# Nitridosilicate

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Class of chemical compounds

The **nitridosilicates** are chemical compounds that have anions with [nitrogen](/source/Nitrogen) bound to [silicon](/source/Silicon). Counter [cations](/source/Cation) that balance the electric charge are mostly [electropositive](/source/Electropositive) metals from the [alkali metals](/source/Alkali_metal), [alkaline earths](/source/Alkaline_earth) or [rare earth elements](/source/Rare_earth_elements). Silicon and nitrogen have similar [electronegativities](/source/Electronegativities), so the bond between them is covalent. Nitrogen atoms are arranged around a silicon atom in a [tetrahedral](/source/Tetrahedral) arrangement.[1]

Related compounds include pnictogenidosilicates :[phosphidosilicates](/source/Phosphidosilicates), [arsenidosilicates](/source/Arsenidosilicate) and [antimonosilicates](https://en.wikipedia.org/w/index.php?title=Antimonosilicate&action=edit&redlink=1); pnictogenidogernamates: [phosphidogermanates](/source/Phosphidogermanate). By replacing silicon, there are also [nitridogermanates](/source/Nitridogermanate), [nitridostannates](https://en.wikipedia.org/w/index.php?title=Nitridostannate&action=edit&redlink=1), [nitridotantalates](https://en.wikipedia.org/w/index.php?title=Nitridotantalate&action=edit&redlink=1) and [nitridotitanates](https://en.wikipedia.org/w/index.php?title=Nitridotitanate&action=edit&redlink=1).

## Use

Nitridosilicates are used as host substances for [europium](/source/Europium) in [LED](/source/LED) [phosphors](/source/Phosphor). Examples include CASN ([calcium aluminium silicide nitride](https://en.wikipedia.org/w/index.php?title=Calcium_aluminium_silicide_nitride&action=edit&redlink=1)) (CaAlSiN3), SCASN (SrCaAlSiN3) and SCSN (SrCaSiN3). These fluoresce red.[2]

## Production

Nitridosilicates can be made in a [solid state reaction](/source/Solid_state_reaction) by heating [silicon nitride](/source/Silicon_nitride) with metallic [nitrides](/source/Nitride) in a nitrogen atmosphere at over 1300 °C. If the mixtures are exposed to oxygen or air, then oxides or [oxynitridosilicates](https://en.wikipedia.org/w/index.php?title=Oxynitridosilicate&action=edit&redlink=1) are produced instead. Instead of metal nitrides, ammine complexes, [amides](/source/Metal_amides) or [imides](/source/Inorganic_imide) can be used instead. In place of the highly stable silicon nitride, [silicon diimide](https://en.wikipedia.org/w/index.php?title=Silicon_diimide&action=edit&redlink=1) can be used.[3] Carbothermal reduction involves using a metal oxide or carbonate heated with carbon in a nitrogen atmosphere.[4]

## Properties

The ratio of silicon to nitrogen varies from 1:4 to 7:10 (0.25 to 0.7) with increased condensation, and fewer sites for metals with high silicon content. At a ratio of 3:4 (0.75) there is no longer capacity for metal, as that is [silicon nitride](/source/Silicon_nitride).[5] The more condensed substances, with lower nitrogen content, have greater number of silicon atoms surrounding the nitrogen. This coordination number can vary from one to four, with the most common being three. The silicon atom always is coordinated by four nitrogen atoms. In the [silicates](/source/Silicate), silicon is surrounded by four oxygen atoms, but each oxygen is only connected to one or two silicon atoms, and only very rarely three. So nitridosilicates can form more diverse structures than the silicates.[6]

Nitridosilicates with higher proportion of silicon (more condensed) are more resistant to attack by water and oxygen, and so can be exposed to the atmosphere without decomposition.[6] These condensed nitridosilicates are mechanically strong, and resistant to heat, acids and alkalis.[1]

SiN4 tetrahedra can be connected to each other via vertices or edges. This differs from SiO4 which only connects via vertices.[1]

## Use

Nitridosilicates have been used to make [abrasives](/source/Abrasive), [turbine blades](/source/Turbine_blade), [cutting tools](/source/Cutting_tool) and phosphors.[4]

