Wikipedia

Silicon

Not to be confused with the silicon-containing synthetic polymersilicone.
For other uses, seeSilicon (disambiguation).
"Element 14" redirects here. For other uses, seeElement 14 (disambiguation).

Siliconis achemical element;it hassymbolSiandatomic number14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is atetravalentmetalloidandsemiconductor.It is a member ofgroup 14in the periodic table:carbonis above it; andgermanium,tin,lead,andfleroviumare below it. It is relatively unreactive. Silicon is a significant element that is essential for several physiological and metabolic processes in plants. Silicon is widely regarded as the predominant semiconductor material due to its versatile applications in various electrical devices such as transistors, solar cells, integrated circuits, and others. These may be due to its significant band gap, expansive optical transmission range, extensive absorption spectrum, surface roughening, and effective anti-reflection coating.[14]

Silicon,14Si
Silicon
Pronunciation
AllotropesseeAllotropes of silicon
Appearancecrystalline, reflective with bluish-tinged faces
Standard atomic weightAr°(Si)
Silicon in theperiodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
C
↑
Si
↓
Ge
aluminium←silicon→phosphorus
Atomic number(Z)14
Groupgroup 14 (carbon group)
Periodperiod 3
Blockp-block
Electron configuration[Ne] 3s23p2
Electrons per shell2, 8, 4
Physical properties
PhaseatSTPsolid
Melting point1687K​(1414 °C, ​2577 °F)
Boiling point3538 K ​(3265 °C, ​5909 °F)
Density(at 20° C)2.329085 g/cm3[3]
when liquid (atm.p.)2.57 g/cm3
Heat of fusion50.21kJ/mol
Heat of vaporization383 kJ/mol
Molar heat capacity19.789 J/(mol·K)
Vapor pressure
P(Pa) 1 10 100 1 k 10 k 100 k
atT(K) 1908 2102 2339 2636 3021 3537
Atomic properties
Oxidation statescommon:−4, +4
−3,[4]−2,[4]−1,[4]0,[5]+1,[4][6]+2,[4]+3[4]
ElectronegativityPauling scale: 1.90
Ionization energies
  • 1st: 786.5 kJ/mol
  • 2nd: 1577.1 kJ/mol
  • 3rd: 3231.6 kJ/mol
  • (more)
Atomic radiusempirical: 111pm
Covalent radius111 pm
Van der Waals radius210 pm
Color lines in a spectral range
Spectral linesof silicon
Other properties
Natural occurrenceprimordial
Crystal structure​face-centered diamond-cubic(cF8)
Lattice constant
Diamond cubic crystal structure for silicon
a= 543.0986 pm (at 20 °C)[3]
Thermal expansion2.556×10−6/K (at 20 °C)[3]
Thermal conductivity149 W/(m⋅K)
Electrical resistivity2.3×103Ω⋅m (at 20 °C)[7]
Band gap1.12eV(at 300 K)
Magnetic orderingdiamagnetic[8]
Molar magnetic susceptibility−3.9×10−6cm3/mol (298 K)[9]
Young's modulus130–188 GPa[10]
Shear modulus51–80 GPa[10]
Bulk modulus97.6 GPa[10]
Speed of soundthin rod8433 m/s (at 20 °C)
Poisson ratio0.064–0.28[10]
Mohs hardness6.5
CAS Number7440-21-3
History
Namingafter Latinsilexorsilicis,meaning 'flint'
PredictionAntoine Lavoisier(1787)
Discoveryand first isolationJöns Jacob Berzelius[11][12](1823)
Named byThomas Thomson(1817)
Isotopes of silicon
Main isotopes[13] Decay
abun­dance half-life(t1/2) mode pro­duct
28Si 92.2% stable
29Si 4.7% stable
30Si 3.1% stable
31Si trace 2.62 h β− 31P
32Si trace 153 y β− 32P
Category: Silicon
|references

Because of its high chemical affinity for oxygen, it was not until 1823 thatJöns Jakob Berzeliuswas first able to prepare it and characterize it in pure form. Itsoxidesform a family ofanionsknown assilicates.Its melting and boiling points of 1414 °C and 3265 °C, respectively, are the second highest among all the metalloids and nonmetals, being surpassed only byboron.[a]

Silicon is the eighthmost common elementin the universe by mass, but very rarely occurs as the pure element in the Earth's crust. It is widely distributed throughout space in cosmicdusts,planetoids,andplanetsas various forms ofsilicon dioxide(silica) orsilicates.More than 90% of the Earth's crust is composed ofsilicate minerals,making silicon thesecond most abundant elementin the Earth's crust (about 28% by mass), afteroxygen.

Most silicon is used commercially without being separated, often with very little processing of the natural minerals. Such use includes industrial construction withclays,silica sand,andstone.Silicates are used inPortland cementformortarandstucco,and mixed with silica sand andgravelto makeconcretefor walkways, foundations, and roads. They are also used in whitewareceramicssuch asporcelain,and in traditionalsilicate-basedsoda–lime glassand many other specialtyglasses.Silicon compounds such assilicon carbideare used as abrasives and components of high-strength ceramics. Silicon is the basis of the widely used synthetic polymers calledsilicones.

