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Binary compounds of silicon
Any binary chemical compound containing just silicon and another chemical element

Binary silicon compounds are chemical compounds containing silicon and one other element. Silicides specifically involve silicon bonded to a more electropositive element. These compounds include saltlike silicides with s-block metals, covalent silicides with hydrogen and groups 10–17 elements, and metallic silicides formed by transition metals (except silver, gold, and group 12). Their general formula is MnSi or MSin, where M is a metal. Silicides tend to be brittle, hydrolysis-resistant intermetallics that conduct electricity; some, like CrSi2 and Mg2Si, are semiconductors. Their heat capacities follow the Kopp–Neumann law, being proportional to their silicon content.

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Group 1

Silicides of group 1 elements are saltlike silicides, except for silane (SiH4) whose bonds to hydrogen are covalent. Higher silane homologues are disilane and trisilane. Polysilicon hydride is a two-dimensional polymer network.

Many cluster compounds of lithium silicides are known, such as Li13Si4, Li22Si5, Li7Si3 and Li12Si7.2 Li4.4Si is prepared from silicon and lithium metal in high-energy Ball mill process.3 Potential uses include electrodes in lithium batteries. Li12Si7 has a Zintl phase with planar Si56− rings. Li NMR spectroscopy suggests these rings are aromatic.4

Other group 1 elements also form clusters: sodium silicide can be represented by NaSi, NaSi2 and Na11Si365 and potassium silicide by K8Si46. Group 1 silicides are in general high melting, metallic grey, with moderate to poor electrical conductance and prepared by heating the elements. Superconducting properties have been reported for Ba8Si46.6 Several silicon Zintl ions (Si4−4, Si4−9, Si2−5) are known with group 1 counterions.7

Group 2

Silicides of group 2 elements are also saltlike silicides except for beryllium whose phase diagram with silicon is a simple eutectic (1085 °C @ 60% by weight silicon).8 Again there is variation in composition: magnesium silicide is represented by Mg2Si,9 calcium silicide can be represented by Ca2Si, CaSi, CaSi2, Ca5Si3 and by Ca14Si19,10 strontium silicide can be represented by Sr2Si, SrSi2 and Sr5Si311 and barium silicide can be represented by Ba2Si, BaSi2, Ba5Si3 and Ba3Si4.12 Mg2Si, and its solid solutions with Mg2Ge and Mg2Sn, are good thermoelectric materials and their figure of merit values are comparable with those of established materials.

Transition and inner transition metals

The transition metals form a wide range of silicon intermetallics with at least one binary crystalline phase. Some exceptions exist. Gold forms a eutectic at 363 °C with 2.3% silicon by weight (18% atom percent) without mutual solubility in the solid state.13 Silver forms another eutectic at 835 °C with 11% silicon by weight, again with negligible mutual solid state solubility. In group 12 all elements form a eutectic close to the metal melting point without mutual solid-state solubility: zinc at 419 °C and > 99 atom percent zinc and cadmium at 320 °C (< 99% Cd).

Commercially relevant intermetallics are group 6 molybdenum disilicide, a commercial ceramic mostly used as an heating element. Tungsten disilicide is also a commercially available ceramic with uses in microelectronics. Platinum silicide is a semiconductor material. Ferrosilicon is an iron alloy that also contains some calcium and aluminium.

MnSi, known as brownleeite, can be found in outer space. Several Mn silicides form a Nowotny phase. Nanowires based on silicon and manganese can be synthesised from Mn(CO)5SiCl3 forming nanowires based on Mn19Si33.14 or grown on a silicon surface151617 MnSi1.73 was investigated as thermoelectric material18 and as an optoelectronic thin film.19 Single-crystal MnSi1.73 can form from a tin-lead melt20

In the frontiers of technological research, iron disilicide is becoming more and more relevant to optoelectronics, specially in its crystalline form β-FeSi2.2122 They are used as thin films or as nanoparticles, obtained by means of epitaxial growth on a silicon substrate.2324