## Nitridosilicates

name formula formula weight crystal system space group unit cell volume density comments ref LiSi2N3 [5] Li2SiN2 [7] Li5SiN3 [7] Li8SiN4 [8] Li18Si3N10 [7] Li21Si3N11 I4 a=9.4584 c=9.5194 antifluorite structure [7] BeSiN2 [9] MgSiN2 [5] NaSi2N3 [9] Ca2Si5N8 332.64 monoclinic Cc a = 14.3280 b = 5.61165 c = 9.69406 β = 112.1484 Z=4 721.92 3.06 Eu orange fluorescence [5][10][4] CaSiN2 [5] Ca3SiN3H monoclinic C2/c a = 5.236 b = 10.461 c = 16.389 β = 91.182° Z = 8 semiconductor: band gap 3.1 eV [11] Ca4SiN4 [5] Ca5Si2N6 [5] Ca12Si4[SiN4] triclinic P1 a 9.0103 b 9.0218 c 13.8252 α 71.053° β 82.738° γ 69.763° black [12] Ca16Si17N34 [5] CaMg3SiN4 I41/a [13] Ca5[Si2Al2N8] orthorhombic Pbcn a = 9.255 b = 6.140 c = 15.578 [14] LiCa3Si2N5 monoclinic C2/c a = 5.145 b = 20.380 c = 10.357 β = 91.24° [15] Li4Ca3Si2N6 288.24 monoclinic C2/m a=5.787 b=9.705 c=5.977 β=90.45 335.7 2.852 [5][16] Li2CaSi2N4 [5] Li2Ca2Mg2Si2N6 [5] Li2Ca3MgSi2N6 [5] CaMg3SiN4 I41/a a = 11.424 c = 13.445 Z=16 [9] CaAlSiN3 orthorhombic Cmc21 Eu yellow fluorescence [17] CaAlSi4N7 orthorhombic Pna21 a = 11.6819, b = 21.0193, c = 4.9177 Å [18] Ca4AlSiN5 orthorhombic Pna21 a 11.2058 b 9.0512 c 6.0203 faint red [12] Ca5Al2Si2N8 orthorhombic Pbca a= 9.255 b = 6.140 c = 15.578 Z=4 885.2 3.171 yellow [9][14] CaScSi4N7 [5] Manganese silicide dinitride MnSiN2 orthorhombic Pna21 a = 5.271, b = 6.521, and c = 5.0706 V=174.26 intense red [8] Fe2Si5N8 364.23 monoclinic Cc a= 14.0408 b = 5.32635 c = 9.5913 β = 110.728 Z=4 decompose 1370K; brown [10] ZnSiN2 [9] SrSiN2 [5] Sr2Si5N8 orthorhombic Pmn21 a = 5.71006 b = 6.81914 c = 9.33599 Z=2 363.52 3.908 Eu red fluorescence [5][4][19] SrSi6N8 [5] SrSi7N10 [18] Sr5Si7P2N16 920.83 Pnma a=5.6748 b=28.0367 c=9.5280 Z=4 1522.1 4.018 [20] SrAlSi4N7 orthorhombic Pna21 a = 11.742 b = 21.391 c = 4.966 Z = 8 1247.2 [21] Li2SrSi2N4 cubic a=10.69 Z=12 1220 [5][22] Li4Sr3Si2N6 monoclinic C2/m a = 6.127, b = 9.687, c = 6.220, β = 90.24° Z=2 369.1 3.876 [16] SrBeSi2N4 p62c a=4.86082 c=9.42264 Z=2 [23] SrMg3SiN4 I41/a a = 11.495 c = 13.512 Z=16 [9][13] Sr8Mg7Si9N22 Cm a 15.280 b 7.4691 c 10.936 β 110.462° [24] SrAlSiN3 Cmc21 [17] SrAlSi4N7 Pna21 [18] SrScSi4N7 [5] YScSi4N6C hexagonal P63mc a=5.9109 c=9.677 [25] CaYSi4N7 [5] SrYSi4N7 [5] Ca8In2SiN4 orthorhombic Ibam a = 12.904 b = 9.688 c = 10.899 Z = 4 metallic [11] BaSiN2 [5] Ba5Si2N6 [9] Ba2Si5N8 orthorhombic Pmn21 Eu red fluorescence [5][4] BaSi6N8 Imm2 a = 7.9316, b = 9.3437, c = 4.8357, Z = 2 358.38 [5][26] BaSi7N10 monoclinic a = 6.8729, b = 6.7129, c = 9.6328, β = 106.269, Z = 2 most condensed [5][27] Ba6Si6N10O2(CN2) P6 a = 16.255, c = 5.469, Z = 3 yellow, grown in liquid sodium [28] BaMg3SiN4 P1 a = 3.451 b = 6.069 c = 6.101 α = 85.200 β = 73.697 γ = 73.566° Z=1 [29] Ba2AlSi5N9 triclinic P1 a = 9.860 b = 10.320 c = 10.346 α = 90.37° β = 118.43° γ = 103.69° Z = 4 [30] Ba5Si11Al7N25 Pnnm a = 9.5923, b = 21.3991, c = 5.8889 Å Z = 2 with Eu yellow emission [31] BaSi4Al3N9 P21/C a = 5.8465, b = 26.726, c = 5.8386 Å, β = 118.897° and Z = 4 with Eu blue emission [31] BaScSi4N7 [5] BaYSi4N7 [5] LaSi3N5 orthorhombic P212121 a=7.853 b=11.264 c=4.8172 [5][32] La3Si6N11 tetragonal P4bm [5] La5Si3N9 [9] La7Si6N15 [9] Li5La5Si4N12 tetragonal P4b2 a = 11.043 c = 5.573 Z = 2 [33] calcium lanthanum nitridosilicate CaLaSiN3 Ca can be substituted by Yb or Eu [34] CaLaSi4N7 [5] CeSi3N5 orthorhombic P212121 [9][32] Ce3Si6N11 tetragonal P4bm [9] Ce3Si5N9 [9] Ce7Si6N15 triclinic [9] Ce7Si6N15 trigonal [9] Li5Ce5Si4N12 tetragonal P4b2 a = 10.978 c = 5.514 Z = 2 [33] PrSi3N5 orthorhombic P212121 [32] Pr3Si6N11 tetragonal P4bm [9] Pr5Si3N9 [9] Pr7Si6N15 [9] NdSi3N5 orthorhombic P212121 [32] Nd3Si6N11 tetragonal P4bm [32] Ba2Nd7Si11N23 dark blue [35] Sm3Si6M11 tetragonal P4bm a=9.997 c=4.836 [9][32] Ca3Sm3[Si9N17] cubic P4_3m a=7.3950; Z=1 404.4 [36] Eu2SiN3 Cmca a = 5.42, b = 10.610, c = 11.629, Z = 8 [9][37] dieuropium penta siliconoctanitride Eu2Si5N8 orthorhombic Pnm21 a=5.7094 b=6.8207 c=9.3291 Z=2 363.29 5.087 red [9][38] EuMg3SiN4 I41/a a = 11.511 c = 13.552 Z=16 [13] Ca3Yb3[Si9N17] cubic P4_3m a=730.20 Z=1 389.3 [36] BaYbSi4N7 includes NSi4 clusters [9][39] europium ytterbium tetrasiliconheptanitride EuYbSi4N7 hexagonal P63mc a=5.9822 c=9.7455 302.03 5.887 brown [9][38] SrYbSi4N7 [9] EuYbSi4N7 [9] CaLuSi4N7 [5] SrLuSi4N7 [5] BaLuSi4N7 [5] Pb2Si5N8 666.90 orthorhombic Pmn21 a = 5.774 b = 6.837 c = 9.350 269.11 6.001 Pb-Pb dumbbells [19]

