Selenogallate

Selenogallates (or selenidogallates) are chemical compounds which contain anionic units of selenium connected to gallium. They can be considered as gallates where selenium substitutes for oxygen. Similar compounds include the thiogallates and selenostannates. They are in the category of chalcogenotrielates or more broadly chalcogenometallates. ^[1]

Formation

Selenogallates may be produced by heating a metal azide with gallium monoselenide and selenium in a sealed tube. ^[1]

Selenogallates containing Se₂ units are formed by heating with selenium. Conversely, by heating, extra selenium vapour can be lost forming a compound with less selenium. ^[2]

Properties

Most selenogallates are semiconductors. Their resistance drops on exposure to light. Also selenogallates are often coloured, most often red.

Selenogallate structures can include rings such as the four-membered ring: [_GaSeGaSe] or the five-membered [_GaSeSeGaSe]. These can be linked into chains.

Use

Selenogallates are primarily of research interest. They are being researched for photovoltaic cells where efficiencies over 20% are possible, ^[3] and for photoconductors, and non-linear optical devices.

List

name	chem	mw	crystal system	space group	unit cell Å	volume	density	comment	CAS no	references
	LiGaSe2	234.581	orthorhombic	Pna21	a=6.8478 b=8.2575 c=6.5521 Z=4	370.5	4.206	band gap 3.39; SHG		[4]
	[H2dap]4Ga4Se10 dap = 1,2-diaminopropane		monoclinic	C2/c	a 10.821 b 10.820 c 21.386, β 97.265°					[5]
	[(dienH2)(dienH)3]Ga5Se10 dien = diethylenetriamine		monoclinic	P21/c	a 6.3116 b 13.748 c 47.890 β 90.640°			chain		[6]
	[(tetaH2)3(teta)]Ga6Se12 teta = triethylenetetramine		monoclinic	Cc	a 20.566 b 25.896 c 12.785 β 125.568°			chain		[6]
	[bappH2][Ga2Se4] bapp =1,4-Bis-(3-aminopropyl)piperazine	657.63	triclinic	P1	a=6.3517 b=7.8498 c=10.7818 α=71.457° β=84.925° γ=72.084° Z=1	484.93	2.30	yellow;		[7]
	[1,3-pdaH2][Ga2Se2(Se2)(Se3)] 1,3-pda = 1,3-diaminopropane		monoclinic	P21	a 7.5724 b 12.3856 c 8.0889 β 94.120°			band gap 2.08 eV; GaSeSeSeGaSe & GaSeSeGaSe rings; red		[8]
	[1,4-bdaH2][Ga2Se3(Se2)] 1,4-bda = 1,4-diaminobutane		monoclinic	C2/c	a 11.7660 b 11.7743 c 10.9763 β 110.170°			band gap 2.32 eV; orange		[8]
	[Me2NH2]2[Ga2Se2(Se2)2]		monoclinic	P21/c	a 14.13 b 8.456 c 14.07 β 100.32°			band gap 2.07 eV; red		[8]
	α-[AEPH]2[Ga2Se2(Se2)2] AEP = N-(2-aminoethyl)piperazine		monoclinic	Pn	a 6.981 b 15.436 c 11.831 β 91.462°			band gap 1.93 eV; red		[8]
