Chemical vapor deposition

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For the scientific journal named Chemical Vapor Deposition, see Chemical Vapor Deposition
(journal).

DC plasma (violet) enhances the growth of carbon nanotubes in laboratory-scale PECVD apparatus

Chemical vapor deposition (CVD) is a chemical process used to produce high quality, highperformance, solid materials. The process is often used in the semiconductor industry to
produce thin films. In typical CVD, 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.
Microfabrication processes widely use CVD to deposit materials in various forms,
including: monocrystalline, polycrystalline,amorphous, and epitaxial. These materials
include: silicon (SiO2, germanium, carbide, nitride, oxynitride), carbon
(fiber,nanofibers, nanotubes, diamond and graphene), fluorocarbons, filaments, tungsten, titanium
nitride and various high-k dielectrics.
Contents
[hide]

1Types

2Uses

3Commercially important materials prepared by CVD

o

3.1Polysilicon

3.2Silicon dioxide

3.2.1Silicon nitride

3.3Metals

3.4Graphene

3.5Diamond

4Chalcogenides

5See also

6References

7Further reading

Types[edit]

Hot-wall thermal CVD (batch operation type)

Plasma assisted CVD

CVD is practiced in a variety of formats. These processes generally differ in the means by which
chemical reactions are initiated.

Classified by operating pressure:

Atmospheric pressure CVD (APCVD) CVD at atmospheric

pressure.

Low-pressure CVD (LPCVD) CVD at sub-atmospheric

pressures.[1] Reduced pressures tend to reduce unwanted gasphase reactions and improve film uniformity across the wafer.

Ultrahigh vacuum CVD (UHVCVD) CVD at very low pressure,

typically below 106 Pa (~108 torr). Note that in other fields, a
lower division between high and ultra-high vacuum is common,
often 107 Pa.

Most modern CVD is either LPCVD or UHVCVD.

Classified by physical characteristics of vapor:

Aerosol assisted CVD (AACVD) CVD in which the precursors

are transported to the substrate by means of a liquid/gas
aerosol, which can be generated ultrasonically. This technique
is suitable for use with non-volatile precursors.

Direct liquid injection CVD (DLICVD) CVD in which the

precursors are in liquid form (liquid or solid dissolved in a
convenient solvent). Liquid solutions are injected in a
vaporization chamber towards injectors (typically car injectors).
The precursor vapors are then transported to the substrate as
in classical CVD. This technique is suitable for use on liquid or
solid precursors. High growth rates can be reached using this
technique.

Plasma methods (see also Plasma processing):

Microwave plasma-assisted CVD (MPCVD)

Plasma-Enhanced CVD (PECVD) CVD that utilizes plasma to

enhance chemical reaction rates of the precursors.[2] PECVD
processing allows deposition at lower temperatures, which is
often critical in the manufacture of semiconductors. The lower
temperatures also allow for the deposition of organic coatings,
such as plasma polymers, that have been used for nanoparticle
surface functionalization.[3]

Remote plasma-enhanced CVD (RPECVD) Similar to PECVD

except that the wafer substrate is not directly in the plasma
discharge region. Removing the wafer from the plasma region
allows processing temperatures down to room temperature.

Atomic-layer CVD (ALCVD) Deposits successive layers of

different substances to produce layered, crystalline films.
See Atomic layer epitaxy.

Combustion Chemical Vapor Deposition (CCVD) Combustion

Chemical Vapor Deposition or flame pyrolysis is an openatmosphere, flame-based technique for depositing high-quality thin
films and nanomaterials.

Hot filament CVD (HFCVD) also known as catalytic CVD (CatCVD) or more commonly, initiated CVD (iCVD), this process uses a
hot filament to chemically decompose the source gases.[4] The
filament temperature and substrate temperature thus are
independently controlled, allowing colder temperatures for better
adsorption rates at the substrate and higher temperatures
necessary for decomposition of precursors to free radicals at the
filament.[5]

Hybrid Physical-Chemical Vapor Deposition (HPCVD) This

process involves both chemical decomposition of precursor gas
and vaporization of a solid source.

Metalorganic chemical vapor deposition (MOCVD) This CVD

process is based on metalorganic precursors.

Rapid thermal CVD (RTCVD) This CVD process uses heating

lamps or other methods to rapidly heat the wafer substrate. Heating
only the substrate rather than the gas or chamber walls helps
reduce unwanted gas-phase reactions that can lead
to particle formation.

