5/6/2014 Silicon carbide - Wikipedia, the free encyclopedia

Silicon carbide
From Wikipedia, the free encyclopedia

Silicon carbide (SiC), also known as carborundum /kɑrbəˈrʌndəm/, is a

Silicon carbide
compound of silicon and carbon with chemical formula SiC. It occurs in
nature as the extremely rare mineral moissanite. Silicon carbide powder has
been mass-produced since 1893 for use as an abrasive. Grains of silicon
carbide can be bonded together by sintering to form very hard ceramics
that are widely used in applications requiring high endurance, such as car
brakes, car clutches and ceramic plates in bulletproof vests. Electronic
applications of silicon carbide as light-emitting diodes (LEDs) and
detectors in early radios were first demonstrated around 1907, and today
SiC is widely used in high-temperature/high-voltage semiconductor
electronics. Large single crystals of silicon carbide can be grown by the
Lely method; they can be cut into gems known as synthetic moissanite.
Silicon carbide with high surface area can be produced from SiO2
Preferred IUPAC name
contained in plant material.
Silicon carbide

Contents Other names

Carborundum
1 Discovery and early production Moissanite

1.1 Early experiments Identifiers

1.2 Wide scale production CAS number 409-21-2
2 Natural occurrence
PubChem 9863
3 Production
ChemSpider 9479
4 Structure and properties
EC number 206-991-8
4.1 Electrical conductivity
MeSH Silicon+carbide
5 Uses
ChEBI CHEBI:29390
5.1 Abrasive and cutting tools
RTECS VW0450000
5.2 Structural material
number
5.3 Automobile parts
Gmelin 13642
5.4 Electric systems Reference
5.5 Electronic circuit elements Jmol-3D Image 1
5.5.1 Power electronic devices images (http://chemapps.stolaf.edu/jmol/jmol.php?
5.5.2 LEDs model=%5BC-%5D%23%5BSi%2B%5D)
5.6 Astronomy SMILES
5.7 Thin filament pyrometry InChI
5.8 Heating elements Properties
5.9 Nuclear fuel particles Molecular CSi
formula
5.10 Nuclear fuel cladding
Molar mass 40.10 g mol−1
5.11 Jewelry
5.12 Steel production Appearance Colorless crystals
Density 3.21 g·cm−3 (all polytypes )[1]
5.13 Catalyst support
5.14 Carborundum printmaking Melting 2,730 °C (4,950 °F; 3,000 K)
point (decomposes)
5.15 Graphene production
Electron ~900 cm2/V·s (all polytypes)
6 See also
mobility
7 References
Refractive 2.55 (infrared; all polytypes)[2]
8 External links index (nD)

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Hazards
EU Not listed
classification
Discovery and early production
NFPA 704
0
Early experiments 1 0
Non-systematic, less-recognized, and often unverified syntheses of silicon
carbide include Except where noted otherwise, data are given for
materials in their standard state (at 25 °C (77 °F),
J. J. Berzelius's reduction of potassium fluorosilicate by potassium 100 kPa)
(1810) (verify) (what is: / ?)
César-Mansuète Despretz's passing an electric current through a Infobox references
carbon rod embedded in sand (1849)
Robert Sydney Marsden's (1856–1919) dissolution of silica in molten silver in a graphite crucible (1881)
Albert Colson's heating of silicon under a stream of ethylene (1882)
Paul Schuetzenberger's heating of a mixture of silicon and silica in a graphite crucible (1881).[3]

Wide scale production

Wide-scale production is credited to Edward Goodrich Acheson in 1890.[4] Acheson

was attempting to prepare artificial diamonds when he heated a mixture of clay
(aluminum silicate) and powdered coke (carbon) in an iron bowl. He called the blue
crystals that formed Carborundum, believing it to be a new compound of carbon and
aluminum, similar to corundum. In 1893, Henri Moissan discovered the very rare
naturally-occurring SiC mineral while examining rock samples found in the Canyon
A replication of H.J. Round's LED Diablo meteorite in Arizona. The mineral was named moissanite in his honor. Moissan
experiments also synthesized SiC by several routes, including dissolution of carbon in molten silicon,
melting a mixture of calcium carbide and silica, and by reducing silica with carbon in an
electric furnace.

