Chemical vapor deposition

Chemical vapor deposition

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
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, carbon fiber, carbon
nanofibers, fluorocarbons, filaments, carbon nanotubes, SiO2,
silicon-germanium, tungsten, silicon carbide, silicon nitride, silicon
oxynitride, titanium nitride, and various high-k dielectrics. CVD is also
used to produce synthetic diamonds.

DC plasma (violet) enhances the growth of

carbon nanotubes in laboratory-scale PECVD
apparatus

Types
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.

Hot-wall thermal CVD (batch operation type)

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

pressures. Reduced pressures tend to reduce unwanted gas-phase
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.

Plasma assisted CVD

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.

Chemical vapor deposition

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. 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.
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 open-atmosphere, flame-based technique for depositing high-quality thin films and nanomaterials.
Hot filament CVD (HFCVD) also known as catalytic CVD (Cat-CVD) or more commonly, initiated CVD
(iCVD), this process uses a hot filament to chemically decompose the source gases. 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.
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.

Uses
CVD is commonly used to deposit conformal films and augment substrate surfaces in ways that more traditional
surface modification techniques are not capable of. 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 nitrides confer wear-resistance.[1] 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.

Commercially important materials prepared by CVD

Polysilicon
Polycrystalline silicon is deposited from trichlorosilane (SiHCl3) or silane (SiH4), using the following reactions:
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
7080% 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

Chemical vapor deposition

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
Silicon dioxide (usually called simply "oxide" in the semiconductor industry) may be deposited by several different
processes. Common source gases include silane and oxygen, dichlorosilane (SiCl2H2) and nitrous oxide[2] (N2O), or
tetraethylorthosilicate (TEOS; Si(OC2H5)4). The reactions are as follows Wikipedia: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.

Chemical vapor deposition

Silicon nitride
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 200nm. 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).

Metals
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[3], 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 triisobutylaluminium (TIBAL) and related organoaluminium
compounds.
CVD for molybdenum, tantalum, titanium, nickel is widely usedWikipedia: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 decomposition 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 decomposition of niobium(V) ethoxide with the loss of
diethyl ether according to the equation:
2 Nb(OC2H5)5 Nb2O5 + 5 C2H5OC2H5

Chemical vapor deposition

Diamond
Chemical vapor deposition (CVD) can be used to produce a synthetic
diamond by creating the circumstances necessary for carbon atoms in a
gas to settle on a substrate in crystalline form.
CVD production of diamonds has received a great deal of attention in
the materials sciences because it allows many new applications of
diamonds that had previously been considered too difficult to make
economical. CVD diamond growth typically occurs under low pressure
(127 kPa; 0.1453.926 psi; 7.5-203 Torr) and involves feeding
varying amounts of gases into a chamber, energizing them and
providing conditions for diamond growth on the substrate. The gases
Colorless gem cut from diamond grown by
always include a carbon source, and typically include hydrogen as
chemical vapor deposition
well, though the amounts used vary greatly depending on the type of
diamond being grown. Energy sources include hot filament,
microwave power, and arc discharges, among others. The energy source is intended to generate a plasma in which
the gases are broken down and more complex chemistries occur. The actual chemical process for diamond growth is
still under study and is complicated 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 temperature (HPHT) techniques 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 centimeters (six inches) diameter have been achieved and much larger areas are likely to
be successfully coated with diamond in the future. Improving this process is key to enabling several important
applications.
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 highest thermal conductivity of any bulk material, layering diamond onto high heat
producing electronics (such as optics and transistors) allows the diamond to be used as a heat sink. Diamond films
are being grown on valve rings, cutting tools, and other objects that benefit from diamond's hardness and
exceedingly 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 conductivity, combined with a lower
coefficient of thermal expansion than Pyrex glass, a coefficient of friction close to that of Teflon
(Polytetrafluoroethylene) and strong lipophilicity would make it a nearly ideal non-stick coating for cookware if
large substrate areas could be coated economically.
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 description of any material primarily made up of sp3 bonded carbon, and there are many
different types of diamond included in this. By regulating the processing parametersespecially the gases
introduced, but also including the pressure the system is operated under, the temperature of the diamond, and the
method of generating plasmamany different materials that can be considered diamond can be made. Single crystal
diamond can be made containing various dopants. Polycrystalline diamond consisting of grain sizes from several
nanometers to several micrometers can be grown. Some polycrystalline diamond grains are surrounded by thin,
non-diamond carbon, while others are not. These different factors affect the diamond's hardness, smoothness,
conductivity, optical properties and more.

Chemical vapor deposition

Chalcogenides
Commercially, mercury cadmium telluride is of continuing interest for detection of infrared radiation. Consisting of
an alloy of CdTe and HgTe, this material can be prepared from the dimethyl derivatives of the respective elements.

References
[1] Georg Wahl, Paul B. Davies, Rointan F. Bunshah, Bruce A. Joyce, Colin D. Bain, Gerhard Wegner, Markus Remmers, Francis C. Walsh,
Konrad Hieber, Jan-Eric Sundgren, Peter K. Bachmann, Shintaro Miyazawa, Alfred Thelen and Heiner Strathmann "Thin Films" Ullmann's
Encyclopedia of Industrial Chemistry 2000, Wiley-VCH, Weinheim.
[2] Proceedings of the Third World Congress of Chemical Engineering, Tokyo, p. 290 (1986)
[3] http:/ / en. wikipedia. org/ w/ index. php?title=Chemical_vapor_deposition& action=edit

Further reading
Jaeger, Richard C. (2002). "Film Deposition". Introduction to Microelectronic Fabrication (2nd ed.). Upper
Saddle River: Prentice Hall. ISBN0-201-44494-1.
Smith, Donald (1995). Thin-Film Deposition: Principles and Practice. MacGraw-Hill. ISBN0-07-058502-4.
Dobkin and Zuraw (2003). Principles of Chemical Vapor Deposition. Kluwer. ISBN1-4020-1248-9.
K. Okada "Plasma-enhanced chemical vapor deposition of nanocrystalline diamond" Sci. Technol. Adv. Mater. 8
(2007) 624 (http://dx.doi.org/10.1016/j.stam.2007.08.008) free-download review
T. Liu, D. Raabe and S. Zaefferer "A 3D tomographic EBSD analysis of a CVD diamond thin film" Sci. Technol.
Adv. Mater. 9 (2008) 035013 (http://dx.doi.org/10.1088/1468-6996/9/3/035013) free-download
Christoph Wild "CVD Diamond Properties and Useful Formula" CVD Diamond Booklet (2008) PDF (http://
www.diamond-materials.com/downloads/cvd_diamond_booklet.pdf) free-download
Dennis W. Hess, CHEMICAL VAPOR DEPOSITION OF DIELECTRIC AND METAL FILMS (http://www.
dtic.mil/cgi-bin/GetTRDoc?AD=ADA204709#page=74)free-download from Electronic Materials and
Processing: Proceedings of the First Electronic Materials and Processing Congress held in conjunction with the
1988 World Materials Congress Chicago, Illinois, USA, 2430 September 1988, Edited by Prabjit Singh
(Sponsored by the Electronic Materials and Processing Division of ASM INTERNATIONAL)

External links
Fundamentals of Chemical Vapor Deposition (http://www.timedomaincvd.com/CVD_Fundamentals/
Fundamentals_of_CVD.html), by TimeDomain CVD, Inc.
Traditional Coating Technologies (http://www.ngimat.com/technology/ccvd.html)
Chemical vapor deposition with atmospheric plasma (http://www.acxys.com/processes/coating)

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