Silicon carbide

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"Carborundum" redirects here. Not to be confused with Corundum.

Silicon carbide
monocrystal
Names
Preferred IUPAC name
Silicon carbide
Other names
Carborundum
Moissanite
Identifiers
3D model (
JSmol
)
ChEBI
ChemSpider
ECHA InfoCard
 100.006.357 Edit this at Wikidata
EC Number
  • 206-991-8
13642
MeSH Silicon+carbide
RTECS number
  • VW0450000
UNII
  • InChI=1S/CSi/c1-2 checkY
    Key: HBMJWWWQQXIZIP-UHFFFAOYSA-N checkY
  • Key: HBMJWWWQQXIZIP-UHFFFAOYAF
  • InChI=1/CSi/c1-2
  • [C-]#[Si+]
Properties
SiC
Molar mass 40.096 g/mol
Appearance Yellow to green to bluish-black, iridescent crystals[1]
Density 3.16 g⋅cm-3 (hex.)[2]
Melting point 2,830 °C (5,130 °F; 3,100 K)[2] (decomposes)
Solubility Insoluble in water, soluble in molten alkalis and molten iron[3]
Electron mobility ~900 cm2/(V⋅s) (all polytypes)
−12.8 × 10−6 cm3/mol[4]
2.55 (infrared; all polytypes)[5]
Hazards
GHS labelling:fibres[6]
GHS08: Health hazard
Danger
H350i
P201, P202, P260, P261, P264, P270, P271, P280, P281, P302+P352, P304+P340, P305+P351+P338, P308+P313, P312, P314, P321, P332+P313, P337+P313, P362, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1
0
0
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 15 mg/m3 (total) TWA 5 mg/m3 (resp)[1]
REL (Recommended)
 TWA 10 mg/m3 (total) TWA 5 mg/m3 (resp)[1]
IDLH
(Immediate danger)
 N.D.[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

Silicon carbide (SiC), also known as carborundum (

ceramic plates in bulletproof vests. Large single crystals of silicon carbide can be grown by the Lely method
and they can be cut into gems known as synthetic moissanite.

Electronic applications of silicon carbide such as

detectors
in early radios were first demonstrated around 1907. SiC is used in semiconductor electronics devices that operate at high temperatures or high voltages, or both.

Natural occurrence

Moissanite single crystal (≈1 mm in size)

Naturally occurring moissanite is found in only minute quantities in certain types of meteorite, 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

saw blades that were already on the market at that time.[8]

While rare on Earth, silicon carbide is remarkably common in space. It is a common form of

beta-polymorph. Analysis of SiC grains found in the Murchison meteorite, a carbonaceous chondrite meteorite, has revealed anomalous isotopic ratios of carbon and silicon, indicating that these grains originated outside the solar system.[9]

History

Early experiments

Non-systematic, less-recognized and often unverified syntheses of silicon carbide include:

  • César-Mansuète Despretz's passing an electric current through a carbon rod embedded in sand (1849)
  • Robert Sydney Marsden's dissolution of silica in molten silver in a graphite crucible (1881)
  • Paul Schuetzenberger's heating of a mixture of silicon and silica in a graphite crucible (1881)
  • Albert Colson's heating of silicon under a stream of ethylene (1882).[10]

Wide-scale production

A replication of H. J. Round's LED experiments

Wide-scale production is credited to Edward Goodrich Acheson in 1891.[11] Acheson was attempting to prepare artificial diamonds when he heated a mixture of clay (aluminium 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 aluminium, similar to corundum. Moissan 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.[12] 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.[13] 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".[14]

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.

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. The effect was later rediscovered by O. V. Losev in the Soviet Union in 1923.[16]

Production

Synthetic SiC crystals ~3 mm in diameter
Two six-inch wafers made of silicon carbide

Because natural moissanite is extremely scarce, most silicon carbide is synthetic. Silicon carbide is used as an abrasive, as well as a

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.[17] The silica fume, which is a byproduct of producing silicon metal and ferrosilicon alloys, can also be converted to SiC by heating with graphite at 1,500 °C (2,730 °F).[18]

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.[19]

Synthetic SiC Lely crystals

Pure silicon carbide can be made by the

Lely process,[20] in which SiC powder is sublimed 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,[21]
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 section 81 times larger compared to the conventional Lely process.[22]

Cubic SiC is usually grown by the more expensive process of chemical vapor deposition (CVD) of silane, hydrogen and nitrogen.

