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Chemical Vapor Deposition

BY GROUP 1
ARBI FIKRI IRSYAD
FRANS W. SITUMORANG
KHALISHA PRAMONO
TSAOME INDAH SUSIMAH
OUTLINE
INTRODUCTION
THERMODYNAMICS AND KINETICS OF CVD
TYPES OF CVD PROCESS
ADVANTAGES AND DISADVANTAGES
APPLICATION OF CVD ON CORROSION
PROTECTION
Introduction

Chemical Vapor Deposition or CVD is one kind of


coating processes. Its done by depositing a solid on a
heated surface of substrate through chemical
reaction in the vapor phase
The deposition usually takes place at temperature of
1000oC for structural component applications
An Example of a CVD System

Three main equipment for CVD:


1. A gas distribution and mixing system
2. A reaction chamber and its system for providing the conditions
3. A neutralization system
An Example of a CVD Model
1. Mass transport of reactant
gaseous species to substrate
2. Diffusion of the reactant to
substrate surface
3. Adsorption
4. Surface migration
5. Desorption of by-product
species
6. Diffusion of by-product
species
7. Transport of by-product
species away from substrate
(exhaust)
Thermodynamics and Kinetics of
CVD
Thermodynamics

A CVD reaction is governed by thermodynamics, that


is driving force which indicates the direction the
reaction is going to proceed, and by kinetics, which
defines the transport process and how fast it is going
Thermodynamics

To calculate dG reaction, it is necessary to know the thermodynamics of each


component, specifically their free energies of formation

dG of formation is a function of several parameters which include the type of


reactants, the molar ratio of these reactants, the process temperature, and the
process pressure
Such program that is used widely in equilibrium calculations in CVD
system

SOLGASMIX
EKVICALC
EKVIBASE
Kinetics

Deposition Sequence
1. Reactant gases enter the reactor by forced flow.

2. Gases diffuse through the boundary layer.

3. Gases come in contact with surface of substrate.

4. Deposition reaction takes place on surface of substrate.

5. Gaseous by-products of the reaction are diffused away from


the surface, through the boundary layer.
These steps occur in the sequence shown and the
slowest step determines the deposition rate. This can
be determined by either
a) the surface reaction kinetics,
b) the mass transport,
c) gas-phase kinetics.
Surface Reaction Kinetics

In the case of by surface reaction


kinetics, the rate is dependent on the
amount of reactant gases available
The Mass Transport

The diffusion rate of the reactant gases through


the boundary layer controls the reaction; it will
be mass transport phenomena.
the boundary layer is thicker making it more difficult for the reactants to
reach the deposition surface. The diffusion rate through the boundary layer
then becomes the rate limiting step
Precursor of CVD

Halides Carbonyls

Hybrides
Halide
Carbonyls
Hybrides
Purity of Reactant
Impurity
Major cause of defect on deposit
It is preferable to purify and filter the gases at the point of use
Catalytic >> reduce H2, O2, CO, and hydrocarbons impurities, < 10ppb
Palladium Diffusion >> purify hydrogen
Gettering (Zr, Ti alloy) >> O2, H2O, N2, H2, CO, CO2,
and hydrocarbons, <10ppb
Filtering >> post purifying process
Type of CVD Process

Thermal Laser

Photon Plasma
Thermal condition (High temperature 800-2000 C)

Hot Wall Reactor (isothermal, close temperature control, deposition occurs on reactors wall)
Cold Wall Reactor (induction heating, low pressure 100mbar - 1atm
Pressure Condition
1) Atmospheric (deposition is diffusion limited)
Reactor is diluted with inert gas

2) Low-Pressure (deposition is limited by surface reaction)


Ultra High Vacum Reactor
greater uniformity
better step coverage
Reduced impurity
Laser CVD

Laser CVD occurs as a result


of the thermal energy from
the laser coming in contact
with and heating an
absorbing substrate.

The wavelength of the laser


is such that little or no
energy is absorbed by the
gas molecules.
Photo CVD

The chemical reaction is


activated by the action
of photons, specifically
ultraviolet (UV)
radiation
No heat is required,
Can be opaque,
absorbent, or
transparent materials
Slow rate deposition
Plasma CVD

the reaction is activated


by a plasma and the
deposition temperature
is substantially lower
Plasma is gaseous state
of ionized atom (positive
charge ions, negative
charge electrons)
Glow-Discharge (Microwave) Plasma

A glow-discharge (non-
isothermal) plasma is
generated in a gas by a high-
frequency electric field,
such as microwave (2.45
GHz), at relatively low
pressure
Electron Cyclotron Resonance (ECR)

Frequency of the alternating


electric field is made to
match the natural
frequency of the electrons
orbiting the lines of force of the
magnetic field.
This occurs at the standard
microwave frequency of 2.45
GHz when it is coupled with a
magnetic field of 875 Gauss.
Plasma CVD characteristic

Relatively low temperature


Materials can be coated with or without diffusion
Low residual stress
High rate of deposition
Good uniformity (at low pressure process)
Growth and Structure of Deposit

Epitaxy - growth of a crystalline film on a crystalline


substrate, with the substrate acting as a seed crystal
Thermal Expansion
Microstructure
Microstructure

Ceramics and dielectric


materials are likely
amorphous or [C]

Metals are likely [A] or [B]


Advantages and Disadvantages
Advantages

Not restricted
to a line-of-
sight
deposition,
resulting in a
good
conformity or
uniform
thickness of the
coating
Advantages

