Gallium(III) sulfide

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Gallium(III) sulfide
Gallium(III) sulfide.png
Names
Other names
gallium sesquisulfide
Identifiers
3D model (JSmol)
ECHA InfoCard 100.031.526 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 234-688-0
PubChem CID
  • InChI=1S/2Ga.3S/q2*+3;3*-2
    Key: BVSHTEBQPBBCFT-UHFFFAOYSA-N
  • [S-2].[S-2].[S-2].[Ga+3].[Ga+3]
Properties
Ga2S3
Molar mass 235.644 g/mol
Appearanceyellow (α-)
Density 3.77 g/cm3 [1]
Melting point 1,090 °C (1,990 °F; 1,360 K) [1]
Reacts [2]
-80·10−6 cm3/mol
Related compounds
Related compounds
Gallium(II) sulfide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Gallium(III) sulfide, Ga2S3, is a compound of sulfur and gallium, that is a semiconductor that has applications in electronics and photonics.

Contents

Structure

There are four polymorphs, α (hexagonal), α' (monoclinic), β(hexagonal) and γ(cubic). The alpha form is yellow. The crystal structures are related to those of ZnS with gallium in tetrahedral positions. [3] [2] [4] The alpha and beta forms are isostructural with their aluminium analogues. [5] The similarity in crystal form of gamma- with sphalerite (zinc blende), ZnS is believed to explain the enrichment of gallium in sphalerite ores. [5]

Preparation and chemical properties

Ga2S3 can prepared by reacting the elements at high temperature or as a white solid by heating Ga in a stream of H2S at high temperature (950 °C). [2]

It may also prepared by a solid state reaction of GaCl3 and Na2S. [5]

The method of production can determine the polymorphic form produced, the reaction of Ga(OH)3 with H2S at different temperatures is reported to produce a different polymorph depending on the temperature, α- 1020 K, β- 820 K and γ- above 873 K [6]

Ga2S3 decomposes at high temperature forming the non-stoichiometric sulfide, Ga4Sx (4.8 < x < 5.2). [5] Ga2S3 dissolves in aqueous acids and decomposes slowly in moist air forming H2S. [2]

Ga2S3 dissolves in aqueous solutions of potassium sulfide, K2S to form K8Ga4S10 containing the (Ga4S10)8− anion which has an adamantane, molecular P4O10 structure. [5]

Ternary sulfides MIGaS2, MIIGa2S4 and MIIIGaS3 respectively have been of interest due to their unusual electrical properties and some of these can be prepared by reactions of Ga2S3 with metal sulfides e.g. CdGa2S4:- [5]

Ga2S3 + CdS → CdGa2S4

Although by itself Ga2S3 is not a glass former it can be reacted with rare earth sulfides to form glasses e.g. the reaction with lanthanum sulfide, La2S3, forms gallium lanthanum sulfide glass which has interesting optical properties and is a semiconductor. [7]

Related Research Articles

<span class="mw-page-title-main">Gallium</span> Chemical element, symbol Ga and atomic number 31

Gallium is a chemical element with the symbol Ga and atomic number 31. Discovered by the French chemist Paul-Émile Lecoq de Boisbaudran in 1875, gallium is in group 13 of the periodic table and is similar to the other metals of the group.

<span class="mw-page-title-main">Sphalerite</span> Zinc-iron sulfide mineral

Sphalerite is a sulfide mineral with the chemical formula (Zn,Fe)S. It is the most important ore of zinc. Sphalerite is found in a variety of deposit types, but it is primarily in sedimentary exhalative, Mississippi-Valley type, and volcanogenic massive sulfide deposits. It is found in association with galena, chalcopyrite, pyrite, calcite, dolomite, quartz, rhodochrosite, and fluorite.

<span class="mw-page-title-main">Zinc sulfide</span> Inorganic compound

Zinc sulfide is an inorganic compound with the chemical formula of ZnS. This is the main form of zinc found in nature, where it mainly occurs as the mineral sphalerite. Although this mineral is usually black because of various impurities, the pure material is white, and it is widely used as a pigment. In its dense synthetic form, zinc sulfide can be transparent, and it is used as a window for visible optics and infrared optics.

<span class="mw-page-title-main">Zinc chloride</span> Chemical compound

Zinc chloride is the name of inorganic chemical compounds with the formula ZnCl2. It forms hydrates. Zinc chloride, anhydrous and its hydrates are colorless or white crystalline solids, and are highly soluble in water. Five hydrates of zinc chloride are known, as well as four forms of anhydrous zinc chloride. This salt is hygroscopic and even deliquescent. Zinc chloride finds wide application in textile processing, metallurgical fluxes, and chemical synthesis. No mineral with this chemical composition is known aside from the very rare mineral simonkolleite, Zn5(OH)8Cl2·H2O.