	β-[AEPH]2[Ga2Se2(Se2)2]		monoclinic	P21/c	a 10.623 b 16.495 c 7.163 β 94.93°			band gap 2.10 eV; red		[8]
	[Ga(en)3][Ga3Se7(en)] · H2O	1090.02	orthorhombic	Pna21	a=14.279 b=9.616 c=19.676 Z=4	2701.6	2.680	bicyclic Ga3Se7		[9]
	NaGaS2		monoclinic	C2/c	a 10.226 b 10.227 c 13.506 β 100.926°	1389.9				[10]
	NaGaS2•H2O		monoclinic	C2/c	a=9.5160 b=113986 c=17.8761 β=101.590	1899				[10]
	NaGa3Se5	626.95	orthorhombic	P212121	a=9.764 b=13.624 c=27.000 Z=16	3591.6	4.638			[11]
	KGaSe2	266.74	monoclinic	C2/c	a = 10.878, b = 10.872, c = 15.380, β = 100.18° Z=16	1790.3	3.959	air stable; light yellow; mp=965 °C; [Ga4Se10]8− units connected into sheets; band gap 2.60 eV		[12]
	Cr2.37Ga3Se8		monoclinic	C2/m				magnetic semiconductor; band gap 0.26 eV		[13]
	MnGa2Se4							band gap 2.7 eV		[14]
	[Mn(en)3][Ga2Se5] en = Ethylenediamine	771.51	orthorhombic	Pbcn	a=9.772 b=15.297 c=13.749 Z=4	2055.2	2.50	red; {[Ga2Se5]2-}∞ chains Ga2Se2 and Ga2Se3 rings		[7]
	[Mn(dap)3]0.5GaSe2		orthorhombic	Cmcm	a 9.645 b 16.754 c 12.891					[5]
	[Mn(atep)]Ga2S4 atep = 4-(2-aminoethyl)triethylenetetramine		monoclinic	P21/n	a 9.909 b 11.947 c 14.831, β 102.268°					[5]
	[Co(en)3]Ga2Se		orthorhombic	Cmcm	a 9.692 b 15.631 c 12.698			band gap 3.27 eV		[6]
	{[Ni(tepa)]2SO4}[Ni(tepa)(Ga4S6(SH)4)] tepa = tetraethylenepentamine		monoclinic	C2/c	a 38.829 b 12.290 c 22.471 β 98.398°					[5]
cupric selenogallate	CuGaSe2	291.186	tetragonal		a = 5.5963 c = 11.0036 Z=4	344.617	5.612	metallic grey		[15]
	ZnGa2Se4		tetragonal	I42m						[16]
	ZnGa2Se4		cubic	Fm3m				>15.5GPa		[16]
	Na3Zn2Ga2Se4	519.90	tetragonal	I41acd	a 13.481 c 19.26 Z=16	3500	3.946	red		[17]
	Na6Zn3Ga2Se9		monoclinic	C2/c	a 16.71 b 16.69 c 13.79 β 101.346°					[18]
	KZn4Ga5Se12			R3				SHG		[19]
	LiGaGe2Se6	695.60	orthorhombic	Fdd2	a 12.5035 b 23.710 c 7.1177	2110.1	4.336	brown; band gap 2.64 eV; mp=710 °C		[20] [21]
	Li2Ga2GeS6		orthorhombic	Fdd2	a=12.0796 b=22.73 c=6.84048					[22]
	NaGaGe3Se8		monoclinic	P21/c	a 7.233 b 11.889 c 17.550 β 101.75°					[23]
	KGaGeSe4	497.25	monoclinic	P21/c	a=7.3552 b=12.4151 c=17.6213 β =97.026 Z=8	1597.02	4.136	yellow		[24]
	RbGaSe2	313.11	monoclinic	C2/c	a = 10.954, b = 10.949, c = 16.064, β = 99.841° Z=16	1898.2	4.382	colourless; mp=930 °C; ∞2[Ga4Se88−] layers of supertetrahedra;		[1]
	RbZn4Ga5Se12			R3				SHG		[19]
	RbGaGeSe4	543.62	orthorhombic	Pnma	a=17.5750 b=7.4718 c=12.4449 Z=8	1634.23	4.419	orange		[24]