Acheson patented the method for making silicon carbide powder on February 28, 1893.[5] Acheson also developed the electric
batch furnace by which SiC is still made today and formed The Carborundum Company to manufacture bulk SiC, initially for use
as an abrasive.[6] In 1900 the company settled with the Electric Smelting and Aluminum Company when a judge's decision gave
"priority broadly" to its founders "for reducing ores and other substances by the incandescent method".[7] It is said that Acheson
was trying to dissolve carbon in molten corundum (alumina) and discovered the presence of hard, blue-black crystals which he
believed to be a compound of carbon and corundum: hence carborundum. It may be that he named the material "carborundum" by
analogy to corundum, which is another very hard substance (9 on the Mohs scale).

The first use of SiC was as an abrasive. This was followed by electronic applications. In the beginning of the 20th century, silicon
carbide was used as a detector in the first radios,[8] and in 1907 Henry Joseph Round produced the first LED by applying a
voltage to a SiC crystal and observing yellow, green and orange emission at the cathode. Those experiments were later repeated
by O. V. Losev in the Soviet Union in 1923.[9]

Natural occurrence
Naturally occurring moissanite is found in only minute quantities in certain types of meteorite and in corundum deposits and
kimberlite. Virtually all the silicon carbide sold in the world, including moissanite jewels, is synthetic. Natural moissanite was first
found in 1893 as a small component of the Canyon Diablo meteorite in Arizona by Dr. Ferdinand Henri Moissan, after whom the
material was named in 1905.[10] Moissan's discovery of naturally occurring SiC was initially disputed because his sample may have
been contaminated by silicon carbide saw blades that were already on the market at that time.[11]

While rare on Earth, silicon carbide is remarkably common in space. It is a common form of stardust found around carbon-rich
stars, and examples of this stardust have been found in pristine condition in primitive (unaltered) meteorites. The silicon carbide
found in space and in meteorites is almost exclusively the beta-polymorph. Analysis of SiC grains found in the Murchison meteorite,

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a carbonaceous chondrite meteorite, has revealed anomalous isotopic ratios of carbon and silicon, indicating an origin from outside
the solar system; 99% of these SiC grains originate around carbon-rich asymptotic giant branch stars.[12] SiC is commonly found
around these stars as deduced from their infrared spectra.[13]

Production
Because of the rarity of natural moissanite, most silicon carbide is synthetic. It is used as an abrasive, and more recently as a
semiconductor and diamond simulant of gem quality. The simplest manufacturing process is to combine silica sand and carbon in an
Acheson graphite electric resistance furnace at a high temperature, between 1,600 °C
(2,910 °F) and 2,500 °C (4,530 °F). Fine SiO2 particles in plant material (e.g. rice
husks) can be converted to SiC by heating in the excess carbon from the organic
material.[14] The silica fume, which is a byproduct of producing silicon metal and
ferrosilicon alloys, also can be converted to SiC by heating with graphite at 1,500 °C
(2,730 °F).[15]