[19][23] Homoepitaxial and heteroepitaxial SiC layers can be grown employing both gas and liquid phase approaches.[24]

To form complexly shaped SiC,

inert atmosphere at relatively 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.[27][28][29][30]

SiC can also be made into wafers by cutting a single crystal either using a diamond wire saw or by using a laser. SiC is a useful semiconductor used in power electronics.[31]

Structure and properties

Main article: Polymorphs of silicon carbide
Structure of major SiC polytypes.
(β)3C-SiC 4H-SiC (α)6H-SiC
Silicon carbide, image taken under a stereoscopic microscope.

Silicon carbide exists in about 250 crystalline forms.

preceramic polymers, silicon carbide in a glassy amorphous form is also produced.[33] 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.[34]

Alpha silicon carbide (α-SiC) is the most commonly encountered

heterogeneous catalysts
, owing to its higher surface area compared to the alpha form.

Properties of major SiC polytypes[5][27]
Polytype 3C (β) 4H 6H (α)
Crystal structure Zinc blende (cubic) Hexagonal Hexagonal
Space group T2d-F43m C46v-P63mc C46v-P63mc
Pearson symbol cF8 hP8 hP12
Lattice constants (Å) 4.3596 3.0730; 10.053 3.0810; 15.12
Density (g/cm3) 3.21 3.21 3.21
Bandgap
(eV) 		2.36 3.23 3.05
Bulk modulus (GPa) 250 220 220
Thermal conductivity (W⋅m−1⋅K−1)
@300 K (see [36][37]
for temp. dependence) 		320 348 325
Thermal Expansion Coefficient (10−6 K−1)
@300 K (see [38] for temp. dependence) 		-- 2.28 (⊥ c); 2.49 (∥ c) 2.25

Pure SiC is colorless. The brown to black color of the industrial product results from iron impurities.[39] The rainbow-like luster of the crystals is due to the thin-film interference of a passivation layer of silicon dioxide that forms on the surface.

The high sublimation temperature of SiC (approximately 2700 °C) makes it useful for

coefficient of thermal expansion of about 2.3 × 10−6 K−1 near 300 K (for 4H and 6H SiC) and experiences no phase transitions in the temperature range 5 K to 340 K that would cause discontinuities in the thermal expansion coefficient.[19][38]

Electrical conductivity

Silicon carbide is a semiconductor, which can be doped n-type by nitrogen or phosphorus and p-type by beryllium, boron, aluminium, or gallium.[5] Metallic conductivity has been achieved by heavy doping with boron, aluminium or nitrogen.

type-I, as is 6H-SiC:B. Thus the superconducting properties seem to depend more on dopant (B vs. Al) than on polytype (3C- vs 6H-). In an attempt to explain this dependence, it was noted that B substitutes at C sites in SiC, but Al substitutes at Si sites. Therefore, Al and B "see" different environments, in both polytypes.[42]

Uses

Abrasive and cutting tools

Cutting disks made of SiC

In the arts, silicon carbide is a popular abrasive in modern

water-jet cutting and sandblasting. SiC provides a much sharper and harder alternative for sand blasting as compared to aluminium oxide. Particles of silicon carbide are laminated to paper to create sandpapers and the grip tape on skateboards.[43]

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 made from this alumina and silicon carbide whisker-reinforced composite were introduced into the market.[44]

Structural material

Silicon carbide is used for trauma plates of ballistic vests

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.[45] However, none of these projects resulted in a production quantity, mainly because of its low impact resistance and its low fracture toughness.[46]

Like other hard ceramics (namely alumina and

Pinnacle Armor, used disks of silicon carbide.[47] Improved fracture toughness in SiC armor can be facilitated through the phenomenon of abnormal grain growth
or AGG. The growth of abnormally long silicon carbide grains may serve to impart a toughening effect through crack-wake bridging, similar to whisker reinforcement. Similar AGG-toughening effects have been reported in Silicon nitride (Si3N4).[48]

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.[49]

In December 2015, infusion of silicon carbide nano-particles in molten magnesium was mentioned as a way to produce a new strong and plastic alloy suitable for use in aeronautics, aerospace, automobile and micro-electronics.[50]

