Thermal evaporation method

In this method the source material to be deposited is 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.
The main disadvantages are:
1. According to this fact that, the energy of reached atoms to substrate have low energy. Layers
which formed by this method have generally low density.
2. The impossibility of coating for refractory material, due to the limitation of generated heat in
the boat.
3. The possibility of combining the material with the boat, during the coating.

The main advantages of this method include:

1. Very simple method.
2. The maximum use of this method, compared to other physical and chemical methods.
3. The low cost of this system compared to other coating systems.
4. Impurity concentration in the film will be minimum.
5. Materials sublime at lower temperature under vacuum.
6. Mean free path of the vapour atoms is considerably large at lower pressure and hence a sharp
pattern of the film is obtained.
7. Selection of the substrates is wide.
8. Another advantage of this method is that evaporation yields a large number of films of uniform
thickness.

General consideration:

Principle: Thermal evaporation technique is the most widely used technique for preparation of thin
film. The physical stages of film formation consists of several distinguishable steps as (1) sublimation of
the material to be deposited to the vapour phase, (2) transfer of vapours from the evaporant to the
substrate, (3) condensation of vapours upon arrival on the substrate and (4) their rearrangement or
modifications of their binding on the substrate surface.
The characteristics of the films are influenced by rate of evaporation, pressure during deposition,
thickness of the film, angle of evaporation, temperature of the substrate and residual atmosphere. All
these parameters can be controlled in the thermal evaporation technique. The factors, which influence
the nature and properties of evaporated films, are discussed below:

1 Effect of Residual Gases

Because of the collisions with ambient gas molecules, a fraction of the vapour, proportional to exp (-
d/s), is scattered and hence randomized in direction within a distance‘d’ during their transfer through
the gas. To ensure a straight line path for most of the evaporated atoms, a pressure of 10-4 Torr and
source to substrate distance of 10 to 15 cm are necessary.
Table 2.4.1 Data on the residual air at 298 K in a typical vacuum used for film deposition:

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2. Effect of Vapour Beam Intensity
The rate of evaporations and hence condensation can vary over wide limits depending upon the type of
material and source being used. There exists a critical vapour beam density below that no condensation
occurs and also a critical substrate temperature above that no film could be formed except at very high
beam intensities.

3. Effect of Substrate Surface

The quality of the surface is the most important property of a substrate; since it is here that the film
substrate interaction occurs. The nature of the condensed film depends on the structure of the
substrate, its temperature and cleanliness. Condensing atoms align according to the structure of the
underlying surface, forming amorphous or polycrystalline layers on amorphous substrate and a single
crystal substrate respectively. The adhesion of a film to the substrate is strongly dependent on the
cleanliness and microscopic topography of the substrate surface.
Presence of contaminants on the substrate surface may increase or decrease the adhesion depending
on whether absorption energy is increased or decreased.

4. Effect of Evaporation Rate

The rate of free evaporation of atoms from a clean surface of unit area in vacuum is given by Langmuir-
Dushman equation
Ne = 3.513 x 1022 Pe( 1 / MT )1/2 moles/c.m2
where P, is the equilibrium vapour pressure of evaporant under saturated vapour conditions at a
temperature T and M is the molecular weight of vapour.
The rate of deposition depend; not only on the evaporation rate but also on the source geometry, its
position relative to the substrate and condensation coefficient. An increase in the source temperature
increases the kinetic energy of the incident vapour atoms, the surface mobility and grain size.

5. Contamination from Vapour Source

Heating of materials can be carried out directly or indirectly. Vapour sources of various types,
geometries and size can be fabricated or commercially obtained. Choke of the element is mainly
determined by the evaporation temperature and the chemical reaction of the support material with
evaporant, which may contaminate the films. The evaporants used are silver or gold for electrical
contacts. Indium, Tin, Alloy of Indium and Tin, are the evaporants for the preparation of the films.

6. Purity of the Evaporating Materials

The deposited thin films will be contaminated if the evaporant itself is impure. Usually high purity
materials are used.