Have greater flexibility of using a wide range


of chemical precursors
Including metals, non-metallic elements, and polymers.
CVD has been developed in industrial application and now is
available to deposit around 70% elements in the periodic table,
some of their oxides, ceramic materials, etc.
Advantages

Requires relatively low deposition


temperature
for example, refractory materials such as SiC (sublimation
point: 2700oC) can be deposited at about 1000oC but the
deposition temperature could be significantly decreased to
around 300oC by the enhancement techniques such as using
plasma
Advantages

Controllable crystal structure, stoichiometry, surface


morphology and orientation of the CVD manufactured
products
Advantages

Deposition rate is high and thick coatings can


be readily obtained
For protective coatings, it prefers high deposition rate and can
be greater than tens of micrometers per hour
For some cases, CVD is more economical than PVD
Advantages

The equipment does not normally require


ultra-high vacuum working environments
and is flexible compared to PVD
Disadvantages

Requires chemical precursors as the


essential reactants
Can often present safety and health hazards
Some can be expensive (especially the metal-organic ones)
Producing exhaust gases that can also present safety and
health hazards, the treatment can be costly.
Disadvantages

Quite complex Reactants

Requires numerous test runs


to determine the right Gas
Energy
flow
parameters rates
supplied

Parameters

Ratio of Substrate
reactants temperature

etc
APPLICATIONS OF CVD ON
CORROSION
Corrosion is defined as the wearing of a surface by a
chemical action
The main problem posed by CVD is that the thermal
expansion coefficient of the substrate metal and the
coating metal should agree
The substrate should withstand the required deposition
temperature
CVD application for corrosion includes CVD Borides,
CVD Carbides, CVD Nitrides, and CVD Oxides
CVD Borides

Typical borides are HfB2, Mo2B5,


NbB2, TaB2, TiB2, W2B5, and
ZrB2
Borides are relatively inert,
especially to non-oxidizing
reagents
Borides react violently with
fluorine
Borides are generally resistant to
molten metals
CVD Carbides

TiC, SiC, and Cr7C3 are commonly used


TiC has good resistance in sulfuric acid
TiC can form a passivating oxide layer up to a
potential 1.8 V at which point the corrosion becomes
very severe
TiC is very resistant to sea water, neutral industrial
waste, and human sweat
Cr7C3 is even more corrosion resistant
Cr7C3 is used widely as a passivating layer
CVD Nitrides

CVD TiN, ZrN, and HfN are the most commonly used
TiN, ZrN, and HfN have high thermal and chemical
stability
TiN, ZrN, and provide a good barrier to diffusion
TiN, ZrN, and HfN is resistant to acids
TiN is extremely resistant to sea water and human
sweat
CVD Oxides

Al2O3, HfO2, SiO2, TiO, and ZrO2


have characteristic excellent
oxidation resistance
TiO2 increases the pitting and
general corrosion resistance of
steel
CVD Films for Corrosion Protection Coatings

CVD processes, which employ vapor-transport and heat


treatment of a stabilized alloy substrate to deposit
protection coatings, have performed extremely well
Corrosion resistance of structural iron-base alloys in
high-temperature environments is typically achieved by
formation of a continuous protective oxide scale
The formation acts as a diffusion barrier between the
environment and the alloys
The use of reactive elements, such as
yttrium, influences the properties of both
the scale and the alloy substrate during
high temperature oxidation
The reactive elements tend to inhibit grain
growth
The reactive elements stabilize the alloy
substrate during high-temperature
oxidation
Reactive elements in Fe-Cr alloys inhibit
grain growth in the alloy and suppress Fe
diffusion through the scale
x = oxide thickness
x2 = kpt t = diffusion time
kp = parabolic rate constant

This assumption could be applicable only if no open voids or micro


cracks are present in the scale
To improve the protective scale, we must slow the diffusion of either
cations or anions through the film to the modified alloy surface
Al2O3, Cr2O3, dan SiO2 are thermodinamically stable oxides
Al2O3, Cr2O3, dan SiO2 have low diffusivity and will provide an
excellent diffusion barrier
Coatings on high-temperature
alloys could be produced by CVD
with a vapor source
The process is followed by
annealing to diffuse the vapor
into the bulk alloy
Exposure to reactant vapor to
form a stable phase by chemical
reaction at the surface
Example of CVD application for coating
That is all, Thank you!
References
Yan, Xiu-Tian. and Xu, Yongdong. Chemical Vapour Deposition: An Integrated
Engineering Design for Advanced Materials. London: Springer, 2010.
Park, J.H. and Cho, W.D. CVD Films for Corrosion Protection Coatings. Surface
Engineering Series: Chemical Vapor Deposition. 2: 421-434, 2001.
Sathiyanarayanan, S. et al. 2005. Corrosion Protection by Chemical Vapor
Deposition: A Review. Corrosion Reviews. 23: 355-370, 2005.
Campos, R.A. et al. Influence of Boriding Process in Adhesion of CVD Diamond
Films on Tungsten Carbide Substrates. Materials Research. Vol 18. 2015.
Sui, Jian. And Liu, Xiufang. Preparation and characterization of a dual-layer
carbon film on 6H-SiC wafer using carbide-derived carbon process with
subsequent chemical vapor deposition. Surface & Coatings Technology. 235: 469-
474, 2013.
Pierson, Hugh O.. 1999. Handbook of chemical vapor deposition. the United States
of America : Noyes Publications / William Andrew Publishing, LLC