Chemical Vapor

Deposition (CVD)
NANO54
Foothill College
 Overview

• What is CVD?
• Types of CVD
– MO-CVD, PE-CVD, etc
• CVD process / applications
• PVD process / applications
• CVD vs. PVD
• Plasma Polymerization
Family of CVD Technologies
 What is CVD?
• Chemical vapor deposition (CVD) is a
chemical process used to produce high-purity,
high-performance solid materials. The
process is often used in the
semiconductor industry to produce thin films.
In a typical CVD process, the wafer
(substrate) is exposed to one or more volatile
precursors, which react and/or decompose on
the substrate surface to produce the desired
deposit. Frequently, volatile by-products are
also produced, which are removed by gas
flow through the reaction chamber.
http://en.wikipedia.org/wiki/Chemical_vapor_deposition
CVD Process Applications
• Microfabrication processes widely use CVD
to deposit materials in various forms,
including: monocrystalline, polycrystalline,
amorphous, and epitaxial. These materials
include: silicon, carbon fiber,
carbon nanofibers, filaments,
carbon nanotubes, SiO2, silicon-germanium,
tungsten, silicon carbide, silicon nitride,
silicon oxynitride, titanium nitride, and various
high-k dielectrics. The CVD process is also
used to produce synthetic diamonds.

http://en.wikipedia.org/wiki/Chemical_vapor_deposition
 What is CVD Process?
• Chemical Vapor Deposition is the formation of a non-
volatile solid film on a substrate by the reaction of vapor
phase chemicals (reactants) that contain the required
constituents.

• The reactant gases are introduced into a reaction

chamber and are decomposed and reacted at a heated
surface to form the thin film.
Chemical Vapor Deposition
• CVD => Chemical Vapor Deposition
• PE-CVD => Plasma Enhanced CVD
• MO-CVD => Metal Organic CVD
• Atmospheric pressure CVD (AP-CVD)
• Low-pressure CVD (LP-CVD)
• Ultrahigh vacuum CVD (UHV-CVD)
• Aerosol assisted CVD (AA-CVD)
• Direct liquid injection CVD (DLICVD)
 Plasma Enhanced CVD
• Microwave plasma-assisted CVD (MP-CVD)
• Plasma-Enhanced CVD (PE-CVD)
• Remote plasma-enhanced CVD (RPE-CVD)
 Other Types of Chemical
Vapor Deposition
• Atomic layer CVD (ALCVD)
• Combustion Chemical Vapor Deposition (CCVD)
• Hot wire CVD (HWCVD)
• Metal organic chemical vapor deposition (MOCVD)
• Hybrid Physical-Chemical Vapor Deposition
(HPCVD)
• Rapid thermal CVD (RTCVD)
• Vapor phase epitaxy (VPE)
Applications of CVD
 CVD Reactors

Horizontal APCVD Reactor

Thermal CVD Reactor

Chemical Vapor Deposition Apparatus

http://en.wikipedia.org/wiki/Chemical_vapor_deposition
Chemical Vapor Deposition
CVD Growth Model
The flow of reactants F is F  DG -1
 Plasma Enhanced (PE)CVD

As the thermal budget gets more constrained while more layers are added for
multi-layer metallization, we want to come down with the temperature for the oxide
( or other) CVD processes. One way for doing this is to supply the necessary
energy for the chemical reaction by ionizing the gas, thus forming a plasma.
PVD Apparatus

Physical Vapor Deposition Apparatus

http://en.wikipedia.org/wiki/Physical_vapor_deposition
 PVD Film Properties

Benefits Trade-offs
• Low substrate temperature • Not stoichiometric film
• Conformal film
• By-products incorporated
• Relatively fast process
• Comparatively low cost • Outgassing
• Cracking
• Peeling
 CVD vs. PVD
• Chemical Vapor Deposition (CVD) relies
on chemical reactions between reactants
in the gas phase and/or on the substrate
surface.
• Physical Vapor Deposition (PVD) is a
thermal evaporation driven or energy
driven process.
(PVD) Apparatus
 Silicon CVD ‘Epitaxy’
• When SiH4 gas is used in a CVD reactor, a Si
layer is deposited on the wafer surface. The size
of the crystallites depends on the deposition
temperature.
• At high enough temperature, the ad-atoms have
enough kinetic energy to move on the surface
and align themselves with the underlying Si.
• This is an epitaxial layer, and the process is
called Epitaxy instead of CVD.
• At lower deposition temperatures, the layer is
poly-crystalline Si (consisting of small crystallites)
Silicon Epitaxy Process