Vapor-phase epitaxy (VPE)

Photo-initiated CVD (PICVD) This process uses UV light to

stimulate chemical reactions. It is similar to plasma processing,
given that plasmas are strong emitters of UV radiation. Under
certain conditions, PICVD can be operated at or near atmospheric
pressure.[6]

Uses[edit]
CVD is commonly used to deposit conformal films and augment substrate surfaces in ways that
more traditional surface modification techniques are not capable of. CVD is extremely useful in the
process of atomic layer deposition at depositing extremely thin layers of material. A variety of
applications for such films exist. Gallium arsenide is used in some integrated circuits (ICs) and
photovoltaic devices. Amorphous polysilicon is used in photovoltaic devices.
Certain carbides and nitridesconfer wear-resistance.[7] Polymerization by CVD, perhaps the most
versatile of all applications, allows for super-thin coatings which possess some very desirable
qualities, such as lubricity, hydrophobicity and weather-resistance to name a few.[8] CVD of metalorganic frameworks, a class of crystalline nanoporous materials, has recently been demonstrated.
[9]
Applications for these films are anticipated in gas sensing and low-k dielectrics

Commercially important materials prepared by CVD[edit]

Polysilicon[edit]
Polycrystalline silicon is deposited from trichlorosilane (SiHCl3) or silane (SiH4), using the following
reactions:[10]
SiH3Cl Si + H2 + HCl
SiH4 Si + 2 H2
This reaction is usually performed in LPCVD systems, with
either pure silane feedstock, or a solution of silane with 70
80% nitrogen. Temperatures between 600 and 650 C and
pressures between 25 and 150 Pa yield a growth rate between
10 and 20 nm per minute. An alternative process uses
a hydrogen-based solution. The hydrogen reduces the growth
rate, but the temperature is raised to 850 or even 1050 C to
compensate. Polysilicon may be grown directly with doping, if
gases such as phosphine, arsine or diborane are added to the

CVD chamber. Diborane increases the growth rate, but arsine

and phosphine decrease it.

Silicon dioxide[edit]
Silicon dioxide (usually called simply "oxide" in the
semiconductor industry) may be deposited by several different
processes. Common source gases
include silaneand oxygen, dichlorosilane (SiCl2H2) and nitrous
oxide[11] (N2O), or tetraethylorthosilicate (TEOS; Si(OC2H5)4). The
reactions are as follows[citation needed]:
SiH4 + O2 SiO2 + 2 H2
SiCl2H2 + 2 N2O SiO2 + 2 N2 + 2 HCl
Si(OC2H5)4 SiO2 + byproducts
The choice of source gas depends on the thermal
stability of the substrate; for instance, aluminium is
sensitive to high temperature. Silane deposits
between 300 and 500 C, dichlorosilane at around
900 C, and TEOS between 650 and 750 C,
resulting in a layer of low- temperature oxide (LTO).
However, silane produces a lower-quality oxide
than the other methods (lower dielectric strength,
for instance), and it deposits nonconformally. Any
of these reactions may be used in LPCVD, but the
silane reaction is also done in APCVD. CVD oxide
invariably has lower quality than thermal oxide, but
thermal oxidation can only be used in the earliest
stages of IC manufacturing.
Oxide may also be grown with impurities
(alloying or "doping"). This may have two purposes.
During further process steps that occur at high
temperature, the impurities may diffuse from the
oxide into adjacent layers (most notably silicon)
and dope them. Oxides containing 515%
impurities by mass are often used for this purpose.
In addition, silicon dioxide alloyed with phosphorus
pentoxide ("P-glass") can be used to smooth out
uneven surfaces. P-glass softens and reflows at
temperatures above 1000 C. This process
requires a phosphorus concentration of at least 6%,
but concentrations above 8% can corrode
aluminium. Phosphorus is deposited from
phosphine gas and oxygen:
4 PH3 + 5 O2 2 P2O5 + 6 H2
Glasses containing both boron and phosphorus
(borophosphosilicate glass, BPSG) undergo
viscous flow at lower temperatures; around
850 C is achievable with glasses containing
around 5 weight % of both constituents, but
stability in air can be difficult to achieve.
Phosphorus oxide in high concentrations

