Chemical Vapour Deposition (CVD) is a process where one or more volatile precursors are

transported via the vapour phase to the reaction chamber where they decompose on a heated
substrate. This results in a deposition of a solid thin film.

Materials deposited by CVD include metals and certain multi element materials such as
borides, carbides, silicides, nitrides, phosphides, arsenides, oxides and sulphides.

EXAMPLE:

CVD of TiB2 films occurs at about 1000 degree centigrade, substantially below the
material’s melting point (i.e., 3325 oC)

Equation:

TiCl4 + 2BCl3 + 5H2 -----------> TiB2 + 10HCl

TiB2 has outstanding properties as an armour material.

APPLICATIONS OF CVD:

1. Hard coatings to improve the life and performance of cutting tools.

2. Coatings for aircraft engine components.
3. In microelectronics industry to build electronic components.
4. In glass industry to coat large panels of glass with SnO2, TiN and SiO2.
5. Layers in solar cells
6. Optical layers in waveguides
7. Coatings for catalysis.
8. Synthetic gold coating( non-stoichiometric TiN) on jewellery

Glass panels are formed on a float line in which the hot glass is transported on top of molten
tin. The panels pass through several CVD reactors in which reactants are directed towards the
hot substrate, where they form coatings.
Steps involved in CVD process:
1. Transport of the reagents in gaseous phase, often in carrier gas, to the deposition zone.
2. Diffusion or convection of gaseous precursors through the boundary layer.
Boundary layer: Hot layer of gas immediately adjacent to the substrate.
3. Adsorption of film precursors on to the growth surface.
4. Surface diffusion of precursors to growth sites.
5. Surface chemical reactions leading to deposition.
6. Desorption of by-products.
7. Transport of gaseous by products out of the reactor.
GAS PHASE REACTIONS:
They occur in the hot boundary layer, prior to the adsorption of precursor on the surface. In
majority of CVD reactions, these gas phase reactions are undesirable.
However, in some cases like in CVD of GaAs, gas phase reactions are beneficial for the film
quality.
The total pressure in the reactor is used to control the gas phase reactions as when it is lowered the
probability of gas-gas collisions becomes smaller.
Surface initiated chemical reactions:
Once the precursors have been adsorbed on to the substrate and has diffused o growth sites, it
should undergo surface initiated chemical reactions to deposit the desired material.
Decomposition pathway is determined and controlled by:
Nature of ligand and type of metal-ligand bond
Properties of an ideal precursor:
It should
1. Be liquid rather than solid or gaseous.
2. Have good volatility.
3. Have good thermal stability in the delivery system.
4. Decompose cleanly and in a controlled manner on the substrate.
5. Be nontoxic and non-pyrophoric.
6. Be readily available at consistent quality and quantity at low cost.
7. Have high purity.
8. Give by products which are stable and readily removed from the reaction zone.
Precursors rarely meet all criteria; compromises have to be made.
What results in a lower thermal stability window?
The requirement of a high reactivity t higher temperatures, to achieve higher deposition rates is
preferred rather than the long-term thermal stability at ordinary temperatures.
Precursors used in CVD:
Industrially important CVD processes utilize simple precursors such as:
Metal hydrides:(SiH4, AsH3)
Metal alkyls: (AliBu3, GaEt3).
Metal halides: (WF6, TiCl4)
Metal organic and organo-metallics compounds.
Metal halides are avoided because:
They require the use of a reducing agent and they are often corrosive or produce corrosive by
products(HX, X2)
OMC CPDS:
They are often more volatile than most organic compounds, but they thermally decompose at
relatively low temperatures which can lead to carbon and other contaminations of the substrate.
How to enhance the volatility of precursors?
Volatility is enhanced by minimizing all types of interactions between the precursor molecules in
the condensed state. These interactions include hydrogen bonds, dipole-dipole interactions and
van der Waals Interactions.
1. Fluorination of ligands or substituents helps to reduce van der Waals interactions between
the molecules.
2. Oligomerization or aggregation of precursors should be avoided, since smaller non-polar
compounds have a higher vapour pressure.
3. Beta diketonate ligands are used in metal-containing precursors. These are chelating
ligands, so they occupy only two coordination sites at the metal center. Thus, beta
diketonate metal complexes of metals with lower coordination numbers are monomeric and
volatile.