	AgGaSe2		tetragonal	I42d	a = 5.9921, c = 10.883		5.71	transparent from 0.71 to 18 µm; band gap ~1.7		[25]
	AgGa5Se8			P42m	a=5.50 c=11.04			band gap 2.1 eV		[25]
	Ag9GaSe6			P213				band gap 0.56 eV		[25]
	Ag9GaSe6		cubic	F43m	a=11.126					[25]
	LixAg1–xGaSe2 (x = 0.2–0.8)		tetragonal	I42d				SHG		[4]
	Na0.45Ag0.55Ga3Se5		trigonal	R32	a=13.466 c=16.495 Z=12	2590.5		SHG 1.9 × AGS		[26]
	KAg3Ga8Se14	2025.91	monoclinic	Cm	a 12.8805 b 11.6857 c 9.6600 β 115.998° Z=2	1306.87	5.148	orange		[27]
	AgGaGe5Se12							red; transparent for 0.6–16.5 μm; band gap 2.2 eV		[28]
	CdGa2Se4		tetragonal	I4	a=5.3167 c=10.2858 Z=2			semiconductor		[29] [30]
	CdGa2Se4		cubic	F43m	a=5.64 Z=4			>21 GPa metallic		[30]
	CdGa2Se4		cubic	Fm3m	a=5.03 Z=4			4-7.4 GPa		[30]
	KCd4Ga5Se12		trigonal	R3	a 14.362 b 14.362 c 9.724					[31]
	RbCd4Ga5Se12		trigonal	R3	a 14.4055 b 14.4055 c 9.7688			band gap 2.19 eV; SHG=19×AgGaS2		[32] [31]
	InGaSe2		tetragonal	I4/mcm	a = 8.051, c = 6.317 Z=4					[33]
	SnGa4Se7	622.08	monoclinic	Pc	a=7.269 b=6.361 c=12.408 β =106.556 Z=2	549.9	3.757	light yellow;SHG 3.8 × AgGaS2		[34]
	KGaSnSe4-cP84	543.35	cubic	Pa3	a=13.5555 Z=12	2490.8	4.347	red		[24]
	RbGaSnSe4-cP84		cubic	Pa3	a=13.7200 Z=12	589.72	4.550			[24]
	RbGaSn2Se6	866.33	trigonal	R3	a=10.4697 c=9.476 Z=3	899.5	4.798	deep red		[35]
	SnGa2GeSe6	804.48	orthorhombic	Fdd2	a = 47.195, b = 7.521, c = 12.183, Z = 16	4324	4.943	red; SHG 1.7 × AgGaS2
	CsGaSe2-mC64		monoclinic	C2/c	a = 11.043, b = 11.015, c = 16.810, β = 99.49°, Z = 16	2016.7		light grey; layers of supertetrahedra ∞2[Ga4Se84–]; band gap 3.5 eV		[36]
	CsGaSe2-mC16		monoclinic	C2/c	a = 7.651, b = 12.552, c = 6.170, β = 113.62°, Z = 4	542.9		over 610 °C; chains ∞1[GaSe2–]		[36]
	CsGaSe3		monoclinic	P21/c	a=7.727, b=13.014, c=6.705, β=106.39°, Z=4			red; chains; band gap 2.25 eV		[37]
	Cs2Ga2Se5	800.07	monoclinic	C2/c	a = 15.3911, b = 7.3577, c = 12.9219, β = 126.395°, Z = 4	1177.89	4.51	yellow; ∞1[Ga2Se3(Se2)2–] band gap 1.95 eV		[38]
	Cs4Ga6Se11		triclinic	P1	a=9.707 b=9.888 c=16.780 α=76.425° β=77.076° γ=60.876°	1356.3		∞1[Ga6Se11]4–		[39]
	Cs6Ga2Se6		monoclinic	P21/c	a=8.480 b=13.644 c=11.115 β =126.22 Z=2			mp=685 °C; isolated double tetrahedra [Ga2Se6]6−		[40]
	Cs8Ga4Se10		triclinic	P1	a= 7.870 b=9.420 c=11.282 α=103.84° β=93.43° γ=80.88° Z=1		4.42	tetrameric		[41]
	Cs10Ga6Se14		monoclinic	C2/m	a=18.233 b=12.889 c=9.668 β=108.20 Z=2		4.39	hexameric		[41]