interacts with ambient moisture to produce

phosphoric acid. Crystals of BPO4 can also
precipitate from the flowing glass on cooling;
these crystals are not readily etched in the
standard reactive plasmas used to pattern
oxides, and will result in circuit defects in
integrated circuit manufacturing.
Besides these intentional impurities, CVD oxide
may contain byproducts of the deposition.
TEOS produces a relatively pure oxide,
whereas silane introduces hydrogen impurities,
and dichlorosilane introduces chlorine.
Lower temperature deposition of silicon dioxide
and doped glasses from TEOS using ozone
rather than oxygen has also been explored
(350 to 500 C). Ozone glasses have excellent
conformality but tend to be hygroscopic that
is, they absorb water from the air due to the
incorporation of silanol (Si-OH) in the glass.
Infrared spectroscopy and mechanical strain as
a function of temperature are valuable
diagnostic tools for diagnosing such problems.
Silicon nitride[edit]
Silicon nitride is often used as an insulator and
chemical barrier in manufacturing ICs. The
following two reactions deposit silicon nitride
from the gas phase:
3 SiH4 + 4 NH3 Si3N4 + 12 H2
3 SiCl2H2 + 4 NH3 Si3N4 + 6 HCl + 6 H2
Silicon nitride deposited by LPCVD
contains up to 8% hydrogen. It also
experiences strong tensile stress,
which may crack films thicker than
200 nm. However, it has
higher resistivity and dielectric strength
than most insulators commonly
available in microfabrication (1016 cm
and 10 MV/cm, respectively).
Another two reactions may be used in
plasma to deposit SiNH:
2 SiH4 + N2 2 SiNH + 3 H2
SiH4 + NH3 SiNH + 3 H2
These films have much less
tensile stress, but worse
electrical properties (resistivity
106 to 1015 cm, and dielectric
strength 1 to 5 MV/cm).[12]

Metals[edit]

CVD for tungsten is achieved

from tungsten
hexafluoride (WF6), which may
be deposited in two ways:
WF6 W + 3 F2
WF6 + 3 H2 W + 6 HF
Other metals, notably
aluminium
and copper, can be
deposited by CVD. As
of 2010, commercially
cost-effective CVD for
copper did not exist,
although volatile
sources exist, such as
Cu(hfac)2. Copper is
typically deposited
by electroplating.
Aluminum can be
deposited
from triisobutylalumini
um (TIBAL) and
relatedorganoaluminiu
m compounds.
CVD
for molybdenum, tanta
lum, titanium, nickel is
widely used[citation needed].
These metals can
form
useful silicides when
deposited onto silicon.
Mo, Ta and Ti are
deposited by LPCVD,
from their
pentachlorides.
Nickel, molybdenum,
and tungsten can be
deposited at low
temperatures from
their carbonyl
precursors. In general,
for an arbitrary
metal M, the chloride
deposition reaction is
as follows:
2 MCl5 + 5 H2 2 M + 10 HCl
whereas the
carbonyl
decomposition

reaction can
happen
spontaneously
under thermal
treatment or
acoustic cavitation
and is as follows:
M(CO)n M + n CO
the
decompositio
n of metal
carbonyls is
often violently
precipitated
by moisture or
air, where
oxygen reacts
with the metal
precursor to
form metal or
metal oxide
along with
carbon
dioxide.
Niobium(V)
oxide layers
can be
produced by
the thermal
decompositio
n
of niobium(V)
ethoxide with
the loss
of diethyl
ether[13][14] acco
rding to the
equation:
2 Nb(OC2H5)5 Nb2O5 + 5 C2H5OC2H5

Graphe
ne[edit]
Many
variations
of CVD
can be
utilized to
synthesiz
e
graphene.
Although

many
advance
ments
have
been
made, the
processes
listed
below are
not
commerci
ally viable
yet.