APPROACHES FOR THE CVD OF MULTI-ELEMENT MATERIALS:

1. Multi-source precursors
2. Single source precursors

MULTI-SOURCE PRECURSORS:
Two or more individual precursors may be used that decompose individually on the substrate
and eventually give a film of the desired multi-element composition. In case of GaAs the
most commonly employed precursors are GaMe3 and AsH3.
Equation:
GaMe3 + AsH3--------> GaAs + 3CH4
Advantage:
Only single by-product is formed and can be removed easily.
Disadvantages:
One problem associated with the multi-source precursor approach is the reproducible control of
film stoichiometry.
This problem arises because the precursors or the intermediates formed during film deposition
have different reactivities and volatilities.
Example: Lead-containing films such as PbTiO3, which can result in the formation of lead
deficient materials due to desorption of volatile PbO.
Solution:
Additional use of single source precursors along with multi-source precursors allows
simplification of the precursor delivery system.

SINGLE SOURCE PRECURSORS:

Single source precursors contain the elements desired in the final film in one component
preferably in the ratio also required in the film.
An example for GaAs is the cyclic compound [Et2Ga-AstBu2]2.

[Et2Ga-AstBu2]2 ------------> GaAs + 4C2H4 + 4CH2=CMe2 + 4H2

In single source precursors, the bond between the film forming components must be stronger
than those to the supporting ligands or substituents. These ligands can be removed cleanly by
selective bond breaking. Otherwise, the advantages of the single source are lost.

Disadvantages:
Single source precursors have higher molecular weights than multi source precursors. Therefore,
they are less volatile.
It is also difficult to deposit films with non-integral stoichiometry, doped films, or materials with
two or more metals.
Stoichiometry of the precursor is not always retained in the film.
EQUIPMENT:
Features common to all CVD reactors include:
1. A precursor delivery system
2. A reactor and
3. An exhaust system to remove by-products.
In conventional CVD processes the substrate temperature varies between 200 and 800 degree
centigrade depending on the nature of the layer and the pressure in the reactor cell between
0.2mbar and 1 bar.
Diagram:
Schematic of a thermal CVD reactor for copper CVD from a Cu(II) precursor
MFC=Mass Flow Controller.
The precursor delivery method plays a critical role because the overall deposition rate can be
limited by the feed rate of the precursor delivery into the reactor. The transport of liquid or solid
precursors with relatively low vapour pressures is controlled by bubbling a carrier gas through
the precursor.
The vapour pressure of liquids should be greater than 0.01bar at 25 degree centigrade for
efficient industrial utilization. If the volatility of the precursors at room temperature is not
sufficient, the storage vessel must be heated. Conventional delivery methods are unsuitable if
the precursors are thermally unstable.
Alternative methods of delivery must then be used such as,
Liquid delivery, aerosol delivery, spray pyrolysis and supercritical fluid delivery.
TWO MAIN REACTOR TYPES IN CONVENTIONAL CVD SYSTEM

1. Hot-wall reactors:

The substrate and the chamber walls are maintained at the same temperature.

Used in industry for CVD of semiconductors ad oxides.

These are primarily used at the laboratory scale.

Advantages:

• Simple to operate.
• Can accommodate several substrates.
• Obtaining a uniform substrate temperature is easy.
• Can be operated under a range of pressure and temperature.
• Different orientations of substrate relative to the gas flow are possible.

Disadvantages:

• Deposition occurs not only on the substrate but also on the reactor walls.
• Large consumption of the precursors makes control of the gas composition more
difficult.
• Gas phase reactions in the heated gas can occur.
2. Cold-wall reactors:
Substrate is maintained at high temperature than the reactor walls.
Most metal CVD in industry is carried out using these reactors.
Advantages:
• Pressure and temperature are controlled.
• Plasma can be used.
• Deposition does not occur on the reactor walls.
• Gas phase reactions are suppressed.
• Higher deposition rates can be obtained.

Because deposition occurs only on the heated substrate (Higher precursor Efficiency)

Disadvantages:

The steep temperature gradients near the substrate surface may lead to severe
convection which results in non-uniform coatings.

PROCESS VARIABLES THAT INFLUENCE FILM PROPERTIES:

 Reactor geometry

Reactant delivery

Total pressure

Gas and substrate temperature

Substrate environment

Gas composition and homogeneity

Nucleation

Density

Thermodynamic and kinetic properties of all involved species

Particularly gas and surface chemistry

Composition of the products

Reaction mechanism etc.

COATING PROPERTIES INFLUENCED BY PROCESS VARIABLES:

Composition
thickness
morphology
density
uniformity
adhesion to the substrate
crystallinity
stress

GROWTH OF CRYSTAL WITH TEMPERATURE

The typical dependence of the film growth on the substrate temperature shows three
different regimes.

1. At low temperatures, the growth rate is surface reaction limited

2. At intermediate temperatures, the growth rate is diffusion or mass transport limited. All
the reactants that reach the substrate decompose. The reaction proceeds more rapidly than
the rate at which reactant is supplied to the surface by diffusion through the boundary
layer.