The chemical reaction that produces the Si

is fairly simple:

SiCl4(g)+2H2(g)=(1000-1200oC)=Si(s)+4HCl(g)

Instead of SiCl4 you may want to

use SiHXCl4-X
 CVD Used in Semiconductors
Layer Reaction equations Temperature (ºC)

SiO2 LTO SiH4 + O2 -> SiO2 + 2H2 400-450

TEOS Si(OC2H5)4 -> SiO2 + gas.RP 650-700
HTO SiCl2H2 + N2O -> SiO2 + 2N2 + 2HCl 850-900
SiH4 + CO2 H2 -> SiO2 + gas.RP 850-950

Si3N4   3SiH2Cl2 + 4NH3 -> Si3N4 + 6HCl + 6H2 700-900

Polysilicon   SiH4 -> Si + 2H2 600-650

selective 2WF6 + 3Si -> 2W + 3SiF4 300

Tungsten
blanket WF6 + SiH4 -> W + SiF4 + 2HF + H2 400-450
 Silicon Oxide CVD Process
There are several possibilities, one is
SiH2CI2 + 2NO2 = (900 °C) = SiO2 + 2HCI + 2N2

While this reaction was used until about 1985, a better reaction is offered by
the "TEOS" process.
Si(C2H5O)4 = (720 °C) = SiO2 + 2H2O + C2H4.

Si(C2H5O)4 has the chemical name Tetraethylorthosilicate

 MO-CVD
• A technique for growing thin layers of
compound semiconductors in which metal
organic compounds, having the formula
MRx, where M is a group III metal and R is
an organic radical, are decomposed near
the surface of a heated substrate wafer, in
the presence of a hydride of a group V
element. Abbreviated MOCVD.
Figure 1: Fabrication of (a) III–V-OI on Si substrate by DWB and (b)
InGaAs-OI MOSFETs with metal S/D structure using Ni–InGaAs alloy.
A first demonstration of a new metal source/drain technology for extremely thin
body (ETB) indium gallium arsenide (InGaAs) transistor channels on insulator
(OI) with silicon substrates has been reported by University of Tokyo, National
Institute of Advanced Industrial Science and Technology and Sumitomo Chemical
Co Ltd [SangHyeon Kim et al, Appl. Phys. Express, vol4, p114201, 2011].
 MO-CVD: TMG + Arsine => GaAs
http://www.hlphys.jku.at/fkphys/epitaxy/mocvd.html

The various techniques of growing epitaxial layers from the vapor phase can be divided
roughly into two categories depending on whether the species are transported physically or
chemically from the source to the substrate. In the physical transport techniques (Physical
Vapor Deposition - PVD), the compound to be grown or its constituents are evaporated and
subsequently transported through the relevant reactor toward the substrate. In the
chemical transport techniques (Chemical Vapor Deposition - CVD), volatile species
containing the constituent elements of the layer to be grown are produced first in- or
outside the reactor and transported as streams of vapor towards the reaction zone near the
substrate. These gaseous species subsequently undergo chemical reactions or dissociate
thermally to form the reactants which participate in the growth of the film. The practical
demand to decrease the growth temperature generated an intensive development trend of
CVD processes based on metal organic compounds, decomposing at lower temperatures.
This process is referred to as Metal Organic Chemical Vapor Deposition (MOCVD) or
Organometallic Vapor Phase Epitaxy. The classical example is the growth of GaAs from
Trimethylgallium (TMG) and Arsine (AsH3). In our laboratory we apply this technique to
grow GaN from TMG and Ammonia. However, this technique is based on a very precise
control of the gas flow as can be estimated from the look into the gas mixing cabinet.
Planetary MOCVD reactor in an industrial setup (Photo
courtesy of Aixtron)
http://www.hlphys.jku.at/fkphys/epitaxy/mocvd.html
Metal Organic
Vapor Phase
Epitaxy MO-VPE
Metal organic vapor phase epitaxy
(MOVPE), also known as
organometallic vapor phase epitaxy
(OMVPE) or metal organic chemical
vapor deposition (MOCVD), is a
chemical vapour deposition method of
epitaxial growth of materials,
especially compound semiconductors
, from the surface reaction of
organic compounds or metalorganics
and metal hydrides containing the
required chemical elements. For
example, indium phosphide could be
grown in a reactor on a substrate by
introducing Trimethylindium ((CH3)3In)
and phosphine (PH3). Formation of
the epitaxial layer occurs by final
pyrolysis of the constituent chemicals
at the substrate surface. In contrast to
molecular beam epitaxy (MBE) the
growth of crystals is by chemical
reaction and not physical deposition.