The late 20th century to early 21st century has been described as the Silicon Age (also known as theDigital AgeorInformation Age) because of the large impact that elemental silicon has on the modern world economy. The small portion of very highly purified elemental silicon used insemiconductor electronics(<15%) is essential to thetransistorsandintegrated circuitchips used in most modern technology such assmartphonesand othercomputers.In 2019, 32.4% of the semiconductor market segment was for networks and communications devices, and the semiconductors industry is projected to reach $726.73 billion by 2027.[15]

Silicon is an essential element in biology. Only traces are required by most animals, but somesea spongesand microorganisms, such asdiatomsandradiolaria,secrete skeletal structures made of silica. Silica is deposited in many plant tissues.[16]

History

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Owing to the abundance of silicon in theEarth's crust,natural silicon-based materials have been used for thousands of years. Siliconrock crystalswere familiar to variousancient civilizations,such as thepredynastic Egyptianswho used it forbeadsand smallvases,as well as theancient Chinese.Glasscontainingsilicawas manufactured by theEgyptianssince at least 1500 BC, as well as by the ancientPhoenicians.Naturalsilicatecompounds were also used in various types ofmortarfor construction of early humandwellings.[17]

Discovery

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Jöns Jacob Berzeliusdiscovered silicon in 1823.

In 1787,Antoine Lavoisiersuspected thatsilicamight be an oxide of a fundamentalchemical element,[18]but thechemical affinityof silicon for oxygen is high enough that he had no means to reduce the oxide and isolate the element.[19]After an attempt to isolate silicon in 1808,Sir Humphry Davyproposed the name "silicium" for silicon, from the Latinsilex,silicisfor flint, and adding the "-ium" ending because he believed it to be a metal.[20]Most other languages use transliterated forms of Davy's name, sometimes adapted to local phonology (e.g.GermanSilizium,Turkishsilisyum,Catalansilici,ArmenianՍիլիցիումorSilitzioum). A few others use instead acalqueof the Latin root (e.g.Russianкремний,fromкремень"flint";Greekπυρίτιοfromπυρ"fire";Finnishpiifrompiikivi"flint",Czechkřemíkfromkřemen"quartz", "flint" ).[21]

Gay-LussacandThénardare thought to have prepared impureamorphous siliconin 1811, through the heating of recently isolatedpotassiummetal withsilicon tetrafluoride,but they did not purify and characterize the product, nor identify it as a new element.[22]Silicon was given its present name in 1817 by Scottish chemistThomas Thomson.He retained part of Davy's name but added "-on" because he believed that silicon was anonmetalsimilar toboronandcarbon.[23]In 1824,Jöns Jacob Berzeliusprepared amorphous silicon using approximately the same method as Gay-Lussac (reducingpotassium fluorosilicatewith molten potassium metal), but purifying the product to a brown powder by repeatedly washing it.[24]As a result, he is usually given credit for the element's discovery.[25][26]The same year, Berzelius became the first to preparesilicon tetrachloride;silicon tetrafluoridehad already been prepared long before in 1771 byCarl Wilhelm Scheeleby dissolving silica inhydrofluoric acid.[19]In 1823 for the first timeJacob Berzeliusdiscoveredsilicon tetrachloride(SiCl4).[27]In 1846 Von Ebelman's synthesizedtetraethyl orthosilicate(Si(OC2H5)4).[28][27]

Silicon in its more common crystalline form was not prepared until 31 years later, byDeville.[29][30]Byelectrolyzinga mixture ofsodium chlorideandaluminium chloridecontaining approximately 10% silicon, he was able to obtain a slightly impureallotropeof silicon in 1854.[31]Later, more cost-effective methods have been developed to isolate several allotrope forms, the most recent beingsilicenein 2010.[32][33]Meanwhile, research on the chemistry of silicon continued;Friedrich Wöhlerdiscovered the first volatile hydrides of silicon, synthesisingtrichlorosilanein 1857 andsilaneitself in 1858, but a detailed investigation of thesilaneswas only carried out in the early 20th century byAlfred Stock,despite early speculation on the matter dating as far back as the beginnings of synthetic organic chemistry in the 1830s.[34][35]Similarly, the firstorganosilicon compound,tetraethylsilane, was synthesised byCharles FriedelandJames Craftsin 1863, but detailed characterisation of organosilicon chemistry was only done in the early 20th century byFrederic Kipping.[19]

Starting in the 1920s, the work ofWilliam Lawrence BraggonX-ray crystallographyelucidated the compositions of the silicates, which had previously been known fromanalytical chemistrybut had not yet been understood, together withLinus Pauling's development ofcrystal chemistryandVictor Goldschmidt's development ofgeochemistry.The middle of the 20th century saw the development of the chemistry and industrial use ofsiloxanesand the growing use ofsiliconepolymers,elastomers,andresins.In the late 20th century, the complexity of the crystal chemistry ofsilicideswas mapped, along with thesolid-state physicsofdopedsemiconductors.[19]

Silicon semiconductors

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The firstsemiconductor devicesdid not use silicon, but usedgalena,including GermanphysicistFerdinand Braun'scrystal detectorin 1874 and Indian physicistJagadish Chandra Bose'sradiocrystal detector in 1901.[36][37]The first silicon semiconductor device was a silicon radio crystal detector, developed by American engineerGreenleaf Whittier Pickardin 1906.[37]

