THIN FILM DEPOSITION TECHNIQUES

Thin solid films may be prepared on metallic or non-metallic supports by

several different techniques. Structures could be designed to interact and be
built at the micron level using different thin film fabrication technology which
comes under three major headings:

1. Physical Method

2.Chemicals Methods

3.Sputtering

The choice of a particular coating technique depends upon several factors,

viz. the substance ,thickness and distribution required.

Each of the above mentioned methods can be used to prepare thin films
from a variety of materials like metals, semiconductors, insulators or
dielectrics and each of them has its own advantages and disadvantages .
From here, onwards we restrict our discussion to only thermal evaporation
method which we have employed to prepare thin films for the present study.

THERMAL EVAPORATION
Among the most widely acceptable techniques for thin film deposition,
thermal evaporation method is a versatile and flexible one for producing
deposits of organic semiconductors. Basically it involves three steps, boiling
or subliming of source to form its vapour, transport of the vapour from the
source to the substrate and condensation of the vapour on the substrate.
The basic physics of the process contains elements of thermodynamics,
kinetic theory of gases and condensation phenomena.

Solid materials are sublimed under high vacuum when heated to sufficiently
high temperature. The condensation of the vapour on to a cooler substrate
yields thin solid films. This method has the following advantages.

1. Impurity concentration in the film is minimum.

2. Material boils at lower temperature under vacuum.

3. Growth can be effectively controlled.

4. Mean free path of the vapour atom is considerably larger at low pressure
and hence a sharp pattern of the film is obtained.

5. Wide variety of substrates.

MEAN FREE PATH OF VAPOUR MOLECULES

As the gas pressure is lowered the average distance traversed by a vapour

molecule before colliding with a gas molecule increases, i.e. the mean free
path of the vapour molecule in the residual gas increases.

The mean free path of the molecules in air is about 45cm at 25o C and at 0.1
micron Hg pressure, and the mean free path of water vapour , the principle
component of the residue gases in a kinetic pumping system ,at the same
pressure and temperature is 34cm. The mean free path of vapour molecules
of metals ,halides and sulphides, etc., in gases at low pressures are generally
unknown , but they are not likely to differ greatly from the mean free path of
gas molecules .
It is shown in standard works on the kinetic theory of gases that the fraction
N of the emitted molecules which traverse a distance l without experiencing
collisions with gas molecules is given by the relation

N=N0exp-(l/L)

Where N0 is the initial number of emitted atoms and L their mean free path in
the residual gas. The ratio N/N0 has been plotted in figure as a function of the
mean free path L, assumed equal to 50cm at 0.1-micron Hg gas pressure,
and for different evaporation distance l.

Usually evaporated films are deposited at gas pressures of the order 0.1-
micron Hg or less, thus only a limited number of collisions between gas and
vapour molecules will occur, as indicated in the figure and this results in the
vapour molecules being propagated rectilinearly.

EFFECT OF GAS MOLECULES STRIKING THE COLLECTOR SURFACE

An evaporated deposit may be badly contaminated by the residual gases in

the coating chamber although the evaporation distance and gas pressure are
sufficiently low that collisions between molecules in transit can be neglected.
Such contamination can arise from the gas molecules impinging on the
substrate during deposition, and this source of contamination has often been
ignored in the numerous investigations of vacuum evaporated coatings.

The evaporation rate and hence the condensation have wide limits,
depending upon the purity of source material used. Characteristics of the
prepared films are determined by parameters such as temperature, type of
substrate, deposition rate and residual atmosphere. All these parameters can
be controlled in the thermal evaporation method. More than that, single
evaporation can give films of different thicknesses. We have used here
molybdenum boats and tungsten baskets for evaporation of materials. Film
of high purity can readily be produced with a minimum of interfering
conditions. The nature and properties of evaporated thin films depend on
factors as shown below