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7. Production of Vacuum
As vacuum is essential in thin film preparation, in order to increase the mean free path of the evaporant
atoms, to reduce surface as well as bulk contaminations and to protect the vapour source from
oxidation and corrosion.
A wide variety of vacuum components, materials and assembly techniques are used to obtain vacuum.
Various levels of vacuum are given below according to their pressure ranges."
Low vacuum: 760 -25 Torr
Medium vacuum: 25 – 10-3 Torr
High vacuum: 10-3-10-6 Torr
Very high vacuum: 1 0-6 – 10-9 Torr
Ultra high vacuum: Below 10-9 Torr
Different types of pumps are used for obtaining different levels of vacuum. Similarly for the
measurement of vacuum, different gauges are used.

Film quality and vacuum system pressure are inseparably connected. Uniformity and purity are the main
elements in determining a film's quality. The purity of the material prior to deposition is the largest
factor in determining the films purity. The second biggest factor is most likely the gas composition and
pressure of the system in which the film was developed. A substantially low pressure is required to
prevent film oxidation and reduce the contaminant density. A pressure of 10-5 Torr is sufficient, but
lower pressures would help reduce the density of contaminants in the film. At 10-5 Torr the mean free
path of gas in the chamber is approximately 8 meters, which without the unit of measurement is often
referred to as the Knudsen number. The mean free path can be calculated using the following equation

l=
√

where, kB is the Boltzman constant, T is the temperature in Kelvin, d is the diameter of the molecule in
meters, and P is the pressure in Pascals. As the mean free path of the gas particles increases, so does
the Knudsen number. When the Knudsen number is close to or greater than one, gas particles obey
principles of free molecular flow more than viscous flow. The Langmuire-Knudsen equation is founded
on the assumption that the molecules follow a molecular flow regime. The Langmuire-Knudsen equation
is
R m = Cm 𝑐𝑜𝑠𝜃𝑠𝑖𝑛𝜑 (𝑃 (𝑇) − 𝑃)

where Rm is the rate per unit area of the source, Cm = 1.85 x 10-2 mol.K /s.Torr
a constant, M is the gram-molecular mass of the deposition material, T is the
temperature of the deposition material, ϴ is the angle between the normal of
the source and the substrate, Ф is the angle normal to the surface of the
substrate and crucible, r is the distance between the crucible and substrate,
and P and Pe are the system pressure and evaporant partial pressure in Torr
respectively.

Figure: Langmuire-Knudsen angle dependence.

Another assumption of the Langmuire-Knudsen equation is that the evaporant molecules will travel
from the crucible where they are heated to the substrate without “picking" up any other gas particles in
the chamber. Subsequently, a decrease in the base pressure of the vacuum will also reduce the number
of particles “picked" up as they flow towards the substrate to be deposited.

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The Langmuire-Knudsen equation necessitates the use of other methods and equations to calculate an
accurate deposition rate. Among these is Stefan-Boltzman equation for blackbody radiation:

P = IV = 𝝈𝝐AT4
where P is the electrical power through the crucible, I is the current, V is the voltage, 𝜎 is the Stefan-
Boltzman constant, 𝜖 is the emissivity, A is the surface area of the black body, and T is the temperature.
Solving for T we find

T=
𝝈𝝐𝐀

Understanding the fundamentals of vacuum theory can prevent many of the complications that diminish
the accuracy and precision of collected data.
Recognizing the sources of leaks in a vacuum system is one item that is of particular interest for
experimental lists. A variety of sources lead to unwanted gas added to the chamber by leaks. Vacuum
leaks are often due to the pressure gradient that exists within a vacuum, which creates a surplus of
interesting and inimical problems. Thus vacuum leaks should be addressed prior to experimentation. At
a standard temperature and pressure, almost everything absorbs water vapor and other gases. One
factor that affects how much water vapor is absorbed by a material is the humidity. Inside a vacuum,
these materials release the gases they absorbed because the same forces that helped trap gasses in
them have diminished.
All materials will experience some outgassing within a vacuum chamber. A judicious selection of
materials will reduce the effects of outgassing, or leaking of gas, from materials that are used. For this
reason, conditioning of the vacuum chamber and, if possible, all the materials used in the chamber is
also an important step of experimentation. Chemical cleaning or pre-exposure to vacuum pressures are
both ways to condition materials for use in vacuum.
For understanding the influence of ambient gas on the properties of films, the impingement rate of gas
atoms or molecules is needed which is given by the kinetic theory of gases under equilibrium conditions
as:
𝜌
𝑁 = 3.513 × 10 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠/(𝑐𝑚 )(𝑠𝑒𝑐)
𝑀 𝑇