In 1940,Russell Ohldiscovered thep–n junctionandphotovoltaic effectsin silicon. In 1941, techniques for producing high-puritygermaniumandsilicon crystalswere developed forradarmicrowavedetector crystals duringWorld War II.[36]In 1947, physicistWilliam Shockleytheorized afield-effect amplifiermade from germanium and silicon, but he failed to build a working device, before eventually working with germanium instead. The first working transistor was apoint-contact transistorbuilt byJohn BardeenandWalter Brattainlater that year while working under Shockley.[38]In 1954,physical chemistMorris Tanenbaumfabricated the first siliconjunction transistoratBell Labs.[39]In 1955,Carl Froschand Lincoln Derick at Bell Labs accidentally discovered thatsilicon dioxide(SiO
2) could be grown on silicon.[40][41]By 1957 Frosch and Derick published their work on the first manufacturedSiO
2semiconductor oxide transistor: the first planar transistors, in which drain and source were adjacent at the same surface.[42]

Silicon Age

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TheMOSFET,also known as the MOS transistor, is the key component of the Silicon Age. The first silicon semiconductor oxide planar transistor was made by Frosch and Derick in 1957.[43]

The "Silicon Age" refers to the late 20th century to early 21st century.[44][45][46]This is due to silicon being the dominant material of the Silicon Age (also known as theDigital AgeorInformation Age), similar to how theStone Age,Bronze AgeandIron Agewere defined by the dominant materials during their respectiveages of civilization.[44]

Because silicon is an important element in high-technology semiconductor devices, many places in the world bear its name. For example, theSanta Clara Valleyin California acquired the nicknameSilicon Valley,as the element is the base material in thesemiconductor industrythere. Since then, many other places have been similarly dubbed, includingSilicon Wadiin Israel;Silicon Forestin Oregon;Silicon Hillsin Austin, Texas;Silicon Slopesin Salt Lake City, Utah;Silicon Saxonyin Germany;Silicon Valleyin India;Silicon Borderin Mexicali, Mexico;Silicon Fenin Cambridge, England;Silicon Roundaboutin London;Silicon Glenin Scotland;Silicon Gorgein Bristol, England;Silicon Alleyin New York City; andSilicon Beachin Los Angeles.[47]

Characteristics

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Physical and atomic

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Silicon crystallizes in adiamondcubic crystal structureby formingsp3hybrid orbitals.[48]

A silicon atom has fourteenelectrons.In the ground state, they are arranged in the electron configuration [Ne]3s23p2.Of these, four arevalence electrons,occupying the 3s orbital and two of the 3p orbitals. Like the other members of its group, the lightercarbonand the heaviergermanium,tin,andlead,it has the same number of valence electrons as valence orbitals: hence, it can complete itsoctetand obtain the stablenoble gasconfiguration ofargonby formingsp3hybrid orbitals,forming tetrahedralSiX
4derivatives where the central silicon atom shares an electron pair with each of the four atoms it is bonded to.[49]The first fourionisation energiesof silicon are 786.3, 1576.5, 3228.3, and 4354.4 kJ/mol respectively; these figures are high enough to preclude the possibility of simple cationic chemistry for the element. Followingperiodic trends,its single-bond covalent radius of 117.6 pm is intermediate between those of carbon (77.2 pm) and germanium (122.3 pm). The hexacoordinate ionic radius of silicon may be considered to be 40 pm, although this must be taken as a purely notional figure given the lack of a simpleSi4+
cation in reality.[50]

Electrical

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At standard temperature and pressure, silicon is a shinysemiconductorwith a bluish-grey metallic lustre; as typical for semiconductors, its resistivity drops as temperature rises. This arises because silicon has a small energy gap (band gap) between its highest occupied energy levels (the valence band) and the lowest unoccupied ones (the conduction band). TheFermi levelis about halfway between thevalence and conduction bandsand is the energy at which a state is as likely to be occupied by an electron as not. Hence pure silicon is effectively an insulator at room temperature. However,dopingsilicon with apnictogensuch asphosphorus,arsenic,orantimonyintroduces one extra electron per dopant and these may then be excited into the conduction band either thermally or photolytically, creating ann-type semiconductor.Similarly, doping silicon with agroup 13 elementsuch asboron,aluminium,orgalliumresults in the introduction of acceptor levels that trap electrons that may be excited from the filled valence band, creating ap-type semiconductor.[51]Joining n-type silicon to p-type silicon creates ap–n junctionwith a common Fermi level; electrons flow from n to p, while holes flow from p to n, creating a voltage drop. This p–n junction thus acts as adiodethat can rectify alternating current that allows current to pass more easily one way than the other. Atransistoris an n–p–n junction, with a thin layer of weakly p-type silicon between two n-type regions. Biasing the emitter through a small forward voltage and the collector through a large reverse voltage allows the transistor to act as atriodeamplifier.[51]

Crystal structure

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Main article:Allotropes of silicon