3. At high temperatures, the growth rate decreases due to an increased desorption rate of
film components and due to depletion of reactants by reaction on the reactor walls.
ROLE OF TOTAL PRESSURE ON CVD:
1. For the precursors with low vapour pressure, the deposition rate is limited by the
feed rate of the precursor delivery into the reactor. So, the transport of liquid or
solid precursors with relatively low vapour pressures is controlled by bubbling a
carrier gas through the precursor.
2. The pressure of the CVD reactor determines the relative importance of each of the
regimes in the growth process.

For example:

There is a significant boundary layer at atmospheric to intermediate pressures(e.g.,

0.2bar). Therefore, growth can be characterized by the intermediate and high
temperature regimes.

However, as the pressure in the reactor is lowered (low pressure CVD less than 1
millibar), layer growth is essentially surface reaction controlled as in the low
temperature region.

PVD Physical vapour deposition

Chemical vapour deposition
CVD
Plasma-assisted CVD
PACVD
Plasma enhanced CVD
PECVD
Laser induced CVD
LCCVD
 Low pressure CVD
LPCVD
Remote plasma CVD
RPCVD
Metal organic CVD
MOCVD
Metal organic VPE
MOVPE
Organometallic CVD
OMCVD
Organometallic VPE
OMVPE
Atomic layer epitaxy
ALE
Vapour phase epitaxy
VPE
Chemical vapour infiltration
CVI
Chemical beam epitaxy
CBE also called
Metal organic molecular beam epitaxy
MOMBE

Metal CVD:

Applications of Metal coatings:

Metal coatings on various substances are needed for a variety of applications like:
1. Oxidation, corrosion, or abrasion protection films
2. Reflective or conductive coatings or electrodes.
3. The purpose of metallization in microelectronics is to provide interconnections
between various circuit composites. These interconnection materials do not
react with the material they connect.
Electromigration:
When copper is coated on silicon substrate some amount of Silicon may diffuse into
the solid film to form metal solutions or metal silicides during thermal processing or
by electromigration. Aluminium and silver show more electromigration than copper.
To suppress electromigration,
Suitable substrate and reaction conditions are selected so that the film is durable.
 diffusion barrier layer is often introduced between the metal and the semiconductor.
Common materials that suppress this migration for Si/Al contacts are TiN, Ti, TiW,
ZrN and RuO2.

CVD of Copper:

Advantages:

1. Resistant to electromigration as compared to Al and Ag

2. Better thermal expansion coefficient (resists high temperature)
3. High melting point
4. Low electrical resistivity

Disadvantages:

1. Fast diffusion in Silicon and drift SiO2 based insulating materials.

2. Poor adhesion.
3. Lack of suitable etch process.
Cu(II) Precursors:
Best investigated complex:
Cu(hfac)2 or hexafluoro acetylacetonate complex
The volatility of beta diketonate complexes increases with the number of fluorine
atoms. H atoms in the ligand are replaced by F atoms so that the inter molecular
interaction is minimized and F-F repulsion is enhanced.

Reactions showing cvd process for Cu(hfac)2 in the presence of hydrogen.

Role of H2: It is used as a reducing agent. If it is not used metal oxide is formed that is
not required. So, hydrogen is used as a carrier gas for the deposition of thin film as metal.
Cu(hfac)2 adsorbed dissociatively under cvd conditions. The hfac ligands spread over the
Cu surface. The reverse rxns leading to desorption of complex.
Ligand is adsorbed on the substrate surface. It then reacts with the adsorbed H2 to form
hfac ligand which evolves out as a by-product leaving behind pure metallic film.

Cu(I) Precursors:

It is mostly liquid and have lower vapour pressure and lower decomposition temperature
with no reducing agent.

The most widely studied family are Lewis base stabilized Cu(I) beta diketonate.

L is neutral Cu +1, LIGAND+1

The deposition process given below:

A disproportionation reaction, in which half of the the unstable Cu(I) complex

decomposes into Cu(II) complex (higher oxidation state) and half of the Cu(I)
decomposes into Cu(0) metallic film ( the lower oxidation state) and ligand molecules are
released as by products.

CVD of Aluminium:

Uses of aluminium films:

Used for food packing.

Interconnector in electronics

PRECURSORS:

The precursor should have moderate stability. It should not so highly stable because n that
case it would not decompose on the substrate surface. Also it should not be so unstable
that it decomposes before higher oxidation state reaching the substrate surface.

Al precursors are volatile and decompose easily and are moderately stable as well. The
most widely used deposition reaction is the pyrolysis of an aluminium alkyl such as:

1. Tri-isobutyaluminium or TIBA, (C4H9)3Al

2. Tri-methylaluminium or TMA, (CH3)3Al
3. Tri-ethylaluminium or TEA, (C2H5)3Al
4. Di-methylaluminium hydride or DMAH, (CH3)2AlH

1. Using Tri-isobutylaluminium as precursor:

• The isobutyl group is removed by beta hydride elimination at temperature=50
degree centigrade.
• The di-isobutylaluminium formed. Its formation in precursor vessel and the gas
tubings can be suppressed by the addition of isobutene to the carrier gas because
the beta elimination process is reversible.