Boat
Boats or vapour sources of various types , geometries
and sizes can be easily constructed or obtained
commercially and are used in a various forms such as
filament, boat and a basket, depending on the type of
material, shape and its evaporation volume.
Their material is often made from refractory metals
such as tungsten, molybdenum, and tantalum, and
Nb. If there is the possibility of reacting with them,
dielectric boats are use such as crucible of quartz,
graphite, alumina, beryllia and zirconia.

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 Construction: Vacuum Coating Unit
The type of vacuum equipment needed
depends on the desired purity of the film.
Basically the vacuum system consists of 0.4 m
diffusion pump in conjunction with an oil
sealed rotary pump. The ultimate pressure
achieved in a 0.3 m diameter stainless steel
bell jar is of the order of 6 x 10-6Torr. It has
set-ups for electron beam evaporation and
flash evaporation. Substrates can be cleaned
by ion bombardment. A low tension
transformer of 10 V-100 A is used for filament
heating. Most of the evaporations are carried
out at pressures of (1 -8) x 10-4 Torr. The
pressure obtained by the rotary pump is
measured by means of a Pirani gauge and the
diffusion vacuum is measured by a Penning
gauge.
The Pirani gauge (A6STM) has two gauge
heads, which facilitate the measurements of
the fore vacuum and roughing vacuum.
Change of pressure in the vacuum system brings about a rise or fall in the number of gas molecules
present and hence a rise or fall in the thermal conductivity of the gas.

Working: Thermal evaporation method is used for the preparation of thin films. The films are deposited
onto clean substrates. In thermal evaporation, the material is heated to vapour form by means of
resistive heating. On heating the materials in vacuum, sublimation takes place and the atoms are
transported and get deposited onto the cleaned substrates held at suitable distance at desired
temperatures. The material for deposition is supported onto a vapour source, which is heated to
produce desired vapour pressure. The requirements for the vapour source are that it should have a low
vapour pressure at the deposition temperature and should not react with the evaporant. Tungsten

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helical baskets and tantalum boats are used as the vapour sources. The evaporant materials in the
powder form are kept in the tantalum boat.
The low tension (LT) supply for evaporation source is obtained from a 230V input transformer by means
of parallel connections in the secondary side of the transformer. The LT output from the transformer is
fed through a current meter and a selector switch to LT feed-through and filament holders. The unit is
connected to the 10 V-100 A ratings of the transformer. After that, the vacuum reaches to desired value,
(about 10-5 - 10-6 Torr), required heat can be adjusted by controlling the electric current. The evaporant
is deposited onto a substrate to form a film.

Thermal evaporation may be achieved directly or indirectly by variety of physical methods:

1. Resistive heating:

This method consists of heating the material with a

resistivity heated filaments or boat, generally made
of refractory metals such as W, Mo, Ta and Nb with
or without ceramic coatings. Crucible of quartz,
graphite, aluminia, beryllia and zirconia are used
with indirect heating. The choice of support
material is primarily determined by the evaporation
temperature and resistance to alloying and /or
chemical reactions with the evaporant.

Resistance evaporation method is used usually, for

materials with a melting point less than 1500 °C.
Between dielectric SiO, MgF2 and ZnS and between the metals, iron, nickel, aluminum, copper, tin,
silver, gold and platinum, are evaporated usually with this way easily.

The process include heating a source material under vacuum until it evaporates or sublimates.
Evaporation should be done inside the vacuum chamber. After that, the vacuum reaches to desired
value, (about 10-5 - 10-6 Torr), required heat can be adjusted by controlling the electric current.

2. Flash evapoartion

Flash evaporation is one of the prominent techniques for

the deposition of thin films of multicomponent alloys
whose constituents have different vapor pressures. This
technique requires only one boat maintained at sufficiently
high temperature to evaporate the least volatile
component of the alloy. The main advantage of FE is that it
does not require maintaining the critical vapor pressures of
the components and temperatures of the boats unlike
multisource thermal evaporation. Dispensing the powder
onto the boat is a crucial part of the FE technique.