The material formed in the Acheson furnace varies in purity, according to its distance
from the graphite resistor heat source. Colorless, pale yellow and green crystals have the
highest purity and are found closest to the resistor. The color changes to blue and black
at greater distance from the resistor, and these darker crystals are less pure. Nitrogen
and aluminium are common impurities, and they affect the electrical conductivity of
SiC.[16] Moissanite single crystal (≈1 mm in
size)
Pure silicon carbide can be made by the so-called Lely process,[17] in which SiC
powder is sublimated into high-temperature species of silicon, carbon, silicon dicarbide
(SiC2), and disilicon carbide (Si2C) in an argon gas ambient at 2500 °C and redeposited
into flake-like single crystals,[18] sized up to 2×2 cm, at a slightly colder substrate. This
process yields high-quality single crystals, mostly of 6H-SiC phase (because of high
growth temperature). A modified Lely process involving induction heating in graphite
crucibles yields even larger single crystals of 4 inches (10 cm) in diameter, having a Synthetic SiC crystals ~3 mm in
section 81 times larger compared to the conventional Lely process.[19] Cubic SiC is diameter
usually grown by the more expensive process of chemical vapor deposition
(CVD).[16][20] Homoepitaxial and heteroepitaxial SiC layers can be grown employing
both gas and liquid phase approaches.[21] Pure silicon carbide can also be prepared by
the thermal decomposition of a polymer, poly(methylsilyne), under an inert atmosphere at
low temperatures. Relative to the CVD process, the pyrolysis method is advantageous
because the polymer can be formed into various shapes prior to thermalization into the
ceramic.[21][22][23][24]
Synthetic SiC Lely crystals
Structure and properties
Structure of major SiC polytypes.

(β)3C-SiC 4H-SiC (α)6H-SiC

Silicon carbide exists in about 250 crystalline forms.[25] The polymorphism of SiC is characterized by a large family of similar
crystalline structures called polytypes. They are variations of the same chemical compound that are identical in two dimensions and
differ in the third. Thus, they can be viewed as layers stacked in a certain sequence.[26]

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Alpha silicon carbide (α-SiC) is the most commonly encountered polymorph; it is formed at temperatures greater than 1700 °C
and has a hexagonal crystal structure (similar to Wurtzite). The beta modification (β-SiC), with a zinc blende crystal structure
(similar to diamond), is formed at temperatures below 1700 °C.[27] Until recently, the beta form has had relatively few commercial
uses, although there is now increasing interest in its use as a support for heterogeneous catalysts, owing to its higher surface area
compared to the alpha form.

Pure SiC is colorless. The

brown to black color of Properties of major SiC polytypes [2][21]
industrial product results Polytype 3C (β) 4H 6H (α)
from iron impurities. The Crystal structure Zinc blende (cubic) Hexagonal Hexagonal
rainbow-like luster of the
crystals is caused by a Space group T2d -F43m C46v -P63mc C46v -P63mc
passivation layer of silicon
dioxide that forms on the
surface. Pearson symbol cF8 hP8 hP12
The high sublimation Lattice constants (Å) 4.3596 3.0730; 10.053 3.0810; 15.12
temperature of SiC Density (g/cm3 ) 3.21 3.21 3.21
(approximately 2700 °C)
makes it useful for bearings Bandgap (eV) 2.36 3.23 3.05
and furnace parts. Silicon Bulk modulus (GPa) 250 220 220
carbide does not melt at any
known pressure. It is also Thermal conductivity (W cm−1 K−1 )
highly inert chemically. There 3.6 3.7 4.9
is currently much interest in @ 300K (see [28] for temp. dependence)
its use as a semiconductor
material in electronics, where
its high thermal conductivity, high electric field breakdown strength and high maximum current density make it more promising than
silicon for high-powered devices.[29] SiC also has a very low coefficient of thermal expansion (4.0 × 10−6/K) and experiences no
phase transitions that would cause discontinuities in thermal expansion.[16]

Electrical conductivity

Silicon carbide is a semiconductor, which can be doped n-type by nitrogen or phosphorus and p-type by aluminium, boron, gallium
or beryllium.[2] Metallic conductivity has been achieved by heavy doping with boron, aluminium or nitrogen. Superconductivity has
been detected in 3C-SiC:Al, 3C-SiC:B and 6H-SiC:B at the same temperature of 1.5 K.[27][30] A crucial difference is however
observed for the magnetic field behavior between aluminium and boron doping: SiC:Al is type-II, same as Si:B. On the contrary,
SiC:B is type-I. In attempt to explain this difference, it was noted that Si sites are more important than carbon sites for
superconductivity in SiC. Whereas boron substitutes carbon in SiC, Al substitutes Si sites. Therefore, Al and B "see" different
environment that might explain different properties of SiC:Al and SiC:B.[31]