Silicon crystallises in a giant covalent structure at standard conditions, specifically in adiamond cubiccrystal lattice (space group 227). It thus has a high melting point of 1414 °C, as a lot of energy is required to break the strong covalent bonds and melt the solid. Upon melting silicon contracts as the long-range tetrahedral network of bonds breaks up and the voids in that network are filled in, similar to water ice when hydrogen bonds are broken upon melting. It does not have any thermodynamically stable allotropes at standard pressure, but several other crystal structures are known at higher pressures. The general trend is one of increasingcoordination numberwith pressure, culminating in ahexagonal close-packedallotrope at about 40gigapascalsknown as Si–VII (the standard modification being Si–I). An allotrope called BC8 (or bc8), having abody-centred cubiclattice with eight atoms per primitive unit cell (space group 206), can be created at high pressure and remains metastable at low pressure. Its properties have been studied in detail.[52]

Silicon boils at 3265 °C: this, while high, is still lower than the temperature at which its lighter congenercarbonsublimes (3642 °C) and silicon similarly has a lowerheat of vaporisationthan carbon, consistent with the fact that the Si–Si bond is weaker than the C–C bond.[51]

It is also possible to constructsilicenelayers analogous tographene.[32][33]

Isotopes

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Main article:Isotopes of silicon

Naturally occurring silicon is composed of three stableisotopes,28Si (92.23%),29Si (4.67%), and30Si (3.10%).[13]Out of these, only29Si is of use inNMRandEPR spectroscopy,[53]as it is the only one with a nuclear spin (I=⁠1/2⁠).[34]All three are produced inType Ia supernovae[54][55]through theoxygen-burning process,with28Si being made as part of thealpha processand hence the most abundant. The fusion of28Si with alpha particles byphotodisintegrationrearrangement in stars is known as thesilicon-burning process;it is the last stage ofstellar nucleosynthesisbefore the rapid collapse and violent explosion of the star in question in atype II supernova.[56]

Twenty-tworadioisotopeshave been characterized, the two stablest being32Si with ahalf-lifeof about 150 years, and31Si with a half-life of 2.62 hours.[13]All the remainingradioactiveisotopes have half-lives that are less than seven seconds, and the majority of these have half-lives that are less than one-tenth of a second.[13]Silicon has one knownnuclear isomer,34mSi, with a half-life less than 210 nanoseconds.[13]32Si undergoes low-energybeta decayto32Pand then stable32S.31Si may be produced by theneutron activationof natural silicon and is thus useful for quantitative analysis; it can be easily detected by its characteristic beta decay to stable31P,in which the emitted electron carries up to 1.48MeVof energy.[34]

The known isotopes of silicon range inmass numberfrom 22 to 46.[13][57]The most commondecay modeof the isotopes with mass numbers lower than the three stable isotopes isinverse beta decay,primarily forming aluminium isotopes (13 protons) asdecay products.[13]The most common decay mode for the heavier unstable isotopes is beta decay, primarily forming phosphorus isotopes (15 protons) as decay products.[13]

Silicon can enter the oceans through groundwater andriverinetransport. Large fluxes of groundwater input have an isotopic composition which is distinct from riverine silicon inputs. Isotopic variations in groundwater and riverine transports contribute to variations in oceanic30Si values. Currently, there are substantial differences in the isotopic values of deep water in the world'socean basins.Between the Atlantic and Pacific oceans, there is a deep water30Si gradient of greater than 0.3 parts per thousand.30Si is most commonly associated with productivity in the oceans.[58]

Chemistry and compounds

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Main article:Silicon compounds
C–X and Si–X bond energies (kJ/mol)[34]
X = C Si H F Cl Br I O– N<
C–X 368 360 435 453 351 293 216 ~360 ~305
Si–X 360 340 393 565 381 310 234 452 322

Crystalline bulk silicon is rather inert, but becomes more reactive at high temperatures. Like its neighbour aluminium, silicon forms a thin, continuous surface layer ofsilicon dioxide(SiO
2) that protects the metal from oxidation. Thus silicon does not measurably react with the air below 900 °C, but formation of thevitreousdioxide rapidly increases between 950 °C and 1160 °C and when 1400 °C is reached, atmosphericnitrogenalso reacts to give the nitrides SiN andSi
3N
4.Silicon reacts with gaseoussulfurat 600 °C and gaseousphosphorusat 1000 °C. This oxide layer nevertheless does not prevent reaction with thehalogens;fluorineattacks silicon vigorously at room temperature,chlorinedoes so at about 300 °C, andbromineandiodineat about 500 °C. Silicon does not react with most aqueous acids, but is oxidised and complexed byhydrofluoric acidmixtures containing eitherchlorineornitric acidto formhexafluorosilicates.It readily dissolves in hot aqueous alkali to formsilicates.[59]At high temperatures, silicon also reacts withalkyl halides;this reaction may be catalysed bycopperto directly synthesiseorganosiliconchlorides as precursors tosiliconepolymers. Upon melting, silicon becomes extremely reactive, alloying with most metals to formsilicides,and reducing most metal oxides because theheat of formationof silicon dioxide is so large. In fact, molten silicon reacts virtually with every known kind of crucible material (except its own oxide,SiO
2).[60]: 13 This happens due to silicon's high binding forces for the light elements and to its high dissolving power for most elements.[60]: 13 As a result, containers for liquid silicon must be made ofrefractory,unreactive materials such aszirconium dioxideor group 4, 5, and 6 borides.[51][61]