Atomic numberNameSymbolGroupPeriodBlockPhases
21ScandiumSc34dSc5Si3, ScSi, Sc2Si3,25262728
22TitaniumTi44dTi5Si3, TiSi, TiSi2, TiSi3, Ti6Si429
23VanadiumV54dV3Si, V5Si3, V6Si5, VSi2, V6Si53031
24ChromiumCr64dCr3Si, Cr5Si3, CrSi, CrSi23233
25ManganeseMn74dMnSi, Mn9Si2, Mn3Si, Mn5Si3, Mn11Si934
26IronFe84dFeSi2, FeSi3536 Fe5Si3, Fe2Si, Fe3Si
27CobaltCo94dCoSi, CoSi2, Co2Si, Co2Si, Co3Si3738
28NickelNi104dNi3Si, Ni31Si12, Ni2Si, Ni3Si2, NiSi (Nickel monosilicide), NiSi23940
29CopperCu114dCu17Si3, Cu56Si11,Cu5Si, Cu33Si7, Cu4Si, Cu19Si6,Cu3Si,Cu87Si134142
30ZincZn124deutectic43
39YttriumY34dY5Si3, Y5Si4, YSi, Y3Si5,4445 YSi1.4.46
40ZirconiumZr45dZr5Si3, Zr5Si4, ZrSi, ZrSi2,47 Zr3Si2, Zr2Si, Zr3Si48
41NiobiumNb55dNb5Si3, Nb4Si49
42MolybdenumMo65dMo3Si, Mo5Si3, MoSi250
43TechnetiumTc75dTc4Si7 (proposed)51
44RutheniumRu85dRu2Si, Ru4Si3, RuSi, Ru2Si35253
45RhodiumRh95dRhSi,54 Rh2Si, Rh5Si3, Rh3Si2, Rh20Si1355
46PalladiumPd105dPd5Si, Pd9Si2, Pd3Si, Pd2Si, PdSi56
47SilverAg115deutectic57
48CadmiumCd125deutectic58
57LanthanumLa6fLa5Si3, La3Si2, La5Si4, LaSi, LaSi259
58CeriumCe6fCe5Si3, Ce3Si2, Ce5Si4, CeSi,60 Ce3Si5, CeSi261
59PraseodymiumPr6fPr5Si3, Pr3Si2, Pr5Si4, PrSi, PrSi262
60NeodymiumNd6fNd5Si3, Nd5Si4, Nd5Si3,NdSi, Nd3Si4, Nd2Si3, NdSix63
61PromethiumPm6f
62SamariumSm6fSm5Si4, Sm5Si3, SmSi, Sm3Si5, SmSi264
63EuropiumEu6f
64GadoliniumGd6fGd5Si3, Gd5Si4, GdSi, GdSi265
65TerbiumTb6fSi2Tb (terbium silicide), SiTb, Si4Tb5, Si3Tb566
66DysprosiumDy6fDy5Si5, DySi, DySi267
67HolmiumHo6fHo5Si3,Ho5Si4,HoSi,Ho4Si5,HoSi268
68ErbiumEr6fEr5Si3, Er5Si4, ErSi, ErSi269
69ThuliumTm6f
70YtterbiumYb6fSi1.8Yb,Si5Yb3,Si4Yb3, SiYb, Si4Yb5, Si3Yb570
71LutetiumLu36dLu5Si371
72HafniumHf46dHf2Si, Hf3Si2, HfSi, Hf5Si4, HfSi27273
73TantalumTa56dTa9Si2, Ta3Si, Ta5Si374
74TungstenW66dW5Si3, WSi275
75RheniumRe76dRe2Si, ReSi, ReSi1.876 Re5Si377
76OsmiumOs86dOsSi, Os2Si3, OsSi278
77IridiumIr96dIrSi, Ir4Si5, Ir3Si4, Ir3Si5, IrSi3. Ir2Si3, Ir4Si7, IrSi27980
78PlatinumPt106dPt25Si7, Pt17Si8, Pt6Si5, Pt5Si2, Pt3Si, Pt2Si, PtSi81
79GoldAu116dEutectic diagram at link82
80MercuryHg126deutectic83
89ActiniumAc7f
90ThoriumTh7fTh3Si2, ThSi, Th3Si5, and ThSi2−x84
91ProtactiniumPa7f
92UraniumU7fU3Si, U3Si2, USi, U3Si5, USi2−x, USi2 and USi385
93NeptuniumNp7fNpSi3, Np3Si2, and NpSi86
94PlutoniumPu7fPu5Si3, Pu3Si2, PuSi, Pu3Si5 and PuSi287
95AmericiumAm7fAmSi, AmSi288
96CuriumCm7fCmSi, Cm2Si3, CmSi289
97BerkeliumBk7f
98CaliforniumCf7f
99EinsteiniumEs7f
100FermiumFm7f
101MendeleviumMd7f
102NobeliumNo7f
103LawrenciumLr37d
104RutherfordiumRf47d
105DubniumDb57d
106SeaborgiumSg67d
107BohriumBh77d
108HassiumHs87d
109MeitneriumMt97d
110DarmstadtiumDs107d
111RoentgeniumRg117d
112CoperniciumCn127d

Group 13

In group 13 boron (a metalloid) forms several binary crystalline silicon boride compounds: SiB3, SiB6, SiBn.90 With aluminium, a post-transition metal, a eutectic is formed (577 °C @ 12.2 atom % Al) with maximum solubility of silicon in solid aluminium of 1.5%. Commercially relevant aluminium alloys containing silicon have at least element added.91 Gallium, also a post-transition metal, forms a eutectic at 29 °C with 99.99% Ga without mutual solid-state solubility;92 indium93 and thallium94 behave similarly.