Automobile parts

The Porsche Carrera GT's silicon carbide "carbon-ceramic" disk brake

Silicon-infiltrated

brake disks, as they are 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 brake disks 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, the McLaren P1,[51] Bentley, Ferrari, Lamborghini and some specific high-performance Audi cars. Silicon carbide is also used in a sintered form for diesel particulate filters.[52] It is also used as an oil additive[dubious – discuss][clarification needed] to reduce friction, emissions, and harmonics.[53][54]

Foundry crucibles

SiC is used in crucibles for holding melting metal in small and large foundry applications.[55][56]

Electric systems

The earliest electrical application of SiC was as a

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 flushing current into the ground.[57]

It was recognized early on[

varistors that use columns of zinc oxide pellets.[58]

Electronic circuit elements

Silicon carbide was the first commercially important semiconductor material. A crystal radio "carborundum" (synthetic silicon carbide) detector diode was patented by Henry Harrison Chase Dunwoody in 1906. It found much early use in shipboard receivers.

Power electronic devices

In 1993 the silicon carbide was considered a

thyristors were described.[40]

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.[59] As a result, devices made of SiC crystals initially displayed poor reverse blocking performance, though researchers have been tentatively finding solutions to improve the breakdown performance.[60] Apart from crystal quality, problems with the interface of SiC with silicon dioxide have hampered the development of SiC-based power MOSFETs and insulated-gate bipolar transistors. Although the mechanism is still unclear, nitriding has dramatically reduced the defects causing the interface problems.[61]

In 2008, the first commercial JFETs rated at 1200 V were introduced to the market,[62] followed in 2011 by the first commercial MOSFETs rated at 1200 V. JFETs are now available rated 650 V to 1700 V with resistance as low as 25 mΩ. Beside SiC switches and SiC Schottky diodes (also Schottky barrier diode, SBD) in the popular TO-247 and TO-220 packages, companies started even earlier to implement the bare chips into their power electronic modules.

SiC SBD diodes found wide market spread being used in

IGBT power modules.[63]
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:

  • Gate drive: SiC devices often require gate drive voltage levels that are different from their silicon counterparts and may be even unsymmetric, for example, +20 V and −5 V.[64]
  • Packaging: SiC chips may have a higher power density than silicon power devices and are able to handle higher temperatures exceeding the silicon limit of 150 °C. New die attach technologies such as sintering are required to efficiently get the heat out of the devices and ensure a reliable interconnection.[65]

Beginning with Tesla Model 3 the inverters in the drive unit use 24 pairs of silicon carbide (SiC) MOSFET chips rated for 650 volts each. Silicon carbide in this instance gave Tesla a significant advantage over chips made of silicon in terms of size and weight. A number of automobile manufacturers are planning to incorporate silicon carbide into power electronic devices in their products. A significant increase in production of silicon carbide is projected, beginning with a large plant opened 2022 by Wolfspeed in upstate New York.[66][67]

Ultraviolet LED (based on InGaN)

LEDs

The phenomenon of

blue LEDs (6H-SiC) worldwide in the 1980s.[69]

Carbide LED production soon stopped when a different material, 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.[69]

Astronomy

The low thermal expansion coefficient,

space observatory
spacecraft subsystems are mounted on a rigid silicon carbide frame, which provides a stable structure that will not expand or contract due to heat.

Thin-filament pyrometry

Main article: Thin-filament pyrometry
Test flame and glowing SiC fibers. The flame is about 7 cm (2.8 in) tall.

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.[72][73]

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

pilot lights for gas heaters, etc.[74]

Heat shielding

The outer thermal protection layer of NASA's LOFTID inflatable heat shield incorporates a woven ceramic made from silicon carbide, with fiber of such small diameter that it can be bundled and spun into a yarn.[75]

Nuclear fuel particles and cladding

Silicon carbide is an important material in

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.[76]

Silicon carbide

light water reactors. One of the reasons for this investigation is that, Zircaloy experiences hydrogen embrittlement as a consequence of the corrosion reaction with water. This produces a reduction in fracture toughness with increasing volumetric fraction of radial hydrides. This phenomenon increases drastically with increasing temperature to the detriment of the material.[77] Silicon carbide cladding does not experience this same mechanical degradation, but instead retains strength properties with increasing temperature. The composite consists of SiC fibers wrapped around a SiC inner layer and surrounded by an SiC outer layer.[78] Problems have been reported with the ability to join the pieces of the SiC composite.[79]

Jewelry

A moissanite engagement ring

As a

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.[81]

Steel production

Piece of silicon carbide used in steel making

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 content. Silicon carbide is cheaper than a combination of ferrosilicon and carbon, produces cleaner steel and lower emissions due to low levels of trace elements, has a low gas content, and does not lower the temperature of steel.[82]

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.[83][84]

Carborundum printmaking

Silicon carbide is used in

intaglio printmaking
. The result is a print of painted marks embossed into the paper.