	(Cs6Cl)6Cs3[Ga53Se96]	16671.51	trigonal	R3m	a = 11.990, c = 50.012 Z=1	6226.5	4.446	yellow; band gap 2.74 eV		[42]
	CsZn4Ga5Se12		trigonal	R3						[19]
	CsGaGeSe4	591.06	orthorhombic	Pnma	a=17.7666 b=7.5171 c=12.6383 Z=8	1687.9	4.652	white		[24]
	Cs2Ge3Ga6Se14	2007.41		P3m1	a=7.6396 c=13.5866 Z=1	686.72	4.854	black		[43]
	CsAgGa2Se4		monoclinic	P21/c	a=11.225, b=7.944, c=21.303, β=103.10, Z=8	1850.3		layered		[44]
	CsCd4Ga5Se12		trigonal	R3	a 14.4204 b 14.4204 c 9.7803			band gap 2.21 eV; SHG=16×AgGaS2		[32] [31]
	BaGa4Se7		monoclinic	Pc	a = 7.625, b = 6.511, c = 14.702, β = 121.24°			transparent between 0.47 and 18.0 μm; melts 968 °C; SHG		[45] [46]
	Ba4Ga2Se8	132.48	monoclinic	P21/c	a=13.2393 b=6.4305 c=20.6432 β =104.3148 Z=4	1702.90	5.151	black air stable; band gap 1.51 eV		[47] [48]
	Ba5Ga2Se8		orthorhombic	Cmca	a 23.433 b 12.461 c 12.214			band gap 2.51 eV		[49]
	Ba5Ga4Se10	1755.18	tetragonal	I4/mcm	a = 8.752, c = 13.971 Z = 2	1070.2	5.447	red; bicyclic ring with Ga-Ga bridge; band gap 2.20 eV		[50]
	Ba3GaSe4Cl		orthorhombic	Pnma	a 12.691 b 9.870 c 8.716					[51]
	Ba3GaSe4Br		orthorhombic	Pnma	a = 12.8248, b = 9.9608, c = 8.7690 Z = 4			band gap 1.7 eV		[52]
	LiBa4Ga5Se12	1852.42	tetragonal	P421c	a 13.591 c 6.515 Z=2	1203.3	5.113	yellow; band gap 2.44 eV; SHG 1.7×AgGaS2		[32] [53]
	NaBaGaSe3		orthorhombic	Pnma	a 20.46 b 9.177 c 7.177	1347		colourless		[54]
	(Na0.60Ba0.70)Ga2Se4		tetragonal	I4cm	a 7.9549 c 6.2836	397.6	4.725	pale yellow		[55]
	KBa3Ga5Se10Cl2		tetragonal	I4	a 8.6341 c 15.644	1166.2		band gap 2.04 eV; SHG=10×AgGaS2		[32] [56]
	MnBa4Ga4Se10Cl2		tetragonal	I4	8.5858 c 15.7739			band gap 2.8 eV; SHG=30×AgGaS2		[32] [57]
	FeBa4Ga4Se10Cl2		tetragonal	I4	a 8.578 c 15.717			band gap 1.88 eV		[32] [57]
	CoBa4Ga4Se10Cl2		tetragonal	I4	a 8.572 c 15.716			band gap 2.02 eV		[32] [57]
	Cu0.5Ba4Ga4.5Se10Cl2		tetragonal	I4	a 8.559 c 15.778			band gap 2.6 eV; SHG=39×AgGaS2		[32] [57]
	CuBa4Ga5Se12			P421c	a = 13.598, c = 6.527, Z = 2			band gap 1.45 eV; SHG=3×AgGaS2		[32] [58]
	ZnBa4Ga4Se10Cl2		tetragonal	I4	a 8.561 c 15.757			band gap 3.08 eV; SHG=59×AgGaS2		[32] [57]
	Ba10Zn7Ga6Se26		tetragonal	I42m	a 11.2907 c 21.760 Z=2	2774.0	5.151	yellow		[59]
	Ba4Ga4GeSe12	1848.35	tetragonal	P421c	a=13.5468 c=6.4915 Z=2	1191.29	5.153	orange yellow; band gap 2.18 eV		[47] [60]
	BaGa2GeSe6			R3						[61]
	RbBa3Ga5Se10Cl2		tetragonal	I4	a 8.6629 c 15.6379			band gap 2.05 eV; SHG=20×AgGaS2		[32] [56]