Uses
Abrasive and cutting tools

In the arts, silicon carbide is a popular abrasive in modern lapidary due to the durability
and low cost of the material. In manufacturing, it is used for its hardness in abrasive
machining processes such as grinding, honing, water-jet cutting and sandblasting.
Particles of silicon carbide are laminated to paper to create sandpapers and the grip tape
on skateboards.[32]

In 1982 an exceptionally strong composite of aluminium oxide and silicon carbide

whiskers was discovered. Development of this laboratory-produced composite to a
commercial product took only three years. In 1985, the first commercial cutting tools
Cutting disks made of SiC
made from this alumina and silicon carbide whisker-reinforced composite were
introduced by the Advanced Composite Materials Corporation (ACMC) and Greenleaf
Corporation.[33]

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Structural material

In the 1980s and 1990s, silicon carbide was studied in several research programs for
high-temperature gas turbines in Europe, Japan and the United States. The components
were intended to replace nickel superalloy turbine blades or nozzle vanes. However,
none of these projects resulted in a production quantity, mainly because of its low impact
resistance and its low fracture toughness.[34]

Like other hard ceramics (namely alumina and boron carbide), silicon carbide is used in
composite armor (e.g. Chobham armor), and in ceramic plates in bulletproof vests.
Dragon Skin, which is produced by Pinnacle Armor, uses disks of silicon carbide.[35]

Silicon carbide is used as a support and shelving material in high temperature kilns such
as for firing ceramics, glass fusing, or glass casting. SiC kiln shelves are considerably
lighter and more durable than traditional alumina shelves.[36]
Silicon carbide is used for trauma
Automobile parts
plates of ballistic vests

Silicon-infiltrated carbon-carbon composite is

used for high performance "ceramic" brake discs, as it is able to withstand extreme
temperatures. The silicon reacts with the graphite in the carbon-carbon composite to
become carbon-fiber-reinforced silicon carbide (C/SiC). These discs are used on some
road-going sports cars, supercars, as well as other performance cars including the
Porsche Carrera GT, the Bugatti Veyron, the Chevrolet Corvette ZR1, Bentleys,
Ferraris, Lamborghinis, some specific high performance Audis, and the McLaren P1.[37]
Silicon carbide is also used in a sintered form for diesel particulate filters.[38] SiC is also
used as an oil additive to reduce friction, emissions, and harmonics.[39]
The Porsche Carrera GT's carbon-
ceramic (silicon carbide) disc brake
Electric systems

The earliest electrical application of SiC was in lightning arresters in electric power systems. These devices must exhibit high
resistance until the voltage across them reaches a certain threshold VT, at which point their resistance must drop to a lower level
and maintain this level until the applied voltage drops below VT.[40]

It was recognized early on that SiC had such a voltage-dependent resistance, and so columns of SiC pellets were connected
between high-voltage power lines and the earth. When a lightning strike to the line raises the line voltage sufficiently, the SiC column
will conduct, allowing strike current to pass harmlessly to the earth instead of along the power line. Such SiC columns proved to
conduct significantly at normal power-line operating voltages and thus had to be placed in series with a spark gap. This spark gap is
ionized and rendered conductive when lightning raises the voltage of the power line conductor, thus effectively connecting the SiC
column between the power conductor and the earth. Spark gaps used in lightning arresters are unreliable, either failing to strike an
arc when needed or failing to turn off afterwards, in the latter case due to material failure or contamination by dust or salt. Usage of
SiC columns was originally intended to eliminate the need for the spark gap in a lightning arrester. Gapped SiC lightning arresters
were used as lightning-protection tool and sold under GE and Westinghouse brand names, among others. The gapped SiC arrester
has been largely displaced by no-gap varistors that use columns of zinc oxide pellets.[41]