1. Nature and Pressure of residual gases.

2. Vapour beam intensity.

3. Nature and conditions of substrate.

4. Temperature of vapour source and velocity of impinging molecule.

5. Material contamination from vapour source.

VACUUM COATING UNIT

The type of vacuum equipment needed obviously depends on the desired
purity of the film. Detailed reviews on various types of vacuum systems and
their ultimate pressures are given by Holland, Carewell Dushaman and Roth.
The vacuum system employed to deposit and characterize thin film in the
present work contains an assortment of pumps, tubes, valves and gauges to
establish and measure the required reduced pressure as shown 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
810-6mbar. It has setups 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 (6 and 7 in Figure) provided with the system. The Pirani
gauge model Hind Hivac-A 6 STM is used to measure vacuum in the range
0.510-3Torr. The Penning gauge model STM 4 is used to measure vacuum in
the range 10-2 to 10-6Torr in two ranges with instant range charger provided
by a toggle switch.
The system is accompanied by a digital thickness monitor model number
DTM-101 having a temperature controller cum monitor to show the interior
dome temperature (300C) at the time of coating and a display setting to
show the rate of coating. A schematic diagram showing
vacuum
chamber with
thickness
monitor is
given in figure.
ROTATRY PUMP

Rotary vane pump is a vacuum pump. Its a positive displacement pump.

Vacuum refers to a state where the pressure is lower than that of its
surrounding atmosphere. Vacuum pump can be described as a device that
removes gas molecules from an enclosure and create a certain partial
pressure. It was invented by Otto von Guericke in 1650. Rotary vane oil
pump can easily create 0.1 Pa (10-3mbar) pressure. From atmosphere to this
particular vacuum range called coarse or rough vacuum.

BASIC MECHANISM OF THE PUMP

1.There is sliding spring-loaded vane in the stator.

2.The vane remains in contact with an eccentric cam that may be called a
rotary piston.

3.The distances between the cam and the stator walls are kept at a practical
minimum.

4.The pumps used by us are having 2or3 sliding vanes placed in the rotor.

5.The oil is being used to affect the seal between inlet and discharge areas,
to lubricate, to fill the area under discharge valve, to serve as a heat transfer
medium etc.

6.In the modern pumps an arrangement is made to interrupt the oil flow
automatically when the motor stops.

7.This prevents filling the pumping mechanism with oil and also prevents air
leakage into the pump and subsequently into the vacuum system.

8.The major limitations with this rotary vane pump are back streaming of the
oil vapors into the vacuum chamber and the destruction of the oil by
corrosive gases.

9.To improve upon the performance with the corrosive gases and the oxygen,
the oil that isused are perfluoroethers and polycholorofluoroethylenes.
OIL DIFFUSION PUMP

An oil diffusion pump is used to achieve higher vacuum (lower pressure) than
is possible by use of positive displacement pumps alone. Although its use
has been mainly associated within the high-vacuum range (down to
109 mbar), diffusion pumps today can produce pressures approaching
1010 mbar when properly used with modern fluids and accessories. The
features that make the diffusion pump attractive for high and ultra-high
vacuum use are its high pumping speed for all gases and low cost per unit
pumping speed when compared with other types of pump used in the same
vacuum range. Diffusion pumps cannot discharge directly into the
atmosphere, so a mechanical fore pump is typically used to maintain an
outlet pressure around 0.1 mbar.

The oil diffusion pump is operated with an oil of low vapor pressure. The
high-speed jet is generated by boiling the fluid and directing the vapor
through a jet assembly. Note that the oil is gaseous when entering the
nozzles. Within the nozzles, the flow changes from laminar,
to supersonic and molecular. Often, several jets are used in series to
enhance the pumping action. The outside of the diffusion pump is cooled
using either air flow or a water line. As the vapor jet hits the outer cooled
shell of the diffusion pump, the working fluid condenses and is recovered and
directed back to the boiler. The pumped gases continue flowing to the base
of the pump at increased pressure, flowing out through the diffusion pump
outlet, where they are compressed to ambient pressure by the secondary
mechanical fore pump and exhausted.