Carbo
n
sourc
e

The most
popular
carbon
source
used to
produce
graphene
is
methane
gas. Less
popular
choices
include
petroleum
asphalt,
notable
for being
inexpensi
ve but
more
difficult to
work with.
[15]

Use
of
cataly
st

The use
of catalyst
is viable
in
changing
the

physical
process
of
graphene
productio
n. Notable
examples
include
iron
nanoparti
cles,
nickel
foam, and
gallium
vapor.
These
catalysts
can either
be used
in situ
during
graphene
buildup,[15]
[16]
or
situated
at some
distance
away at
the
deposition
area.[17] So
me
catalysts
require
another
step to
remove
them from
the
sample
material.
[16]

Physi
cal
condit
ions

Physical
conditions
such as
surroundi
ng

pressure,
temperatu
re, carrier
gas, and
chamber
material
play a big
role in
productio
n of
graphene.
Most
systems
use
LPCVD
with
pressures
ranging
from 1 to
1500 Pa.
[15][17][18][19]
H
owever,
some still
use
APCVD.[16]
Low
pressures
are used
more
commonly
as they
help
prevent
unwanted
reactions
and
produce
more
uniform
thickness
of
deposition
on the
substrate.
On the
other
hand,
temperatu
res used
range
from 8001050 C.

[15][16][17][18][19]

High
temperatu
res
translate
to an
increase
of the rate
of
reaction.
Caution
has to be
exercised
as high
temperatu
res do
pose
higher
danger
levels in
addition
to greater
energy
costs.

Carrie
r gas

Hydrogen
gas and
inert
gases
such as
argon are
flowed
into the
system.[15]
[16][17][18][19]
Th
ese gases
act as a
carrier,
enhancin
g surface
reaction
and
improving
reaction
rate,
thereby
increasing
deposition
of
graphene

onto the
substrate.

Cham
ber
mater
ial

Standard
quartz
tubing
and
chambers
are used
in CVD of
graphene.
[15][16][17][18][19]

Quartz is
chosen
because it
has a
very high
melting
point and
is
chemicall
y inert. In
order
words,
quartz
does not
interfere
with any
physical
or
chemical
reactions
regardles
s of the
conditions
.

Meth
ods of
analy
sis of
result
s

Raman
spectrosc
opy, X-ray
spectrosc

opy,
transmissi
on
electron
microscop
y (TEM),
and
scanning
electron
microscop
y (SEM)
are used
to
examine
and
characteri
ze the
graphene
samples.
[15][16][17][18][19]

Raman
spectrosc
opy is
used to
characteri
ze and
identify
the
graphene
particles;
X-ray
spectrosc
opy is
used to
characteri
ze
chemical
states;
TEM is
used to
provide
fine
details
regarding
the
internal
compositi
on of
graphene;
SEM is
used to
examine
the

surface
and
topograph
y.
Sometime
s, atomic
force
microscop
y (AFM) is
used to
measure
local
properties
such as
friction
and
magnetis
m.[18][19]

Diamon
d[edit]

Colorle
ss gem
cut
from
diamon
d
grown
by
chemic
al
vapor
deposit
ion

Main
article: C
VD
diamond
Chemical
vapor
deposition
(CVD)
can be
used to
produce
a syntheti
c
diamond
by
creating
the
circumsta
nces
necessary
for carbon
atoms in
a gas to
settle on
a
substrate
in
crystalline
form.
CVD
productio
n of
diamonds
has
received
a great
deal of
attention
in the
materials
sciences
because it
allows
many new
applicatio
ns of
diamonds
that had
previously
been
considere
d too

difficult to
make
economic
al. CVD
diamond
growth
typically
occurs
under
low press
ure (127
kPa;
0.145
3.926 psi;
7.5-203 T
orr) and
involves
feeding
varying
amounts
of gases
into a
chamber,
energizin
g them
and
providing
conditions
for
diamond
growth on
the
substrate.
The
gases
always
include a
carbon
source,
and
typically
include
hydrogen
as well,
though
the
amounts
used vary
greatly
dependin
g on the
type of
diamond

being
grown.
Energy
sources
include ho
t
filament,
microwav
e power,
and arc
discharge
s, among
others.
The
energy
source is
intended
to
generate
a plasma
in which
the gases
are
broken
down and
more
complex
chemistrie
s occur.
The
actual
chemical
process
for
diamond
growth is
still under
study and
is
complicat
ed by the
very wide
variety of
diamond
growth
processes
used.
Using
CVD,
films of
diamond
can be
grown

over large
areas of
substrate
with
control
over the
properties
of the
diamond
produced.
In the
past,
when high
pressure
high
temperatu
re (HPHT)
technique
s were
used to
produce a
diamond,
the result
was
typically
very small
free
standing
diamonds
of varying
sizes.
With CVD
diamond
growth
areas of
greater
than
fifteen
centimete
rs (six
inches)
diameter
have
been
achieved
and much
larger
areas are
likely to
be
successfu
lly coated
with