Overall reaction:
3Al(CH2CHMe2)3 ------> [HAltBu2]3 cyclic trimeric intermediate
<------

1ST route: One isobutyl group removed leaving behind cyclic trimeric form as
intermediate. It further decomposes to form aluminium.

2nd route: Three butyl groups are removed in the form of an alkene, Al is separated and
H2 evolved as a by-product.

AlBu3 -----------> Al + 3CH2=CMe2 + 3/2H2

Schematic representation of the thermal decomposition of tri-butylaluminium.

1. The upper pathway (at lower temperature):

1. A low temperature, beta hydride elimination occurs.

Beta hydrogen atom in aluminium alkyl is removed as hydride and gets weakly adsorbed
on the substrate surface. Two neighbouring hydrides then combine to form H2 which is
removed. Olefin from metal alkyl is also released as a by-product.

It results in the clean deposition. So, it is the preferred pathway.

2. The lower pathway (at higher temperature):

At higher temperature, beta methyl elimination occurs.

Beta methyl group is detached from the aluminium alkyl forming a pi bond. The olefin is
removed leaving behind Al thin film. The detached CH3 group strongly binds to the
substrate. On high temperature, only H is removed C still remains on the substrate as an
impurity.

Carbon impurities may be incorporated into the film. If beta methyl elimination pathway
is adopted, impure Aluminium thin film is formed.

3. Using Tri-methylaluminium as precursor:

• This is suitable because beta hydrogen elimination is not possible because no beta
C present. But it contains high amounts of carbon.
 • Thermal decomposition results in the formation of thermodynamically favoured
Al2C2. Or Al4C3 metal carbide formation

H2 as reducing gas used as carrier gas to avoid carbide formation:

Al films with little carbon incorporation are formed when the atmosphere is changed
to hydrogen. As a result, methane is formed which evolves out as a by-product.

REACTIONS:

2Al2Me6 -------------> Al4C3 + 9CH4

Al2Me6 + 3H2---------> 2Al + 6CH4

4. Precursors suitable for Al CVD: TERTIARY AMINE LIGAND ADDUCTS:

• ALH3 is a solid not suited for CVD because it is no stable enough. It decomposes
before reaching the substrate surface.
• So ALH3 is also contained in donor acceptor complexes of the type L-AlH3 where L
is a Lewis base. Here Lewis ligands such as tertiary amines are used as supporting
ligands or stabilizing agents. These ligands help AlH3 to reach the substrate surface.
• For CVD purposes adducts with L=tertiary amines are used, the stability and volatility
of these complexes is influenced by the electronic properties and stearic bulk of L.
Tertiary amines are detach easily than primary than tertiary amines.
• They are easily prepared and are significantly less air-sensitive than are aluminium
alkyls.
• The problem of carbon incorporation is minimized with these precursors because the
compounds contain no Al-C bond and Al-N bond can be easily cleaved.
Thermal decomposition mechanism of Me3NAlH3 on Al surfaces:

• The first step after adsorption is the dissociation of NMe3 and its fast desorption.
Similar to the dispersion of the butyl groups after adsorption of AlBu3, the hydrogen
atoms of AlH3 also disperse over the Al surface.

Al-N bond cleaves easily. NR3 adsorbed on the substrate surface. NR3 is then removed,
neighbouring hydrides combine to form H2 which evolves out.
Expensive process because

1. High energy input required to form plasma having mixture of C and H- radicals.
2. and low pressure is required for this process.

It is latest in research, but no common industrially. Further research is going on to make

the process economical.

Role of Hydrogen in diamond CVD:

During diamond CVD, methane is passed through plasma or electric arc. As a result, it
breaks into Hydrogen radical and Graphite Carbon. Diamond is metastable with respect to
graphite at low pressure. The growth of metastable diamond is possible in the presence of
atomic hydrogen which selectively etches graphite nuclei and leaves diamond.

1. In the presence of extra hydrogen, sp2 carbon of graphite finds a reducing

environment and converts into sp3 hybridized diamondide carbon.

yH. + xC graphite -----------> CxHy

mH. + CxHy ----------> m + y/2H2 + xC diamond.

So, Hydrogen prevents the formation of sp2 hybridized carbon atoms at the growth front
and stabilizes the growing diamond surface.

2. Dissolution rate of graphite and amorphous carbon by hydrogen is about 50 times of

diamond.