Unlike turbomolecular pumps and cryopumps, diffusion pumps

have no moving parts and as a result are quite durable and
reliable. They can function over pressure ranges of 1010 to
102 mbar. They are driven only by convection and thus
have a very low energy efficiency.

One major disadvantage of diffusion pumps is

the tendency to backstream oil into the vacuum
chamber. This oil can contaminate surfaces inside the
chamber or upon contact with hot filaments or
electrical discharges may result in carbonaceous
or siliceous deposits. Due to back streaming, oil
diffusion pumps are not suitable for use with highly sensitive
analytical equipment or other applications which require an
extremely clean vacuum environment, but mercury diffusion
pumps may be in the case of ultra-high vacuum chambers used for metal
deposition. Often cold traps and baffles are used to minimize back streaming,
although this results in some loss of pumping ability.

The oil of a diffusion pump cannot be exposed to the atmosphere when hot.
If this occurs, the oil will burn and has to be replaced.

PIRANI GAUGE

The Pirani gauge is a robust thermal conductivity gauge used for the
measurement of the pressures in vacuum systems.

Working principle A heated metal wire (also called a filament) suspended in

a gas will lose heat to the gas as its molecules collide with the wire and
remove heat. If the gas pressure is

reduced the number of molecules present will fall proportionately and the
wire will lose heat more slowly. Measuring the heat loss is an indirect
indication of pressure.

The electrical resistance of a wire varies with its temperature, so the

resistance indicates the temperature of wire. In many systems, the wire is
maintained at a constant resistance R by controlling the current I through the
wire. The resistance can be set using a bridge circuit. The power delivered to
the wire is I2R, and the same power is transferred to the gas. The current
required to achieve this balance is therefore a measure of the vacuum.

The gauge may be used for pressures between 0.5 Torr to 104 Torr. The
thermal conductivity and heat capacity of the gas may affect the readout
from the meter, and therefore the apparatus may need calibrating before
accurate readings are obtainable. For lower pressure measurement, the
thermal conductivity of the gas becomes increasingly smaller and more
difficult to measure accurately, and other instruments such as a Penning
gauge are used instead.

PENNING GUAGE

The Penning Ionization Gauge, also known as cold cathode gauge is used to
measure vacuum. High voltage between the anode and the cathode causes
gas discharge and the resulting ionic current is measured with an ammeter.
The measured amperes are then converted into pressure units such as
Pascals or Torrs.

SUBSTRATE CLEANING
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. Then it is kept in dilute nitric acid for some time. After this, the
substrates are cleaned using distilled water. Then the substrates are agitated
in acetone. Finally, the substrates are dried in hot air.

THIN FILM PREPARATION

Thin films are evaporated on to clean glass substrates 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 substrates held at suitable
distance at desired temperatures. The material for deposition is supported on
a source which is heated
to produce desired vapour pressure. The requirements 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 material. The semiconductor
is evaporated using Molybdenum boat and Tungsten baskets as the source
for coating electrodes. The unit is operated at 10V/100A ratings of the step-
down transformer.

SUBSTRATE HEATING
Substrate heating can be done within the setup of the coating unit by
connecting Substrate Heating (SH) controller to the substrate holder in
evacuated chamber. The internal settings like placing of copper constantan
thermocouple over the substrate to control the suitable substrate
temperature. The voltage variation in SH controller, is needed to create
suitable temperature. For example, in order to create 100C in the substrate
holder, we have to suitably adjust the SH controller voltage to 40V A.C. with
which it shows a maximum variation of 50C. At that time, there is a change
in the primary current to 2.5A and secondary current to 55A without
changing the base pressure (110-5mbar).