Electronic circuit elements

Power electronic devices

Silicon carbide is a semiconductor in research and early mass-production providing advantages for fast, high-temperature and/or
high-voltage devices. First devices available were Schottky diodes, followed by Junction-gate FETs and MOSFETs for high-
power switching. Bipolar transistors and thyristors are currently developed.[29] A major problem for SiC commercialization has
been the elimination of defects: edge dislocations, screw dislocations (both hollow and closed core), triangular defects and basal
plane dislocations.[42] As a result, devices made of SiC crystals initially displayed poor reverse blocking performance though
researchers have been tentatively finding solutions to improving the breakdown performance.[43] Apart from crystal quality,
problems with the interface of SiC with silicon dioxide have hampered the development of SiC-based power MOSFETs and
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insulated-gate bipolar transistors. Although the mechanism is still unclear, nitridation has
dramatically reduced the defects causing the interface problems.[44] In 2008, the first
commercial JFETs rated at 1200 V were introduced to the market, followed in 2011 by
the first commercial MOSFETs rated at 1200 V. Beside SiC switches and SiC Schottky
diodes (also Schottky barrier diode – SBD) in the popular TO-247 package, companies
started even earlier to implement the bare chips into their power modules. SiC SBD
diodes found wide market spread being used in PFC circuits and IGBT power modules.
Conferences such as the International Conference on Integrated Power Electronics
Systems (CIPS) report regularly about the technological progress of SIC power devices.
Major challenges for fully unleashing the capabilities of SiC power devices are: Ultraviolet LED

gate drive: SiC devices often require gate drive voltage levels that are different
from their silicon counterparts and may be even unsymmetic, e.g. +20V and -5V.
packaging: SiC chips (Die (integrated circuit)) may have a higher power density that silicon power devices and are able to
handle higher temperatures exceeding the silicon limit of 150°C. New die attach technologies as sintering are required to
efficiently get the heat out of the devices and ensure a reliable interconnection.

LEDs

The first LED action was demonstrated in 1907 using SiC and the first commercial LEDs were again based on SiC. Yellow LEDs
made from 3C-SiC were manufactured in the Soviet Union in the 1970s,[45] and blue ones (6H-SiC) worldwide in the 1980s.[46]
The production was soon stopped because gallium nitride showed 10–100 times brighter emission. This difference in efficiency is
due to the unfavorable indirect bandgap of SiC, whereas GaN has a direct bandgap which favors light emission. However, SiC is
still one of the important LED components – it is a popular substrate for growing GaN devices, and it also serves as a heat
spreader in high-power LEDs.[46]

Astronomy

The low thermal expansion coefficient, high hardness, rigidity and thermal conductivity make silicon carbide a desirable mirror
material for astronomical telescopes. The growth technology (chemical vapor deposition) has been scaled up to produce disks of
polycrystalline silicon carbide up to 3.5 meters in diameter, and several telescopes (like the Herschel Space Telescope) are already
equipped with SiC optics.[47][48]

Thin filament pyrometry

Silicon carbide fibers are used to measure gas temperatures in an optical technique called thin filament pyrometry. It involves the
placement of a thin filament in a hot gas stream. Radiative emissions from the filament can be correlated with filament temperature.
Filaments are SiC fibers with a diameter of 15 micrometers; about one fifth that of a human hair. Because the fibers are so thin, they
do little to disturb the flame and their temperature remains close to that of the local gas. Temperatures of about 800–2500 K can
be measured.[49][50]

Heating elements

References to silicon carbide heating elements exist from the early 20th century when they were produced by Acheson's
Carborundum Co. in the U.S. and EKL in Berlin. Silicon carbide offered increased operating temperatures compared with metallic
heaters. Silicon carbide elements are used today in the melting of glass and non-ferrous metal, heat treatment of metals, float glass
production, production of ceramics and electronics components, igniters in pilot lights for gas heaters, etc.[51]