Tetrahedral coordination is a major structural motif in silicon chemistry just as it is for carbon chemistry. However, the 3p subshell is rather more diffuse than the 2p subshell and does not hybridise so well with the 3s subshell. As a result, the chemistry of silicon and its heavier congeners shows significant differences from that of carbon,[62]and thus octahedral coordination is also significant.[51]For example, theelectronegativityof silicon (1.90) is much less than that of carbon (2.55), because the valence electrons of silicon are further from the nucleus than those of carbon and hence experience smaller electrostatic forces of attraction from the nucleus. The poor overlap of 3p orbitals also results in a much lower tendency towardcatenation(formation of Si–Si bonds) for silicon than for carbon, due to the concomitant weakening of the Si–Si bond compared to the C–C bond:[63]the average Si–Si bond energy is approximately 226 kJ/mol, compared to a value of 356 kJ/mol for the C–C bond.[64]This results in multiply bonded silicon compounds generally being much less stable than their carbon counterparts, an example of thedouble bond rule.On the other hand, the presence of radial nodes in the 3p orbitals of silicon suggests the possibility ofhypervalence,as seen in five and six-coordinate derivatives of silicon such asSiX−
5andSiF2−
6.[65][63]Lastly, because of the increasing energy gap between the valence s and p orbitals as the group is descended, the divalent state grows in importance from carbon to lead, so that a few unstable divalent compounds are known for silicon; this lowering of the main oxidation state, in tandem with increasing atomic radii, results in an increase of metallic character down the group. Silicon already shows some incipient metallic behavior, particularly in the behavior of its oxide compounds and its reaction with acids as well as bases (though this takes some effort), and is hence often referred to as ametalloidrather than a nonmetal.[63]Germanium shows more, and tin is generally considered a metal.[19]

Silicon shows clear differences from carbon. For example,organic chemistryhas very few analogies with silicon chemistry, whilesilicateminerals have a structural complexity unseen inoxocarbons.[66]Silicon tends to resemble germanium far more than it does carbon, and this resemblance is enhanced by thed-block contraction,resulting in the size of the germanium atom being much closer to that of the silicon atom than periodic trends would predict.[67]Nevertheless, there are still some differences because of the growing importance of the divalent state in germanium compared to silicon. Additionally, the lower Ge–O bond strength compared to theSi–O bondstrength results in the absence of "germanone" polymers that would be analogous to silicone polymers.[64]

Occurrence

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Olivine

Silicon is the eighth most abundant element in the universe, coming afterhydrogen,helium,carbon,nitrogen,oxygen,iron,andneon.These abundances are not replicated well on Earth due to substantial separation of the elements taking place during the formation of theSolar System.Silicon makes up 27.2% of the Earth's crust by weight, second only to oxygen at 45.5%, with which it always is associated in nature. Further fractionation took place in the formation of the Earth byplanetary differentiation:Earth's core,which makes up 31.5% of the mass of the Earth, has approximate compositionFe
25Ni
2Co
0.1S
3;themantlemakes up 68.1% of the Earth's mass and is composed mostly of denser oxides and silicates, an example beingolivine,(Mg,Fe)
2SiO
4;while the lighter siliceous minerals such asaluminosilicatesrise to the surface and form the crust, making up 0.4% of the Earth's mass.[68][69]

The crystallisation ofigneous rocksfrom magma depends on a number of factors; among them are the chemical composition of the magma, the cooling rate, and some properties of the individual minerals to be formed, such aslattice energy,melting point, and complexity of their crystal structure. As magma is cooled,olivineappears first, followed bypyroxene,amphibole,biotitemica,orthoclase feldspar,muscovite mica,quartz,zeolites,and finally, hydrothermal minerals. This sequence shows a trend toward increasingly complex silicate units with cooling, and the introduction ofhydroxideandfluorideanions in addition to oxides. Many metals may substitute for silicon. After these igneous rocks undergoweathering,transport, and deposition,sedimentary rockslike clay, shale, and sandstone are formed.Metamorphismalso may occur at high temperatures and pressures, creating an even vaster variety of minerals.[68]

There are four sources for silicon fluxes into the ocean: chemical weathering of continental rocks, river transport, dissolution of continental terrigenous silicates, and the reaction between submarine basalts and hydrothermal fluid which release dissolved silicon. All four of these fluxes are interconnected in the ocean's biogeochemical cycle as they all were initially formed from the weathering of Earth's crust.[70]

Approximately 300–900 megatonnes of Aeolian dust is deposited into the world's oceans each year. Of that value, 80–240 megatonnes are in the form of particulate silicon. The total amount of particulate silicon deposition into the ocean is still less than the amount of silicon influx into the ocean via riverine transportation.[71]Aeolian inputs of particulate lithogenic silicon into the North Atlantic and Western North Pacific oceans are the result of dust settling on the oceans from the Sahara and Gobi Desert, respectively.[70]Riverine transports are the major source of silicon influx into the ocean in coastal regions, while silicon deposition in the open ocean is greatly influenced by the settling of Aeolian dust.[71]

Production

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Further information:List of countries by silicon production

Silicon of 96–99% purity is made bycarbothermicallyreducingquartziteor sand with highly purecoke.The reduction is carried out in anelectric arc furnace,with an excess ofSiO
2used to stopsilicon carbide(SiC) from accumulating:[34]