<span class="mw-page-title-main">Cadmium sulfide</span> Chemical compound

Cadmium sulfide is the inorganic compound with the formula CdS. Cadmium sulfide is a yellow solid. It occurs in nature with two different crystal structures as the rare minerals greenockite and hawleyite, but is more prevalent as an impurity substituent in the similarly structured zinc ores sphalerite and wurtzite, which are the major economic sources of cadmium. As a compound that is easy to isolate and purify, it is the principal source of cadmium for all commercial applications. Its vivid yellow color led to its adoption as a pigment for the yellow paint "cadmium yellow" in the 18th century.

Chalcogenide glass is a glass containing one or more chalcogens. Such glasses are covalently bonded materials and may be classified as covalent network solids. Polonium is also a chalcogen but is not used because of its strong radioactivity. Chalcogenide materials behave rather differently from oxides, in particular their lower band gaps contribute to very dissimilar optical and electrical properties.

<span class="mw-page-title-main">Lanthanum oxide</span> Chemical compound

Lanthanum(III) oxide, also known as lanthana, chemical formula La2O3, is an inorganic compound containing the rare earth element lanthanum and oxygen. It is used in some ferroelectric materials, as a component of optical materials, and is a feedstock for certain catalysts, among other uses.

<span class="mw-page-title-main">Iron(III) fluoride</span> Chemical compound

Iron(III) fluoride, also known as ferric fluoride, are inorganic compounds with the formula FeF3(H2O)x where x = 0 or 3. They are mainly of interest by researchers, unlike the related iron(III) chlorides. Anhydrous iron(III) fluoride is white, whereas the hydrated forms are light pink.

<span class="mw-page-title-main">Gallium(III) oxide</span> Chemical compound

Gallium(III) oxide is an inorganic compound and ultra-wide bandgap semiconductor with the formula Ga2O3. It is actively studied for applications in power electronics, phosphors, and gas sensing. The compound has several polymorphs, of which the monoclinic β-phase is the most stable. The β-phase’s bandgap of 4.7–4.9 eV and large-area, native substrates make it a promising competitor to GaN and SiC-based power electronics applications and solar-blind UV photodetectors. Ga2O3 exhibits reduced thermal conductivity and electron mobility by an order of magnitude compared to GaN and SiC, but is predicted to be significantly more cost-effective due to being the only wide-bandgap material capable of being grown from melt. β-Ga2O3 is thought to be radiation hard which makes it promising for military and space applications.

Indium(III) sulfide (Indium sesquisulfide, Indium sulfide (2:3), Indium (3+) sulfide) is the inorganic compound with the formula In2S3.

<span class="mw-page-title-main">Gallium trichloride</span> Chemical compound

Gallium trichloride is the chemical compound with the formula GaCl3. Solid gallium trichloride exists as a dimer with the formula Ga2Cl6. It is colourless and soluble in virtually all solvents, even alkanes, which is truly unusual for a metal halide. It is the main precursor to most derivatives of gallium and a reagent in organic synthesis.

<span class="mw-page-title-main">Gallium(II) sulfide</span> Chemical compound

Gallium(II) sulfide, GaS, is a chemical compound of gallium and sulfur. The normal form of gallium(II) sulfide as made from the elements has a hexagonal layer structure containing Ga24+ units which have a Ga-Ga distance of 248pm. This layer structure is similar to GaTe, GaSe and InSe. An unusual metastable form, with a distorted wurtzite structure has been reported as being produced using MOCVD. The metal organic precursors were di-tert-butyl gallium dithiocarbamates, for example GatBu2(S2CNMe2) and this was deposited onto GaAs. The structure of the GaS produced in this way is presumably Ga2+ S2−.

<span class="mw-page-title-main">Nickel sulfide</span> Chemical compound

Nickel sulfide is any inorganic compound with the formula NiSx. They range in color from bronze (Ni3S2) to black (NiS2). The nickel sulfide with simplest stoichiometry is NiS, also known as the mineral millerite. From the economic perspective, Ni9S8, the mineral pentlandite, is the chief source of mined nickel. Other minerals include heazlewoodite (Ni3S2) and polydymite (Ni3S4). The mineral Vaesite is NiS2. Some nickel sulfides are used commercially as catalysts.

Gallium lanthanum sulfide glass is the name of a family of chalcogenide glasses, referred to as gallium lanthanum sulfide (Ga-La-S) glasses. They are mixtures of La2S3, La2O3, and Ga2S3, which form the basic glass with other glass modifiers added as needed. Gallium-lanthanum-sulfide glasses have a wide range of vitreous formation centered around a 70% Ga2S3 : 30% La2S3 mixture, and readily accept other modifier materials into their structure. This means that Ga-La-S composition can be adjusted to give a wide variety of optical and physical properties.