Nuclear fuel particles

Silicon carbide is an important material in TRISO-coated fuel particles, the type of nuclear fuel found in high temperature gas
cooled reactors (such as the Pebble Bed Reactor). A layer of silicon carbide gives coated fuel particles structural support and is the
main diffusion barrier to the release of fission products.[52]

Nuclear fuel cladding

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Silicon carbide composite material has been investigated for use as a replacement for Zircaloy cladding in light water reactors. The
composite consists of SiC fibers wrapped around a SiC inner layer and surrounded by an SiC outer layer.[53] Problems have been
reported with the ability to join the pieces of the SiC composite.[54]

Jewelry

As a gemstone used in jewelry, silicon carbide is called "synthetic moissanite" or just "moissanite" after the mineral name.
Moissanite is similar to diamond in several important respects: it is transparent and hard (9–9.5 on the Mohs scale, compared to 10
for diamond), with a refractive index between 2.65 and 2.69 (compared to 2.42 for diamond). Moissanite is somewhat harder than
common cubic zirconia. Unlike diamond, moissanite can be strongly birefringent. For this reason, moissanite jewels are cut along
the optic axis of the crystal to minimize birefringent effects. It is lighter (density 3.21 g/cm3 vs. 3.53 g/cm3), and much more
resistant to heat than diamond. This results in a stone of higher luster, sharper facets and good resilience. Loose moissanite stones
may be placed directly into wax ring moulds for lost-wax casting, as can diamond,[55] as moissanite remains undamaged by
temperatures up to 1800 °C. Moissanite has become popular as a diamond substitute, and may be misidentified as diamond, since
its thermal conductivity is closer to diamond than any other substitute. Many thermal diamond-testing devices cannot distinguish
moissanite from diamond, but the gem is distinct in its birefringence and a very slight green or yellow fluorescence under ultraviolet
light. Some moissanite stones also have curved, string-like inclusions, which diamonds never have.[56]

Steel production

Silicon carbide, dissolved in a basic oxygen

furnace used for making steel, acts as a fuel. The
additional energy liberated allows the furnace to
process more scrap with the same charge of hot
metal. It can also be used to raise tap
temperatures and adjust the carbon and silicon
A moissanite ring content. Silicon carbide is cheaper than a
combination of ferrosilicon and carbon, produces
cleaner steel and less emissions due to low levels of trace elements, has a low gas content,
and does not lower the temperature of steel.[57]

Catalyst support

The natural resistance to oxidation exhibited by silicon carbide, as well as the discovery of
new ways to synthesize the cubic β-SiC form, with its larger surface area, has led to
significant interest in its use as a heterogeneous catalyst support. This form has already
been employed as a catalyst support for the oxidation of hydrocarbons, such as n-butane,
to maleic anhydride.[58][59]

Carborundum printmaking

Silicon carbide is used in carborundum printmaking – a collagraph printmaking technique.

Carborundum grit is applied in a paste to the surface of an aluminium plate. When the paste
Image of the test flame and
is dry, ink is applied and trapped in its granular surface, then wiped from the bare areas of
glowing SiC fibers. The flame is
the plate. The ink plate is then printed onto paper in a rolling-bed press used for intaglio
about 7 cm tall.
printmaking. The result is a print of painted marks embossed into the paper.[60]

Graphene production

Silicon carbide is used to produce epitaxial graphene by graphitization at high temperatures. This is considered as one of the
promising methods to synthesize graphene at large scale for practical applications.[61][62]

See also
Reaction bonded silicon carbide

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References

Piece of silicon carbide used in steel

making

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External links
A Brief History of Silicon Carbide (http://img.chem.ucl.ac.uk/www/kelly/moissanite.htm) Dr J F Kelly, University of London
Material Safety Data Sheet (http://www.sciencelab.com/msds.php?msdsId=9924922) for Silicon Carbide
Moissanite on Mindat.org (http://www.mindat.org/min-2743.html)
CDC – NIOSH Pocket Guide to Chemical Hazards (http://www.cdc.gov/niosh/npg/npgd0555.html)

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