SiO
2+ 2 C → Si + 2 CO
2 SiC +SiO
2→ 3 Si + 2 CO
Ferrosilicon alloy

This reaction, known as carbothermal reduction of silicon dioxide, usually is conducted in the presence of scrap iron with low amounts ofphosphorusandsulfur,producingferrosilicon.[34]Ferrosilicon, an iron-silicon alloy that contains varying ratios of elemental silicon and iron, accounts for about 80% of the world's production of elemental silicon, with China, the leading supplier of elemental silicon, providing 4.6 milliontonnes(or 2/3rds of world output) of silicon, most of it in the form of ferrosilicon. It is followed by Russia (610,000 t), Norway (330,000 t), Brazil (240,000 t), and the United States (170,000 t).[72]Ferrosilicon is primarily used by the iron and steel industry (seebelow) with primary use as alloying addition in iron or steel and for de-oxidation of steel in integrated steel plants.[34]

Another reaction, sometimes used, is aluminothermal reduction of silicon dioxide, as follows:[73]

3SiO
2+ 4 Al → 3 Si + 2Al
2O
3

Leaching powdered 96–97% pure silicon with water results in ~98.5% pure silicon, which is used in the chemical industry. However, even greater purity is needed for semiconductor applications, and this is produced from the reduction oftetrachlorosilane(silicon tetrachloride) ortrichlorosilane.The former is made by chlorinating scrap silicon and the latter is a byproduct ofsiliconeproduction. These compounds are volatile and hence can be purified by repeatedfractional distillation,followed by reduction to elemental silicon with very purezincmetal as the reducing agent. The spongy pieces of silicon thus produced are melted and then grown to form cylindrical single crystals, before being purified byzone refining.Other routes use the thermal decomposition ofsilaneortetraiodosilane(SiI
4). Another process used is the reduction ofsodium hexafluorosilicate,a common waste product of the phosphate fertilizer industry, by metallicsodium:this is highly exothermic and hence requires no outside energy source. Hyperfine silicon is made at a higher purity than almost any other material:transistorproduction requires impurity levels in silicon crystals less than 1 part per 1010,and in special cases impurity levels below 1 part per 1012are needed and attained.[34]

Silicon nanostructures can directly be produced from silica sand using conventional metalothermic processes, or the combustion synthesis approach. Such nanostructured silicon materials can be used in various functional applications including the anode of lithium-ion batteries (LIBs), other ion batteries, future computing devices like memristors or photocatalytic applications.[74]

Applications

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Compounds

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Most silicon is used industrially without being purified, often with comparatively little processing from its natural form. More than 90% of the Earth's crust is composed ofsilicate minerals,which are compounds of silicon and oxygen, often with metallic ions when negatively charged silicate anions require cations to balance the charge. Many of these have direct commercial uses, such as clays,silicasand, and most kinds of building stone. Thus, the vast majority of uses for silicon are as structural compounds, either as the silicate minerals or silica (crude silicon dioxide). Silicates are used in makingPortland cement(made mostly of calcium silicates) which is used inbuilding mortarand modernstucco,but more importantly, combined with silica sand, and gravel (usually containing silicate minerals such as granite), to make theconcretethat is the basis of most of the very largest industrial building projects of the modern world.[75]

Silica is used to makefire brick,a type of ceramic. Silicate minerals are also in whitewareceramics,an important class of products usually containing various types of firedclayminerals (natural aluminium phyllosilicates). An example isporcelain,which is based on the silicate mineralkaolinite.Traditionalglass(silica-basedsoda–lime glass) also functions in many of the same ways, and also is used for windows and containers. In addition, specialty silica basedglass fibersare used foroptical fiber,as well as to producefiberglassfor structural support andglass woolforthermal insulation.

Silicones often are used inwaterproofingtreatments,moldingcompounds, mold-release agents,mechanical seals, high temperaturegreasesand waxes, andcaulkingcompounds. Silicone is also sometimes used inbreast implants,contact lenses,explosivesandpyrotechnics.[76]Silly Puttywas originally made by addingboric acidtosilicone oil.[77]Other silicon compounds function as high-technology abrasives and new high-strength ceramics based uponsilicon carbide.Silicon is a component of somesuperalloys.

Alloys

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Elemental silicon is added to moltencast ironasferrosiliconor silicocalcium alloys to improve performance in casting thin sections and to prevent the formation ofcementitewhere exposed to outside air. The presence of elemental silicon in molten iron acts as a sink for oxygen, so that the steel carbon content, which must be kept within narrow limits for each type of steel, can be more closely controlled. Ferrosilicon production and use is a monitor of the steel industry, and although this form of elemental silicon is grossly impure, it accounts for 80% of the world's use of free silicon. Silicon is an important constituent oftransformer steel,modifying itsresistivityandferromagneticproperties.

