nucleation barrier is large, a few large islands are formed initially, which persist up to
relatively high average film thickness, resulting in the formation of a coarse grained
film. Under the small nucleation barrier, large number of islands is formed, which
becomes continuous at relatively low average film thickness and finer grained film is
obtained. As the deposition is continued, the islands grow in their sizes and come to
each other. The large islands appear to grow by coalescence of smaller islands and the
island density decreases monotonically. Surface diffusion is predominant for mass
transfer between the islands during coalescence. Shape and area of an island, which
has just been formed by coalescence, change during and after coalescence. According
to Pashley et al. [57] the driving force for the coalescence process is provided by the
change in the surface energy. As the islands continue to grow by coalescence, change
of shape still occurs particularly in the vicinity of the junction of islands and
consequently islands become elongated and flatten to increase surface coverage. They

35
join to form a network in which the deposited material is separated by long, irregular
and narrow channels. Occasionally, the channels are uniformly wide, homogeneously
distributed and possess approximately matching curvature over small area. The
channels are the uncovered area of substrate. The final stage of the growth is to fill
these empty channels by considerable deposition and as such this is a slow process. If
the uncovered surface area of the channels is large, secondary nuclei are formed in the
channels with the progress of deposition and they grow coalescence and fill in as
before and the film becomes continuous. The growth sequence discussed above was
first deduced by Andrade [58] and was found in remarkable agreement with electron
microscopic observations [59]. In the case of polycrystalline layers, the coalescing
pairs of islands have randomly distributed relative orientations.

2.5 Factors Affecting the Growth, Structure and Film

Properties
Various factors that affect the growth, structure and properties of a deposited
film are nature of the substrate, substrate temperature, source temperature, presence of
gas inside the chamber, annealing, contamination by impurities and presence of
defects on the substrate surface etc. [60]. The temperature of the substrate and
thickness of the film are two very important parameters affecting its properties. The
mobility of the just deposited ad atoms on the substrate surface can be enhanced by
increasing the temperature of the substrates during the deposition process. Higher
mobility of the ad atoms give the ad atoms more chance to grow together in ordered
manner leading to formation of thin films with large crystallites. Low mobility on the
other hand leads to the formation of a film of amorphous nature. If the substrate is the
face of a single crystal, periodic forces of cohesion induce an oriented growth called
the epitaxial growth. Thus, a thin film can be deposited in crystalline, polycrystalline
and amorphous form.

2.6 Requirements of the Thermal Evaporation Technique

The complete deposition process of thin films by thermal evaporation
technique can be divided into three major stages as mentioned bellow.

Transformation of solid material, to be deposited, into gaseous form.

36
 Transport of the created material, to the substrate, from the evaporation
source, in the form of vapor stream and

Deposition of the material on the substrate and growth of the film.

In reference to these steps, the requirement of the thermal evaporation

technique can be discussed. In the first stage, the transformation of the material takes
place from solid to gaseous state. For example, if this is to be accomplished by
resistive heating, then it is always essential that the material of the evaporation source
(i.e. boat) should withstand very high temperatures (which are always greater than the
melting/boiling point of the material to be evaporated). In addition, the power supply
used for such resistive heating should be capable of delivering enough current to the
boat so that it reaches these high temperatures conveniently.

In the second stage, the transport of the gaseous form of the material from the
evaporation source to the substrate takes place. This process can be better
accomplished only if the mean free path of the evaporated gas molecules is greater
than the distance between the evaporation source and the substrate. If this condition is
not fulfilled, then the vapor molecules will be diverted from their normal path due to
collisions with the ambient gas molecules or among themselves. Therefore, it is
always essential that the pressure in the chamber should be reduced substantially.
(The normal desired pressure is always less than 10-5 torr.)

In the third stage, the nucleation and condensation of the vapor molecules on
the substrates takes place to form a continuous film. This process can be optimized if
the rate of incidence of the vapor molecules at the substrate is kept less than the rate
of nucleation. Besides, it is always essential that the rate of impingement of the
ambient gas molecules should be very small compared to that of the evaporated
molecules in order to minimize the incorporation of impurities in the thin film.