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 A rapid evaporation of a multicomponent alloy or compound, which tends to distill fractionally, may
be obtained by continuously dropping fine particles of the material onto hot surfaces so that
numerous discrete evaporation occurs. Alternatively, a mixture of the components in powder form
may be fed into the evaporator. Fine powder (~100 to 200 mesh) is fed into heated Ta or Ir boat by
mechanically or ultrasonically agitating the feed chute. This system has been used for preparing
films of cerments, Bi2Te3, III-IV compounds etc.

There is evidence that flash evaporation films in some cases can show considerable deviation from
the original compositions. Further since the large amount of rapidly released gas produces
spattering of particles from the evaporant, this method is not easily controllable.

3. RF heating: The RF or Induction heating may be supplied to the evaporant directly or indirectly
from the crucible material. By suitable arrangement of the rf coils, the induction-heated material
can be levitated, thereby eliminating the possibility of contamination of the film by supporting
material. The crucible used should be thick enough to screen the melt from excessive coupling of rf
field, thus minimizing the turbulence.

4. Beam evaporation:

The simple resistive heating of an evaporation

source suffers from the disadvantages of possible
contamination from support material and the
limitations of the input power, which make it
difficult to evaporate high melting point materials.
These drawbacks may be overcome by an efficient
source of heating by electron bombardment of
material.

In this method thus, for energy transfer, used a

high-energy electron beam instead of electrical
current, which will focus on the surface of
substance and is located within the boat and
creates heat. This technique causes to temperature range rise very high for evaporate the material and
thus, the evaporation of refractory materials, becomes possible.

Free electrons in a vacuum can be manipulated by electric and magnetic fields to form a fine beam.
Where the beam collides with solid-state matter, electrons are converted into heat or kinetic energy.
This concentration of energy in a small volume of matter can be precisely controlled electronically,
which brings many advantages. The rapid increase of temperature at the location of impact can quickly
melt a target material.
Electron-beam evaporation uses thermionic emission to create a stream of electrons that are
accelerated by a high-voltage cathode and anode arrangement. Electrostatic and magnetic fields focus
and direct the electrons to strike a target. The kinetic energy is transformed into thermal energy at or
near the surface of the material. The resulting heating causes the material to melt and then evaporate.

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Temperatures in excess of 3500 degrees Celsius can be reached. The vapor from the source condenses
onto a substrate, creating a thin film of high-purity material. Film thicknesses from a single atomic layer
to many micrometers can be achieved.

In electron gun, electrons are accelerated toward the boat after that filament is being heated due to
passing free flow by the electrical and Lorentz magnetic fields. The applied force on emitted electrons
given by the following equation:

F=-e. (E + V X B)

That is, V: electron velocity vector, E: electric field intensity, B: magnetic field intensity, And F: the
applied force on electron

In general, the sources evaporation (or sublimation)

process, by electron gun system, can be divided in three
stages:

1. The current passing through the filament (the

cathode), heating it and therefore, the electrons
emission occurs from it toward the anode (used
Transistor for this part is usually 12 volts AC).

2. Giving acceleration to electrons with use of high

voltage power supply. The used power supply is often
between 15-5 kW and maximum required current is
usually 1 amp. Due to the high voltage of power supply in these systems, suitable insulations are
used to prevent system connection to the wall, among which can be pointed out, alumina, zirconia,
silicon nitride, carbide silicon and beryllium oxide.

3. Direction control and focus the electrons on the source.The electron beam after accelerating travels
one 270 degrees direction and then, collide to copper boat. This track is 270 degrees, in order not to
interference vapored particles of inside the vacuum chamber with emitted electron beam of filament.

Electron beam used in this system is produced, in three ways:

1. Thermoionic: The process by which free electrons are emitted from the surface of a metal when
external heat energy is applied is called thermionic emission.
2. The field emission: Field electron emission is emission of electrons induced by an electrostatic field.
3. The combination of thermionic and field emission

However, the most common used method in these systems is thermionic method, in which, for electron
emission use from generated heat by the flow of current through a wire filament. Often tungsten is used
to manufacture of filament and thorium oxide, is used on it to increase its emission.