The properties of silicon may be used to modify alloys with metals other than iron. "Metallurgical grade" silicon is silicon of 95–99% purity. About 55% of the world consumption of metallurgical purity silicon goes for production of aluminium-silicon alloys (siluminalloys) for aluminium partcasts,mainly for use in theautomotive industry.Silicon's importance in aluminium casting is that a significantly high amount (12%) of silicon in aluminium forms aeutectic mixturewhich solidifies with very little thermal contraction. This greatly reduces tearing and cracks formed from stress as casting alloys cool to solidity. Silicon also significantly improves the hardness and thus wear-resistance of aluminium.[78][79]

Electronics

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Main article:Semiconductor device fabrication
Further information:Semiconductor industry
Silicon wafer with mirror finish

Most elemental silicon produced remains as a ferrosilicon alloy, and only approximately 20% is refined to metallurgical grade purity (a total of 1.3–1.5 million metric tons/year). An estimated 15% of the world production of metallurgical grade silicon is further refined to semiconductor purity.[79]This typically is the "nine-9" or 99.9999999% purity,[80]nearly defect-free singlecrystallinematerial.[81]

Monocrystalline siliconof such purity is usually produced by theCzochralski process,and is used to producesilicon wafersused in thesemiconductor industry,in electronics, and in some high-cost and high-efficiencyphotovoltaicapplications.[82]Pure silicon is anintrinsic semiconductor,which means that unlike metals, it conductselectron holesand electrons released from atoms by heat; silicon'selectrical conductivityincreases with higher temperatures. Pure silicon has too low a conductivity (i.e., too high aresistivity) to be used as a circuit element in electronics. In practice, pure silicon isdopedwith small concentrations of certain other elements, which greatly increase its conductivity and adjust its electrical response by controlling the number and charge (positiveornegative) of activated carriers. Such control is necessary fortransistors,solar cells,semiconductor detectors,and othersemiconductor devicesused in the computer industry and other technical applications.[83]Insilicon photonics,silicon may be used as a continuous waveRaman lasermedium to produce coherent light.[84]

In commonintegrated circuits,a wafer of monocrystalline silicon serves as a mechanical support for the circuits, which are created by doping and insulated from each other by thin layers ofsilicon oxide,an insulator that is easily produced on Si surfaces by processes ofthermal oxidationorlocal oxidation (LOCOS),which involve exposing the element to oxygen under the proper conditions that can be predicted by theDeal–Grove model.Silicon has become the most popular material for both high power semiconductors and integrated circuits because it can withstand the highest temperatures and greatest electrical activity without sufferingavalanche breakdown(anelectron avalancheis created when heat produces free electrons and holes, which in turn pass more current, which produces more heat). In addition, the insulating oxide of silicon is not soluble in water, which gives it an advantage overgermanium(an element with similar properties which can also be used in semiconductor devices) in certain fabrication techniques.[85]

Monocrystalline silicon is expensive to produce, and is usually justified only in production of integrated circuits, where tiny crystal imperfections can interfere with tiny circuit paths. For other uses, other types of pure silicon may be employed. These includehydrogenated amorphous siliconand upgraded metallurgical-grade silicon (UMG-Si) used in the production of low-cost,large-area electronicsin applications such asliquid crystal displaysand of large-area, low-cost, thin-filmsolar cells.Such semiconductor grades of silicon are either slightly less pure or polycrystalline rather than monocrystalline, and are produced in comparable quantities as the monocrystalline silicon: 75,000 to 150,000 metric tons per year. The market for the lesser grade is growing more quickly than for monocrystalline silicon. By 2013, polycrystalline silicon production, used mostly in solar cells, was projected to reach 200,000 metric tons per year, while monocrystalline semiconductor grade silicon was expected to remain less than 50,000 tons per year.[79]

Quantum dots

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Silicon quantum dotsare created through the thermal processing of hydrogensilsesquioxaneinto nanocrystals ranging from a few nanometers to a few microns, displaying size dependentluminescentproperties.[86][87]The nanocrystals display largeStokes shiftsconverting photons in the ultraviolet range to photons in the visible or infrared, depending on the particle size, allowing for applications inquantum dot displaysandluminescent solar concentratorsdue to their limited self absorption. A benefit of using silicon basedquantum dotsovercadmiumorindiumis the non-toxic, metal-free nature of silicon.[88][89] Another application of silicon quantum dots is for sensing of hazardous materials. The sensors take advantage of the luminescent properties of the quantum dots throughquenchingof thephotoluminescencein the presence of the hazardous substance.[90]There are many methods used for hazardous chemical sensing with a few being electron transfer,fluorescence resonance energy transfer,and photocurrent generation.[91]Electron transfer quenching occurs when thelowest unoccupied molecular orbital(LUMO) is slightly lower in energy than the conduction band of the quantum dot, allowing for the transfer of electrons between the two, preventing recombination of the holes and electrons within the nanocrystals. The effect can also be achieved in reverse with a donor molecule having itshighest occupied molecular orbital(HOMO) slightly higher than a valence band edge of the quantum dot, allowing electrons to transfer between them, filling the holes and preventing recombination. Fluorescence resonance energy transfer occurs when a complex forms between the quantum dot and a quencher molecule. The complex will continue to absorb light but when the energy is converted to the ground state it does not release a photon, quenching the material. The third method uses different approach by measuring thephotocurrentemitted by the quantum dots instead of monitoring the photoluminescent display. If the concentration of the desired chemical increases then the photocurrent given off by the nanocrystals will change in response.[92]