2.7 Vacuum Coating Unit

The most important factor in thermal evaporation technique is the high

vacuum, which can minimize the interaction between the residual gases and the
sensitive surface of growing films. For preparation of thin films the vacuum pumps
capable of creating pressures around 10-6 torr are required to be connected to the
system. For this purpose, vacuum coating unit model: 12A4D (Make: Hind High

37
Vacuum Co. Ltd. Bangalore) was used. The schematic diagram and photograph of the
deposition system is shown in figure 2.2. The system comprises of conventional
diffusion pump backed by a direct drive rotary pump of pumping speed 300 lit/sec.
The diffusion pump is of diffstack type with liquid nitrogen trap, water cooled
chevron and has a pumping speed of 500 lit/sec. The ultimate vacuum achievable by
the system is ~ 10-7 torr, which is measured at various stages by Pirani and Bayard-
Alpert gauges. The main gadgetries in the work chamber consist of thermal
evaporation sources and flash evaporator assembly with high tension (HT) ion
cleaning facility. It also consists of rotary substrate holder for obtaining uniform
thickness over large substrate area. Operating roughing, backing and baffle valves and
pouring liquid nitrogen in the trap in a proper sequence is required for attaining
ultimate vacuum in minimum time. The vacuum chamber after loading the substrates
to be coated may be allowed to follow ion-cleaning process. For this, the required
level of vacuum is about 10-2 to 10-3 torr. It is desirable to heat the system up to
around 250C for about half an hour to remove the impurities adsorbed on to the walls
of the chamber and then flushed by an inert gas before going to high vacuum, for
which a high purity argon gas cylinder can be connected to the main chamber and the
flow can be controlled by a needle valve.

This is because of the fact that contamination free and chemically non-
interacting processes are necessary to be pursued particularly in case of
semiconductor devices, the vacuum system after achieving the ultimate vacuum is
normally isolated from the pumping system and then the thin film deposition process
may be initiated. The vacuum level can be monitored by Pirani gauge and ultimate
pressure is measured with the help of Bayard Alpert ionization gauge for better
accuracy.

38
 Figure 2.2 Schematic and Photographs of vacuum coating unit (Model: 12A4D).

The thickness of the deposited films can be measured using thin film
deposition controller (INFICONs SQC-310). The supply of power to the evaporation
source and the rate of deposition may be controlled automatically by the deposition
controller. Here as an evaporation source, rectangular tungsten/tantalum boats were
used because its melting point (3410 C / 3020 C) is very high compared to melting
point (861C) of the material, i.e. tin selenide, to be evaporated in present
investigations. Bringing an externally accessible shutter between the source and the
substrate may control thickness at any stage of deposition. The complete unit is fitted
with a number of various safety interlocks for electrical connections, water flow and
proper pressure levels.

2.8 Substrate Selection

Suitable supporting material (substrate) is required for the deposition of thin

films. The surface of the substrate plays a major role in the nucleation and growth
process of the film and thus influences the thin film properties considerably. Idealy
substrate should have the following requirements [61, 62].

The surface should be flat and smooth.

High mechanical strength
High resistivity
High thermal conductivity.

39
 To minimize thermal stress nearly same coefficient of thermal expansion with
that of the film and
Low cost.
Glass is most widely used as substrate material for deposition of
polycrystalline films. In the present study microscopic non conducting glass slides of
thickness 1.35 mm (Sunbeam Glass Works, Vyara-India) were used as substrate
material due to their fulfillment of most of the requirements as good substrates.

2.9 Substrate Cleaning

For proper adhesion of the films and for producing reproducible film
properties, the substrates should be highly cleaned and uncontaminated. Usually the
fine dust particles due to packaging, fingerprints and sticking of different impurity
atoms are the common contaminants. The removal of these contaminants by different
cleaning techniques depends upon the nature of the substrate and the type of
contaminants. The chemical reagents, such as acids, alcohol or alkalis with proper
concentrations remove the contaminants by breaking the bonds between the
contaminant molecules as well as between the contaminants and substrate. Acid
converts oxide layer, if any, and greases into water-soluble compounds. The
ultrasonic cleaning is another recommended process for removing gross contaminants
such as greasy particles and fingerprints. This procedure enhances the dissolution of
residues sticking on the substrate by the intense local stirring action by the shock
waves created in the solvent. Here the glass substrates were first cleaned by ultrasonic
vibrations followed by through washing with detergent and acetone. The drying of
cleaned wet substrates is also critical because of probable recontamination due to
adsorption of gaseous particles and dust. So, necessary precautions were taken in
drying the substrate in an atmosphere free from any air borne contaminants. For that,
the cleaned substrates were kept in a clean pettry dish and then pettry dish containing
substrates was put inside a cleaned closed stainless still oven for drying for an hour at
373 K.

2.10 Substrate Heating

The radiant heater fitted above the substrate holder assembly was used to raise
the temperature of the substrate during deposition to any desired value up to 500C

40
(called substrate temperature). The power to the radiation heater was supplied and
controlled from outside through an autotransformer. The temperature was measured
with the help of a copper-constantan thermocouple which was connected to digital-
temperature controller (Model: DTC-07 DP, ASABA). By this method the substrate
temperature could be raised up to 573 K.