	Ba2GaYSe5		triclinic	P1	a 7.2876Å b 8.6597Å c 9.3876Å, α 103.51° β 103.04° γ 107.43°					[62]
	Ba4AgGaSe6	1199.44	orthorhombic	Pnma	a=9.1006 b=4.472 c=17.7572 Z=2	722.71	5.512	dark red; air stable; band gap 2.50		[63]
	Ba4AgGa5Se12	1953.35	tetragonal	P421c	a 13.6544 c 6.5215 Z=2	1215.9	5.335	yellow		[53]
	Ba7AgGa5Se15		trigonal	P31c	a 10.0467 c 18.689			band gap 2.60 eV		[64]
	CdBa4Ga4Se10Cl2		tetragonal	I4	a 8.611 c 15.805			band gap 3.05 eV; SHG=52×AgGaS2		[32] [57]
	Ba5CdGa6Se12	2401.82	orthorhombic	Ama2	a=24.2458 b=19.1582 c=6.6208 Z=4	3075.4	5.187	yellow; air stable; band gap 2.60 eV; mp=866 °C		[47] [65]
	BaGa2SnSe6	869.23	trigonal	R3	a = 10.145, c = 9.249 Z = 3	824.4	5.253	red; SHG 5.2×AgGaS2		[66]
	Ba4Ga4SnSe12	1894.45	tetragonal	P421c	a 13.607 c 6.509 Z=2	1205.2	5.221	red; band gap 2.16 eV		[67]
	Ba6Ga2SnSe11	1950.73	monoclinic	P21/c	a 18.715 b 7.109 c 19.165, β 103.29°	2481.5	5.221	red; bad gap 1.99 eV		[67]
	Ba2AsGaSe5	814.12	orthorhombic	Pnma	a = 12.632, b = 8.973, c = 9.203, Z = 4	1043.1	5.184	black		[68]
	CsBa3Ga5Se10Cl2		tetragonal	I4	a 8.734 c 15.697	1197.6		band gap 2.08 eV; SHG=100×AgGaS2		[32] [56]
	NaLaGa4Se8		orthorhombic	Fddd	a 21.1979 b 21.1625 c 12.7216					[69]
	La3MnGaSe7	1094.11	hexagonal	P63	a 10.5894 c 6.3458 Z=2	616.25	5.896	black		[70]
	La3FeGaSe7		hexagonal	P63	a=10.5042 c=6.3496	606.74				[71]
	La3CoGaSe7		hexagonal	P63	a=10.5104 c=6.3708	609.48				[71]
	La3NiGaSe7		hexagonal	P63	a=10.4826 c=6.3964	608.71				[71]
	La3CuGaSe7	1102.71	hexagonal	P63	a=10.626 c=6.392 Z=2	626.0	5.859			[47]
	La3ZnGaSe7	1104.54	hexagonal	P63	a=10.630 c=6.374 Z=2	623.7	5.881			[47]
	La3Ag0.6GaSe7		hexagonal	P63	a=10.6, c=6.4 Z=2					[72]
	La3CdGaSe7		hexagonal	P63	a=10.606 c=6.380 Z=2	621.5	6.153			[47]
	Ba2GaLaSe5		orthorhombic	Pnma	a 12.5049 b 9.6288 c 8.7355					[73]
	NaCeGa4Se8		orthorhombic	Fddd	a 21.141 b 21.138 c 12.712					[69]
	Ce3CuGaSe7	1106.34	hexagonal	P63	a=10.6007 c=6.3775 Z=2	620.65	5.920			[47]
	Ba2GaCeSe5		orthorhombic	Fddd	a 12.494 b 9.599 c 8.738					[73]
	Pr3CuGaSe7	1108.71	hexagonal	P63	a=10.4181 c=6.3743 Z=2	599.16	6.146			[47]
	NaNdGa4Se8		orthorhombic	Fddd	a 21.015 b 21.045 c 12.709					[69]
	Nd3FeGaSe7		hexagonal	P63	a 10.2453 c 6.4076 Z=2	582.47				[74]
	Nd3CoGaSe7		hexagonal	P63	a=10.2296 c=6.4272	582.47				[71]
	Nd3NiGaSe7		hexagonal	P63	a=10.2117 c=6.4066	578.57				[71]
	Nd3CuGaSe7	1118.70	hexagonal	P63	a=10.3426 c=6.3869 Z=2	591.7	6.279			[47]
	Ba2GaNdSe5		triclinic	P1	a 7.29Å b 8.7914Å c 9.47Å, α 103.77° β 102.91° γ 107.72°					[62]