http://en.wikipedia.org/wiki/Metalorganic_vapour_phase_epitaxy
MO-CVD Apparatus
 PE-CVD
Plasma-enhanced chemical vapor
deposition (PECVD) is a process used to
deposit thin films from a gas state (vapor) to a
solid state on a substrate. Chemical reactions
are involved in the process, which occur after
creation of a plasma of the reacting gases.
The plasma is generally created by RF (AC)
frequency or DC discharge between two
electrodes, the space between which is filled
with the reacting gases

http://en.wikipedia.org/wiki/Plasma-enhanced_chemical_vapor_deposition
PE-CVD Apparatus
Thermal - chemical vapor deposition
A thermal-CVD system was built for
carbon nanotubes production via gas
phase or on substrate surface. The
sketch of thermal-CVD system consists
of quartz tube furnace which can operate
till 1200 degree centigrade. The sketch
of our equipment is shown in figure 1.
Main advantages of a thermal-CVD are:
the absolute ability for mass production
of nanotubes material and the
controllable growth of carbon nanotubes
at a specific location on a substrate for
incorporation in electronic device.

Plasma Enhanced - chemical vapor

deposition
A controllable method for carbon
nanotubes production is plasma
enhanced-CVD. Such a system is often
used to grow free standing vertically
aligned MWCNT. The set-up which our
laboratory is equipped with is a glow
discharged type. Briefly, two electrodes
are placed in a stainless-steel chamber.
The grounded cathode plays the role of a
substrate holder and Ohmic heater. On
the anode is applied aprox.400V. http://www.fy.chalmers.se/atom/research/nanotubes/experimental.xml
Low Pressure RF Plasma for PECVD of TiO2 on Plastics
http://www.ipe.ethz.ch/laboratories/ltr/research/index_EN
 Plasma Polymerization
• Plasma polymerization deposits molecules
onto a surface as a conformal coating
• The molecules deposited are part of a
network, often highly cross-linked
• Chemistry is tuned by the gas composition
mixture, flow rate, and energy conditions
• A variety of very novel molecular networks
can be formed in a straightforward manner
 Plasma Deposition
Plasma polymerization (or glow discharge
polymerization) uses plasma sources to
generate a gas discharge that provides
energy to activate or fragment gaseous or
liquid monomer, often containing
a vinyl group, in order to
initiate polymerization. Polymers formed
from this technique are generally highly
branched and highly cross-linked, and
adhere to solid surfaces well. The biggest
advantage to this process is that polymers
can be directly attached to a desired
surface while the chains are growing,
which reduces steps necessary for
other coating processes such as grafting.
This is very useful for pinhole-free coatings
of 100 picometers to 1 micrometer
thickness with insoluble polymers.

http://en.wikipedia.org/wiki/Plasma_polymerization
 Plasma Polymerization

Schematic representation of bicyclic step-growth mechanism of plasma polymerization

Plasma Polymerization

Hypothesized model of plasma-polymerized ethylene film (Wikipedia)

Plasma Polymerization
Mechanism and Species
Plasma contains many species such as ions,
free radicals and electrons, so it is important
to look at what contributes to the
polymerization process most. The first
suggested process by Westwood et al. was
that of a cationic polymerization, since in a
direct current system polymerization occurs
mainly on the cathode. However, more
investigation has led to the belief that the
mechanism is more of a radical
polymerization process, since radicals tend to
be trapped in the films, and termination can
be overcome by reinitiation of oligomers.
Other kinetic studies also support this theory.
In polymerization, both gas phase and surface
reactions occur, but mechanism differs
between high and low frequencies. At high
frequencies it occurs in radical intermediates,
whereas at low frequencies polymerization
happens mainly on surfaces.

http://en.wikipedia.org/wiki/Plasma_polymerization
 Summary
• CVD is a family of techniques
– CVD, PVD, PE-CVD, MO-CVD
• Chemistry in the vapor phase
– Surface reactions on the substrate
• Plasma can ‘enhance’ reaction conditions
• Used principally in semiconductor industry
 References
• Microelectronics Processing Course - J.
Salzman - Jan. 2002 . Microelectronics
Processing Chemical Vapor Deposition
• Microelectronics Processing Course - J.
Salzman – Fall 2006 . Microelectronics
Processing . Ion Implantation
• Wikipedia, CVD, PVD, PE-CVD, MO-CVD
• American Vacuum Society (AVS)