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v t e Salts and covalent derivatives of the silicide ion SiH4 +H He LiSi Be2Si SiB3 SiB6 +B SiC +C Si3N4 -N +N SiO2 SiF4 Ne NaSi Mg2Si Al Si4− SiP, SiP2 -P +P SiS2 -S SiCl4 Ar KSi CaSi CaSi2 ScSi Sc5Si3 Sc2Si3 Sc5Si4 TiSi TiSi2 V3Si V5Si3, V6Si5, VSi2, V6Si5 Cr3Si Cr5Si3, CrSi, CrSi2 MnSi, MnSi2, Mn9Si2, Mn3Si, Mn5Si3, Mn11Si9 FeSi2 FeSi Fe5Si3 Fe2Si Fe3Si CoSi, CoSi2, Co2Si, Co3Si NiSi, more… Cu17Si3, Cu56Si11, Cu5Si, Cu33Si7, Cu4Si, Cu19Si6, Cu3Si, Cu87Si13 Zn Ga GeSi +Ge SiAs, SiAs2 -As +As SiSe2 SiSe SiBr4 Kr RbSi SrSi2 YSi Y5Si3, Y5Si4, Y3Si5, YSi1.4 ZrSi Zr5Si3, Zr5Si4, ZrSi2, Zr3Si2, Zr2Si, Zr3Si Nb4Si Nb5Si3 MoSi2 Mo3Si Mo5Si3 Tc RuSi Ru2Si, Ru4Si3, Ru2Si3 RhSi Rh2Si, Rh5Si3, Rh3Si2, Rh20Si13 PdSi Pd5Si, Pd9Si2, Pd3Si, Pd2Si Ag Cd In Sn Sb TeSi2 Te2Si3 SiI4 Xe CsSi Ba2Si BaSi2, Ba5Si3 Ba3Si4 * Lu5Si3 HfSi Hf2Si, Hf3Si2, Hf5Si4, HfSi2 Ta9Si2, Ta3Si, Ta5Si3 WSi2 W5Si3 ReSi Re2Si, ReSi1.8 Re5Si3 OsSi IrSi PtSi Au Hg Tl Pb Bi Po At Rn Fr Ra ** Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og * LaSi2 La5Si3, La3Si2, La5Si4, LaSi CeSi2 Ce5Si3, Ce3Si2, Ce5Si4, CeSi, Ce3Si5 PrSi2 Pr5Si3, Pr3Si2, Pr5Si4, PrSi NdSi Nd5Si3, Nd5Si4, Nd5Si3, Nd3Si4, Nd2Si3, NdSix Pm SmSi2 Sm5Si4, Sm5Si3, SmSi, Sm3Si5 Eu? GdSi2 Gd5Si3, Gd5Si4, GdSi TbSi2 SiTb, Si4Tb5, Si3Tb5 DySi2 DySi HoSi2 Ho5Si3, Ho5Si4, HoSi, Ho4Si5 ErSi2 Er5Si3, Er5Si4, ErSi Tm? YbSi Si1.8Yb, Si5Yb3, Si4Yb3, Si4Yb5, Si3Yb5 ** Ac ThSi PaSi USi2 NpSi2 PuSi Am Cm Bk Cf Es Fm Md No

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