CHAPTER-2

THIN FILM DEPOSITION METHODS

2.1 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 [73].

Thin films are formed by depositing material on a clean suitable substrate to

grown up film thickness instead of thinning down the bulk material [74]. The
mechanical strength of thin films is better than (annealed as well as bulk samples.

2.2 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 [75].
Chemical deposition technique includes the following methods:
i) 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 [76]. The chemical reaction between the

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 substrate and the precursor is continued at high temperature till the desired
thickness of the film is obtained [77-78].
ii) 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 [79-81]. 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
iii) 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 [82]. 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 [83-
84]. 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.
iv) Sol-Gel Method: Sol-Gel is a chemical solution deposition method in
which precursor solutions are highly controlled for the deposition of the
films [85]. 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 [86].

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

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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:

i) 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 [87-88]. 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.
ii) 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 [89]. 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
[90-93].
iii) 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 [94-96]. This results in vaporization of the target material.
The atoms ablated from the target material get deposited on the substrate.
Figure 2.1 shows pulsed laser deposition technique.

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 Figure 2.1: Pulsed Laser Deposition Technique
iv) 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 [97-
99].
v) Thermal Evaporation 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 [100-103].
vi) Electrohydrodynamic Deposition: Electrohydrodynamic deposition is also
known as electrospraying deposition method [104]. 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
[105-107]. Electrospray system for thin layer deposition from a suspension
is shown in figure 2.2.

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 Figure 2.2: Electrospray System for Thin Layer Deposition from a Suspension
An important characteristic of the above deposition techniques to deposit the
BIT films are to overcome the problem of minimizing the processing temperature and
time and to improve the ferroelectric properties like remanent polarization, coercive
field etc.

The requirement for the formation of a proper Bi-layered crystalline phase is

that it has minimum defects, without inclusion of any secondary phases and with
optimum orientation of the crystallites.

Sol-Gel process has more advantages than other methods for film deposition as
discussed above. These advantages are:
(i) Low temperature is required in sol-gel method.
(ii) Sol-Gel technique is an economical method.
(iii) Coating of large surface using sol gel method is very easy.
(iv) Capable of making small thickness films.
(v) It provides high optical and quality films.
(vi) Sol gel method can produce thick coating to provide the corrosion
protection performance.
(vii) Sol-Gel can easily shape material into the complex geometries in the gel
state.

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 (viii) Sol-Gel method has the ability to precisely control the microstructure of the
deposited film like surface area, volume & size of the pores.

Limitations of sol-gel technique are:

(i) Weak Bonding
(ii) Low wear resistance
(iii) High permeability
(iv) Difficult controlling of porosity
(v) More thin film may cause cracks

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2.3 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 [108]. These oxides of Si and
Ti are called precursors. A precursor is a compound that participates in chemical reaction
to produce another compound [109]. 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 [110]. A gel is
said to be colloidal if the solid network is prepared using colloidal sol particles [111].
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 [112-113].

The sol-gel method consists of four steps that are as follows:

a) The desired colloidal particles once dispersed in a liquid to form a sol.
b) The deposition of sol solution produces the coatings on the substrates by
spraying or dipping or spinning. The particles in the sol are polymerized
through the removal of establishing components and produce a gel in a state
of a continuous network.
c) The final heat treatments pyrolyzed the remaining organic or in organic
components and form an amorphous which can be change into crystalline

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 by the use of annealing method [114].
Thin films from sol can be deposited by following methods:
(i) Dip coating
(ii) Spin Coating
(iii) 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.

2.4 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
[115-116]. The dip coating technique is shown in figure 2.3.
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.

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 Figure 2.3: Dip Coating Technique

2.5 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 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 [117].

The spin coating process involves the four stages as shown in figure 2.4. These
stages include deposition, spin up, spin off and evaporation.

In deposition process, excessive amount of fluid is deposited on slowly

spinning substrate. Using a nozzle the fluid is sprayed at the center of the substrate. An
excessive amount of fluid is deposited to avoid coating discontinuities because the fluid
may dry before it reaches the wafer edge [118-119].

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 In the spin up process, the substrate is accelerated to its final spin speed. In
liquid, rotational forces are exerted on the upward direction causing a wave front to be
formed. This wave front flows to the substrate edge by centrifugal force and hence
results in a uniform layer.

The spin off stage is the spin coating stage where the excess solvent is removed
off the substrate surface as it rotates at speeds between 2000 and 8000 rpm. The fluid is
being thinned primarily by centrifugal forces until enough solvent has been removed to
increase viscosity to a level where flow ceases.

In spin coating process, evaporation is the primary method of film thinning

once the fluid flow ceases. Evaporation is the complex process by which a portion of
the excess solvent is absorbed into the atmosphere. If evaporation occurs before the
time it may cause the formation of a solid skin on the fluid surface and results in
coating defects. A variety of film thickness can be deposited by spin coating, due to
film thickness being roughly inversely proportional to the square root of spin speed.

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Figure 2.4: Process of Spin Coating

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ADVANTAGES AND DISADVANTAGES OF SPIN COATING METHOD
Advantages:
1. Thickness of the film can easily be changed by changing the spin speed or
using different viscosity sol.
2. Films of highly uniform film thickness can be obtained.
3. An advantage of spin coating is that a film of liquid tends to become
uniform in thickness during spin off and once uniform, tends to remain so
provided that the viscosity is not shear dependant and does not vary over the
substrate.

Disadvantages:
1. Large substrates cannot be spun at a sufficiently high rate.
2. Another disadvantages is that if the sol viscosity is shear dependent, the
lower shear rate experienced near the center of the substrate causes the
viscosity to be higher there and the film to be thicker.

2.6 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 [120]. Spraying
technique apparatus involves spray nozzle, motor, liquid level monitors, hot plate, gas
regulator value and air tight fiber chamber [121-122] and is shown in figure 2.5.

a) Spray nozzle
It consists of tube filled with solution which is surrounded by the glass bulb. On
applying pressure to the carrier gas, the vacuum is created at the tip of the nozzle.
Hence, the solution is automatically sucked in the solution tube and the spray process
starts.

b) Motor for spray nozzle

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 To control the motion of the spray nozzle over hot plate, the stepper motor is
used.
c) Liquid level monitor
The spray rate at a fixed air pressure depends upon the height of the solution
measured with respect to the tip of the nozzle. The arrangement for the change in
height of the solution forms the liquid level monitor.

e) Gas regulator value

The gas regulator value is used to control the pressure of the carrier gas flowing
through the gas tube of the spray nozzle.

f) Air tight fiber chamber

The spraying system is fixed inside with air tight fiber chamber and is
connected to an exhaust fan to remove the toxic gases produced during the thermal
decomposition of spayed solution.

Spray technique is one of the best methods used for making thin films because
of its simpler construction and efficient output [123].

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Figure 2.5: Spraying Technique Apparatus

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