diamond
in the
future.
Improving
this
process is
key to
enabling
several
important
applicatio
ns.
The
growth of
diamond
directly on
a
substrate
allows the
addition
of many
of
diamond's
important
qualities
to other
materials.
Since
diamond
has the
highestth
ermal
conductivi
ty of any
bulk
material,
layering
diamond
onto high
heat
producing
electronic
s (such as
optics and
transistor
s) allows
the
diamond
to be
used as a
heat sink.
[20][21]
Diam
ond films

are being
grown on
valve
rings,
cutting
tools, and
other
objects
that
benefit
from
diamond's
hardness
and
exceeding
ly low
wear rate.
In each
case the
diamond
growth
must be
carefully
done to
achieve
the
necessary
adhesion
onto the
substrate.
Diamond'
s very
high
scratch
resistance
and
thermal
conductivi
ty,
combined
with a
lower coef
ficient of
thermal
expansion
than Pyre
x glass,
a coefficie
nt of
friction clo
se to that
of Teflon
(Polytetraf

luoroethyl
ene) and
strong lip
ophilicity
would
make it a
nearly
ideal nonstick
coating
for
cookware
if large
substrate
areas
could be
coated
economic
ally.
CVD
growth
allows
one to
control
the
properties
of the
diamond
produced.
In the
area of
diamond
growth,
the word
"diamond"
is used as
a
descriptio
n of any
material
primarily
made up
of sp3bonded c
arbon,
and there
are many
different
types of
diamond
included
in this. By
regulating

the
processin
g
parameter
s
especially
the gases
introduce
d, but
also
including
the
pressure
the
system is
operated
under, the
temperatu
re of the
diamond,
and the
method of
generatin
g plasma
many
different
materials
that can
be
considere
d
diamond
can be
made.
Single
crystal
diamond
can be
made
containing
various d
opants.[22]
Polycryst
alline
diamond
consisting
of grain
sizes from
several n
anometer
s to
several mi
crometers

can be
grown.[20][23]
Some
polycrysta
lline
diamond
grains are
surrounde
d by thin,
nondiamond
carbon,
while
others are
not.
These
different
factors
affect the
diamond's
hardness,
smoothne
ss,
conductivi
ty, optical
properties
and more.

Chalc
ogenid
es[edit]
Commerci
ally, merc
ury
cadmium
telluride is
of
continuing
interest
for
detection
of infrared
radiation.
Consistin
g of
an alloy of
CdTe and
HgTe, this
material
can be
prepared

from the
dimethyl
derivative
s of the
respective
elements.

See
also[edi
t]

Apoll
o
Diam
ond

Metal
organ
ic
Vapo
ur
Phas
e
Epita
xy

Atomi
c
layer
depos
ition

Bubbl
er
cylind
er

Carbo
nyl
metall
urgy

Electr
ostati
c
spray
assist
ed
vapou
r

depos
ition

Elem
ent
Six

Ion
platin
g

Virtua
l
metro
logy

Refere
nces[e
dit]
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Furthe
r

readin
g[edit]

Jaeg
er,
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rd C.
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).
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oduct
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and
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reedownl
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Denni
s W.
Hess,
CHE
MICA
L
VAPO
R
DEP
OSITI
ON
OF
DIEL
ECTR
IC
AND
META
L
FILM
Sfree
downl
oad fr
om
Electr
onic
Mater
ials
and
Proce
ssing:
Proce
eding
s of
the
First

Electr
onic
Mater
ials
and
Proce
ssing
Congr
ess
held
in
conju
nction
with
the
1988
World
Mater
ials
Congr
ess
Chica
go,
Illinoi
s,
USA,
24
30
Septe
mber
1988,
Edite
d by
Prabji
t
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(Spon
sored
by the
Electr
onic
Mater
ials
and
Proce
ssing
Divisi
on of
ASM
INTE
RNAT
IONA
L)

Categorie
s:
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processes
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Glass

coating
and
surface
modificati
on
Industrial

processes
Plasma

processin
g
Semicond

uctor
device
fabricatio
n
Synthetic

diamond
Thin film

deposition
Vacuum

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