CHARACTERIZATION TECHNIQUES
Micro and nano structures, crystallinity, impurity content, chemical
composition, surface morphology, application of light and electromagnetic
field etc. influence various properties of thin films. The characterization of
thin film micro structure is necessary for improving of the performance
quality of various devices. The above mentioned favorable factors strongly
depend on thin film thickness, substrate heating, post deposition air and
vacuum annealing, high energy electromagnetic beam irradiation, choice of
substrates and conditions of thin film preparations. Some of the important
film properties and characterization techniques are as follows

-Conductivity Measurements

YHAN BHI KUCH ADD KARDIO MILE TOH

-XRD
The diffraction of X-rays by micro crystals in powder and film results from a
scattering process mainly due to electrons of corresponding atoms without
change in wavelength (). The intensities of diffracted beams are determined
by the positions of the atoms within the unit cell. So, by measuring the
intensities of the diffracted beams, idea about the atomic positions can be
obtained. The velocity of propagation of X-rays in vacuum is found to be
same as that of electromagnetic radiations and they exhibit dual nature. In
the phenomena of refraction, interference, diffraction and polarization, X-
radiation acts as waves, giving thereby to a real significance. But in the
phenomena of photoelectric effect, Compton effect, the appearance of sharp
spectral lines and a definite short wavelength limit of continuous spectrum,
the energy of X-radiation appears to propagate in quanta defined by the
values of h. When a monochromatic beam of X-radiations having a
wavelength () falls upon the atoms in the Bragg plane, a wavelet of
scattered radiations spreads out from each atom in all directions.

Since X-rays are much more penetrating than ordinary light, it is essential to
consider the reflection at several such layers. At each layer, there is a partial
reflection and the X-ray beam will be completely absorbed after penetrating
a large number of layers. Now these reflected wavelets will reinforce
themselves only when they meet in the same face, the condition for which is
that the path difference between two such rays must be an integral multiple
of wavelength. Thus, the condition for diffraction is

n2d sin

Where d is the distance between adjacent planes in the crystal and is the
glancing angle, n is the order of reflection and is the wavelength of the
incident X-radiation. This characterization is used as a very important tool for
the identification of phases and crystallographic plane of grain growth. From
the XRD data, we attempt to calculate the mean crystalline size, dislocation
density and structural strain from the value and full width at half maximum
(FWHM) of the diffraction peak.

SAFETY DEVICES
The writer is of the opinion that the least possible number of safety devices
should be fitted to any processing plant to protect it against mal-operation.
Otherwise the very purpose of such devices may be defeated because a
comparatively simple apparatus is made into a complicated piece of
machinery requiring frequent maintenance. High vacuum pumps, valves, and
gauges have steadily undergone development until now they are reliable
engineering equipment, and at most only two or three safety devices are
essential on any vacuum plant.

High Tension Hazard: It is necessary to safeguard an operator against

possible electrical shocks from the high-tension source used for glow
discharge cleaning. This can be achieved by connecting in the primary of the
high-tension transformer a pressure controlled switch, e.g. a limit switch
actuated by a metal bellows which expands or contracts accordance with the
coating chamber pressure. Alternatively, a mechanically operated switch
may be made to disconnect the power to the high-tension transformer when
the vacuum chamber is opened to atmosphere.

Cooling Water Failure: Occasionally the water supply to a diffusion pump

may fail, and apart from the pump being damaged by overheating there is a
danger of oil vapour entering the

coating chamber from the uncooled pump. A simple method of preventing

the diffusion pump
from overheating is to mount on the water-cooled pump body a thermo-
statically controlled switch, the contacts of which will open on temperature
rise and either directly or via a relay disconnect the power to the heating
elements.

Rotary Pump Oil Return Valve: The oil in a rotary mechanical pump may
enter the backing pipe-line if the pump is switched off with the system under
vacuum. Many methods have been evolved to prevent such an occurrence.
In the system, an electro-magnetically controlled isolation valve mounted
directly above the pump inlet closes the pump orifice when the pump motor
is switched off. When the mechanical pump oil is in a separate container the
oil may be prevented from flowing into the pump when it is idle and under
vacuum by fitting a magnetically controlled valve in the main oil feed line. In
another system, a chamber of sufficient capacity to act as a reservoir for the
returned oil is fitted in the backing line above the pump inlet.