2.11 Thickness Measurement

For in-situ measurement of thickness of the films, it is required to know the

rate of deposition of the material, which can be known by using crystal oscillator. The
thickness of the film can also be measured even after removing the film from the
vacuum coating unit by mainly two methods. In the first method, the mass of the
deposited material is measured, which, along with the known density of the material,
is used to estimate the thickness while in the second method, the multiple beam
interference pattern is used for exact estimation of the thickness.

The method of in-situ measurement of thickness allows both monitoring and

controlling the deposition rate and film thickness. This is one of the most appropriate
methods which have been used in most of the vacuum system. In present
investigations, the control and estimation of the thickness has been achieved by using
the thin film deposition controller (Model: INFICONs SQC-310 C) connected with a
quartz crystal sensor fitted in the vacuum system using a flexible feed through.

The use of quartz crystal oscillator to determine small quantities of deposited

material was first explored by Sauerbrey in 1957. This is based on the measurement
of changes in the resonant frequency of the quartz crystal oscillator with loading by
evaporated film when operated in a particular mode of vibration.

Thin film deposition controller INFICONs SQC-310 used in this investigation

is shown in figure 2.3. INFICONs SQC-310 series instruments are multi-channel
QCM based deposition controllers. They provide a unique combination of accuracy
and powerful features in a compact, low cost instrument.

The standard SQC-310 can control two evaporation sources using two quartz
crystal sensors simultaneously. Eight process control relays, and eight digital inputs

41
are included to support a broad range of external devices. The number of sensors,
outputs, and digital I/O can be doubled with an optional expansion card.

Figure 2.3 Photograph of SQC-310 deposition controller.

2.12 Preparation of SnSe Thin Films

First of all, the gadgets of the vacuum chamber were cleaned by acetone and
another cleaning process mentioned earlier. After cleaning, the rectangular tungsten/
tantalum boat is fixed between the filament holders from where the high current is
applied to the boat in order to evaporate the material. Then enough quantity of
analytical grade high purity reacted tin selenide (SnSe) powder (99.999%, Alfa Aesar)
is kept in this rectangular boat. High quality, microscopic glass slides are used as
substrates. Substrates were cleaned ultrasonically followed by washing with detergent
and acetone. The cleaned substrates were fixed in the vicinity of quartz crystal sensor
on the substrate holder (with heater) having nearly the same tooling factor for in situ
thickness measurement. Cleaned substrates have been covered by specially designed
masks in order to prepare the thin film sample for different characterizations, for
example whole glass slide was coated for optical characterization where as glass
slides coating with 1 1 cm2 area were used for electrical measurements and for the
fabrication of diode. In addition to this, pure NaCl crystals as substrates have also
been placed close to these glass substrates in order to prepare thin film samples for
electron microscopic studies.

42
 Then the rough vacuum, around 10-3 torr, in the chamber was achieved with the
help of a rotary pump. During this process, only the roughing valve was opened. Once
this was accomplished, the diffusion pump was switched on. The roughing valve was
closed and the backing valve was opened. After sometime (40 - 45 minutes) the baffle
valve was opened. Before deposition, to have a better adhesion, substrates were heated
at 150C for one hour by radiant heater as discussed earlier. When 10-6 torr pressure was
attained in vacuum chamber, the heater connected to the evaporation source was
switched on which in turn slowly heated the source of SnSe to temperatures greater than
the melting point. This allowed the vaporization of SnSe material. The quartz crystal
thickness monitor was switched on before starting the heating process. The thickness of
the deposited films and the rate of evaporation were noted from thickness monitor.

After the whole process was over, the baffle valve was closed and the
diffusion pump was also switched off. When diffusion oil (heater) cooled down to
nearly room temperature, the backing valve was closed. The rotary pump was
switched off and immediately the air inlet valve connected to the rotary pump was
opened to restrict the rotary oil from entering into the system. The chamber was
opened and the deposited films on the glass substrates were taken out with great care
so that they do not get damaged.

Thus, thin films of SnSe at room temperature with 8, 10, 12 and 15 k

thicknesses and thin films of thickness 10 k at different substrate temperatures (308,
338, 368, and 398 K) were deposited on glass substrates using thermal evaporation
technique as mentioned above. Similarly thin films of different stoichiometry i.e.
Sn0.2Se0.8, Sn0.3Se0.7 and Sn0.8Se0.2 were also deposited. These all the films were
studied for their chemical composition and structural, optical as well as electrical
properties which are discussed in subsequent chapters.

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