Carborundum grit is also used in stone Lithography. Its uniform particle size allows it to be used to "Grain" a stone which removes the previous image. In a similar process to sanding, coarser grit Carborundum is applied to the stone and worked with a Levigator, typically a round plate eccentric on a perpendicular shaft, then gradually finer and finer grit is applied until the stone is clean. This creates a grease sensitive surface.[85]

Graphene production

Silicon carbide can be used in the production of graphene because of its chemical properties that promote the production of graphene on the surface of SiC nanostructures.

When it comes to its production, silicon is used primarily as a substrate to grow the graphene. But there are actually several methods that can be used to grow the graphene on the silicon carbide. The confinement controlled sublimation (CCS) growth method consists of a SiC chip that is heated under vacuum with graphite. Then the vacuum is released very gradually to control the growth of graphene. This method yields the highest quality graphene layers. But other methods have been reported to yield the same product as well.

Another way of growing graphene would be thermally decomposing SiC at a high temperature within a vacuum.[86] But this method turns out to yield graphene layers that contain smaller grains within the layers.[87] So there have been efforts to improve the quality and yield of graphene. One such method is to perform ex situ graphitization of silicon terminated SiC in an atmosphere consisting of argon. This method has proved to yield layers of graphene with larger domain sizes than the layer that would be attainable via other methods. This new method can be very viable to make higher quality graphene for a multitude of technological applications.

When it comes to understanding how or when to use these methods of graphene production, most of them mainly produce or grow this graphene on the SiC within a growth enabling environment. It is utilized most often at rather higher temperatures (such as 1300 °C) because of SiC thermal properties.[88] However, there have been certain procedures that have been performed and studied that could potentially yield methods that use lower temperatures to help manufacture graphene. More specifically this different approach to graphene growth has been observed to produce graphene within a temperature environment of around 750 °C. This method entails the combination of certain methods like chemical vapor deposition (CVD) and surface segregation. And when it comes to the substrate, the procedure would consist of coating a SiC substrate with thin films of a transition metal. And after the rapid heat treating of this substance, the carbon atoms would then become more abundant at the surface interface of the transition metal film which would then yield graphene. And this process was found to yield graphene layers that were more continuous throughout the substrate surface.[89]

Quantum physics

Silicon carbide can host point defects in the crystal lattice which are known as

color centers. These defects can produce single photons on demand and thus serve as a platform for single-photon source.[90] Such a device is a fundamental resource for many emerging applications of quantum information science. If one pumps a color center via an external optical source or electric current, the color center will be brought to the excited state and then relax with the emission of one photon.[91][92]

One well known point defect in silicon carbide is the divacancy which has a similar electronic structure as the nitrogen-vacancy center in diamond. In 4H-SiC, the divacancy has four different configurations which correspond to four zero-phonon lines (ZPL). These ZPL values are written using the notation VSi-VC and the unit eV: hh(1.095), kk(1.096), kh(1.119), and hk(1.150).[93]

Fishing rod guides

Silicon carbide is used in the manufacturing of fishing guides because of its durability and wear resistance.[94] Silicon Carbide rings are fit into a guide frame, typically made from stainless steel or titanium which keep the line from touching the rod blank. The rings provide a low friction surface which improves casting distance while providing adequate hardness that prevents abrasion from braided fishing line.[95]

Pottery glazes

Silicon carbide is used as a raw ingredient in some glazes applied to ceramics. At high temperatures it can reduce metal oxides forming silica and carbon dioxide. This can be used to make the glaze foam and crater due to the evolved carbon dioxide gas, or to reduce the colorant oxides and achieve colors such as copper reds otherwise only possible in a fuel powered reduction firing in an electric kiln.[96]

See also

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External links

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