Thermal energy storage

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This section is an excerpt fromThermal energy storage § Hot silicon technology.[edit]
Solid or molten silicon offers much higher storage temperatures than salts with consequent greater capacity and efficiency. It is being researched as a possible more energy efficient storage technology. Silicon is able to store more than 1 MWh of energy per cubic meter at 1400 °C. An additional advantage is the relative abundance of silicon when compared to the salts used for the same purpose.[93][94]

Biological role

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A diatom, enclosed in a silica cell wall

Although silicon is readily available in the form ofsilicates,very few organisms use it directly.Diatoms,radiolaria,andsiliceous spongesusebiogenic silicaas a structural material for their skeletons. Some plants accumulate silica in their tissues and require silicon for their growth, for examplerice.Silicon may be taken up by plants asorthosilicic acid(also known as monosilicic acid) and transported through thexylem,where it forms amorphous complexes with components of the cell wall. This has been shown to improve cell wall strength and structural integrity in some plants, thereby reducing insect herbivory and pathogenic infections. In certain plants, silicon may also upregulate the production of volatile organic compounds and phytohormones which play a significant role in plant defense mechanisms.[95][96][97]In more advanced plants, the silicaphytoliths(opal phytoliths) are rigid microscopic bodies occurring in the cell.[98][99][96]

Severalhorticultural cropsare known to protect themselves againstfungal plant pathogenswith silica, to such a degree thatfungicideapplication may fail unless accompanied by sufficient silicon nutrition. Silicaceous plant defense molecules activate somephytoalexins,meaning some of them are signalling substances producingacquired immunity.When deprived, some plants will substitute with increased production of other defensive substances.[96]

Life on Earth is largely composed ofcarbon,butastrobiologyconsiders thatextraterrestrial lifemay have otherhypothetical types of biochemistry.Silicon is considered an alternative to carbon, as it can create complex and stable molecules with four covalent bonds, required for aDNA-analog, and it is available in large quantities.[100]

Marine microbial influences

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Diatoms use silicon in thebiogenic silica(bSi) form,[101]which is taken up by the silicon transport protein (SIT) to be predominantly used in the cell wall structure as frustules.[102]Silicon enters the ocean in a dissolved form such as silicic acid or silicate.[103]Since diatoms are one of the main users of these forms of silicon, they contribute greatly to the concentration of silicon throughout the ocean. Silicon forms a nutrient-like profile in the ocean due to the diatom productivity in shallow depths.[103]Therefore, concentration of silicon is lower in the shallow ocean and higher in the deep ocean.

Diatom productivity in the upper ocean contributes to the amount of silicon exported to the lower ocean.[104]When diatom cells arelysedin the upper ocean, their nutrients such as iron, zinc, and silicon, are brought to the lower ocean through a process calledmarine snow.Marine snow involves the downward transfer of particulate organic matter by vertical mixing of dissolved organic matter.[105]It has been suggested that silicon is considered crucial to diatom productivity and as long as there is silicic acid available for diatoms to use, the diatoms can contribute to other important nutrient concentrations in the deep ocean as well.[106]

In coastal zones, diatoms serve as the major phytoplanktonic organisms and greatly contribute to biogenic silica production. In the open ocean, however, diatoms have a reduced role in global annual silica production. Diatoms in North Atlantic and North Pacific subtropical gyres only contribute about 5–7% of global annual marine silica production. TheSouthern Oceanproduces about one-third of global marine biogenic silica.[70]The Southern Ocean is referred to as having a "biogeochemical divide"[107]since only minuscule amounts of silicon are transported out of this region.

Human nutrition

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There is some evidence that silicon is important to human health for their nail, hair, bone, and skin tissues,[108]for example, in studies that demonstrate that premenopausal women with higher dietary silicon intake have higherbone density,and that silicon supplementation can increase bone volume and density in patients withosteoporosis.[109]Silicon is needed for synthesis ofelastinandcollagen,of which theaortacontains the greatest quantity in the human body,[110]and has been considered anessential element;[111]nevertheless, it is difficult to prove its essentiality, because silicon is very common, and hence, deficiency symptoms are difficult to reproduce.[112][113]

Silicon is currently under consideration for elevation to the status of a "plant beneficial substance by the Association of American Plant Food Control Officials (AAPFCO)."[114][115]

Safety

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People may be exposed to elemental silicon in the workplace by breathing it in, swallowing it, or having contact with the skin or eye. In the latter two cases, silicon poses a slight hazard as an irritant. It is hazardous if inhaled.[116]TheOccupational Safety and Health Administration(OSHA) has set thelegal limitfor silicon exposure in the workplace as 15 mg/m3total exposure and 5 mg/m3respiratory exposure over an eight-hour workday. TheNational Institute for Occupational Safety and Health(NIOSH) has set arecommended exposure limit(REL) of 10 mg/m3total exposure and 5 mg/m3respiratory exposure over an eight-hour workday.[117]Inhalation ofcrystallinesilica dust may lead tosilicosis,anoccupational lung diseasemarked byinflammationand scarring in the form ofnodular lesionsin the upper lobes of thelungs.[118]

See also

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Notes

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  1. ^Althoughcarbonremains solid at higher temperatures than silicon, itsublimesatatmospheric pressureinstead of melting and boiling, so it has no melting point and boiling point.

References

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