	SmGa2Se4		rhombic		a=21.34, b=21.60, c=12.74					[75]
	Ba2GaSmSe5		triclinic	P1	a 7.3017Å b 8.7635Å c 9.4554Å, α 103.672° β 102.963° γ 107.637°					[62]
	Gd3FeGaSe7		hexagonal	P63	a 10.0762 c 6.4265 Z=2					[74]
	Ba2GaGdSe5		triclinic	P1	a 7.2834Å b 8.7062Å c 9.4079Å, α 103.65° β 103.02° γ 107.52°					[62]
	Dy3FeGaSe7		hexagonal	P63	a 9.9956Å c 6.398 Z=2					[74]
	Ba2GaDySe5		triclinic	P1	a 7.2772Å b 8.6543Å c 9.3792Å, α 103.53° β 103.07° γ 107.43°					[62]
	Ba2GaErErSe5		triclinic	P1	a 7.2721Å b 8.6258Å c 9.3621Å, α 103.41° β 103.13° γ 107.39°					[62]
	Ba2GaTbSe5		triclinic	P1	a 7.309 b 8.719 c 9.433, α 103.548° β 103.039° γ 107.520°					[73]
	Ba2GaHoSe5		triclinic	P1	a 7.2964 b 8.670 c 9.406, α 103.482° β 103.049° γ 107.423°					[73]
	Ba2GaTmSe5		triclinic	P1	a 7.2884 b 8.6376 c 9.3823, α 103.429° β 103.075° γ 107.360°					[73]
	Ba2GaYbSe5		triclinic	P1	a 7.2864 b 8.6257 c 9.3716, α 103.4154° β 103.0369° γ 107.3396°					[73]
	Ba2GaLuSe5		triclinic	P1	a 7.2829 b 8.6120 c 9.368, α 103.362° β 103.051° γ 107.308°					[73]
	HgGa2Se4									[76]
	KHg4Ga5Se12	2137.58	trigonal	R3	a 14.3203 b 14.3203 c 9.7057 Z=3	1723.7	6.178	band gap 1.61 eV; SHG=20×AgGaS2		[32] [77] [78]
	TlGaSe2	432.01	monoclinic	C2/c	a=10.760 b=10.762 c=15.626 β=100.19 Z=16	1780.8	6.445	black; layers of supertetrahedra; mp 804 °C; band gap 1.87 eV		[79]
	TlGaGeSe4	662.52	orthorhombic	Pnma	a=17.4742 b=7.4105 c=11.9406 Z=8	1546.22	5.692			[24]
	Tl2Ga2GeSe6		tetragonal	I4/mmc	a=8.0770 c=6.2572 Z=4					[80]
	Tl0.8Ga0.8Ge1.2Se4-mC112	622.22	monoclinic	C2/c	a=13.5831 b=7.4015 c=30.7410 β =96.066 Z=16	3073.3	5.379	red		[24]
	TlGaSnSe4-mP56	701.04	monoclinic	P21/c	a=7.501 b=12.175 c=18.203 β =97.164 Z=8	1649.4	5.646	red		[24]
	TlGaSnSe4-cP84	708.62	cubic	Pa3	a=13.4755 Z=12	2447.0	5.770	red		[24]
	Tl2Ga2SnSe6		tetragonal	I4/mmc	a=8.095 c=6.402 Z=4					[80]
	TlGaSn2Se6			R3	a=10.3289 c=9.4340	871.64	5.6301	dark grey in bulk; maroon powder		[81]
	PbGa2Se4	662.47	orthorhombic	Fddd	a =12.73 b=21.26 c=21.55 Z=32	5830	6.036	yellow to red; mp 780 °C; band gap 1.83 eV		[82] [83]
	Pb0.72Mn2.84Ga2.95Se8		hexagonal	P6	a 17.550 c 3.8916					[84]
	PbGa2GeSe6		orthorhombic	Fdd2				mp 720 °C biaxial (−)		[61]
	Pb4Ga4GeSe12		tetragonal	P421c	a = 13.064 c = 6.310 Z=2					[85]
	Ba2GaBiSe5		orthorhombic	Pnma	a=12.691 b=9.190 c=9.245 Z=4	1078.2	5.841	yellow		[86]

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