Group 14

Silicon carbide (SiC) is widely used as a ceramic or example in car brakes and bulletproof vests. It is also used in semiconductor electronics. It is manufactured from silicon dioxide and carbon in an Acheson furnace between 1600 and 2500 °C. There are 250 known crystalline forms with alpha silicon carbide the most common. Silicon itself is an important semiconductor material used in microchips. It is produced commercially from silica and carbon at 1900 °C and crystallizes in a diamond cubic crystal structure. Germanium silicide forms a solid solution and is again a commercially used semiconductor material.95 The tin–silicon phase diagram is a eutectic96 and the lead–silicon phase diagram shows a monotectic transition and a small eutectic transition but no solid solubility.97

Group 15

Silicon nitride (Si3N4) is a ceramic with many commercial high-temperature applications such as engine parts. It can be synthesized from the elements at temperatures between 1300 and 1400 °C. Three different crystallographic forms exist. Other binary silicon nitrogen compounds have been proposed (SiN, Si2N3, Si3N)98 and other SiN compounds have been investigated at cryogenic temperatures (SiN2, Si(N2)2, SiNNSi).99 Silicon tetraazide is an unstable compound that easily detonates.

The phase diagram with phosphorus shows SiP and SiP2.100 A reported silicon phosphide is Si12P5 (no practical applications),101102 formed by annealing an amorphous Si-P alloy.

The arsenic–silicon phase diagram measured at 40 Bar has two phases: SiAs and SiAs2.103 The antimony–silicon system comprises a single eutectic close to the melting point of Sb.104 The bismuth system is a monotectic.105

Group 16

In group 16 silicon dioxide is a very common compound that widely occurs as sand or quartz. SiO2 is tetrahedral with each silicon atom surrounded by 4 oxygen atoms. Numerous crystalline forms exist with the tetrahedra linked to form a polymeric chain. Examples are tridymite and cristobalite. A less common oxide is silicon monoxide that can be found in outer space. Unconfirmed reports exist for nonequilibrium Si2O, Si3O2, Si3O4, Si2O3 and Si3O5.106 Silicon sulfide is also a chain compound. Cyclic SiS2 has been reported to exist in the gas phase.107 The phase diagram of silicon with selenium has two phases: SiSe2 and SiSe.108 Tellurium silicide is a semiconductor with formula TeSi2 or Te2Si3.109

Group 17

Binary silicon compounds in group 17 are stable compounds ranging from gaseous silicon fluoride (SiF4) to the liquids silicon chloride (SiCl4 and silicon bromide SiBr4) to the solid silicon iodide (SiI4). The molecular geometry in these compounds is tetrahedral and the bonding mode covalent. Other known stable fluorides in this group are Si2F6, Si3F8 (liquid) and polymeric solids known as polysilicon fluorides (SiF2)x and (SiF)x. The other halides form similar binary silicon compounds.110

The periodic table of the binary silicon compounds

SiH4He
LiSiBeSiB3SiCSi3N4SiO2SiF4Ne
NaSiMg2SiAlSiSiPSiS2SiCl4Ar
KSiCaSi2ScSiTiSiV5Si3Cr5Si3MnSiFeSiCoSiNiSiCu5SiZnGaSi1−xGexSiAsSiSe2SiBr4Kr
RbSiSr2SiYSiZrSiNb5Si3Mo5Si3TcRuSiRhSiPdSiAgCdInSnSbTeSi2SiI4Xe
CsSiBa2SiLuSiHfSiTa5Si3W5Si3ReSi2OsSiIrSiPtSiAuHgTlPbBiPoAtRn
FrRaLrRfDbSgBhHsMtDsRgCnNhFlMcLvTsOg
LaSiCeSiPrSiNdSiPmSmSiEuSiGdSiTbSiDySiHoSiErSiTmYbSi
AcThSi PaUSi NpSiPuSiAmSiCmSiBkCfEsFmMdNo
Binary compounds of silicon
Covalent silicon compoundsmetallic silicides.
Ionic silicidesDo not exist
Eutectic / monotectic / solid solutionUnknown / Not assessed

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