<span class="mw-page-title-main">I-III-VI semiconductors</span>

I-III-VI2 semiconductors are solid semiconducting materials that contain three or more chemical elements belonging to groups I, III and VI (IUPAC groups 1/11, 13 and 16) of the periodic table. They usually involve two metals and one chalcogen. Some of these materials have a direct bandgap, Eg, of approximately 1.5 eV, which makes them efficient absorbers of sunlight and thus potential solar cell materials. A fourth element is often added to a I-III-VI2 material to tune the bandgap for maximum solar cell efficiency. A representative example is copper indium gallium selenide (CuInxGa(1–x)Se2, Eg = 1.7–1.0 eV for x = 0–1), which is used in copper indium gallium selenide solar cells.

<span class="mw-page-title-main">Lithium tetrahydridogallate</span> Chemical compound

Lithium tetrahydridogallate is the inorganic compound with formula LiGaH4. It is a white solid similar to but less thermally robust than lithium aluminium hydride.

<span class="mw-page-title-main">Aluminium compounds</span>

Aluminium (or aluminum) combines characteristics of pre- and post-transition metals. Since it has few available electrons for metallic bonding, like its heavier group 13 congeners, it has the characteristic physical properties of a post-transition metal, with longer-than-expected interatomic distances. Furthermore, as Al3+ is a small and highly charged cation, it is strongly polarizing and aluminium compounds tend towards covalency; this behaviour is similar to that of beryllium (Be2+), an example of a diagonal relationship. However, unlike all other post-transition metals, the underlying core under aluminium's valence shell is that of the preceding noble gas, whereas for gallium and indium it is that of the preceding noble gas plus a filled d-subshell, and for thallium and nihonium it is that of the preceding noble gas plus filled d- and f-subshells. Hence, aluminium does not suffer the effects of incomplete shielding of valence electrons by inner electrons from the nucleus that its heavier congeners do. Aluminium's electropositive behavior, high affinity for oxygen, and highly negative standard electrode potential are all more similar to those of scandium, yttrium, lanthanum, and actinium, which have ds2 configurations of three valence electrons outside a noble gas core: aluminium is the most electropositive metal in its group. Aluminium also bears minor similarities to the metalloid boron in the same group; AlX3 compounds are valence isoelectronic to BX3 compounds (they have the same valence electronic structure), and both behave as Lewis acids and readily form adducts. Additionally, one of the main motifs of boron chemistry is regular icosahedral structures, and aluminium forms an important part of many icosahedral quasicrystal alloys, including the Al–Zn–Mg class.

<span class="mw-page-title-main">Cerium(III) sulfide</span> Chemical compound

Cerium(III) sulfide, also known as cerium sesquisulfide, is an inorganic compound with the formula Ce2S3. It is the sulfide salt of cerium(III) and exists as three polymorphs with different crystal structures.

Gallium compounds are compounds containing the element gallium. These compounds are found primarily in the +3 oxidation state. The +1 oxidation state is also found in some compounds, although it is less common than it is for gallium's heavier congeners indium and thallium. For example, the very stable GaCl2 contains both gallium(I) and gallium(III) and can be formulated as GaIGaIIICl4; in contrast, the monochloride is unstable above 0 °C, disproportionating into elemental gallium and gallium(III) chloride. Compounds containing Ga–Ga bonds are true gallium(II) compounds, such as GaS (which can be formulated as Ga24+(S2−)2) and the dioxan complex Ga2Cl4(C4H8O2)2. There are also compounds of gallium with negative oxidation states, ranging from -5 to -1, most of these compounds being magnesium gallides (MgxGay).

References

  1. 1 2 Handbook of Inorganic Compounds, Dale L. Perry, Taylor & Francis, 2011, ISBN   978-1-4398-1461-1
  2. 1 2 3 4 The Chemistry of Aluminium, Gallium, Indium and Thallium, Anthony John Downs, 1993, ISBN   075140103X , ISBN   978-0751401035
  3. Pardo, M.P.; Guittard, M.; Chilouet, A.; Tomas, A. (1993). "Diagramme de phases gallium-soufre et études structurales des phases solides". Journal of Solid State Chemistry. 102 (2): 423–433. doi:10.1006/jssc.1993.1054. ISSN   0022-4596.
  4. Peter Atkins; T.L. Overton; J.P. Rourke; M.T. Weller; F.A. Armstrong (2010). Inorganic Chemistry (Fifth ed.). New York: W. H. Freeman and Company. p. 346. ISBN   978-1429218207.
  5. 1 2 3 4 5 6 Barron, Andrew R.; MacInnes, Andrew N. (1994). "Gallium: Inorganic chemistry". In King, R. Bruce (ed.). Encyclopedia of Inorganic Chemistry. John Wiley and Sons. pp. 100–110. ISBN   0-471-93620-0.
  6. Semiconductors: Data Handbook 3d Ed., Otfried Madelung, Springer, 2004, ISBN   978-3540404880
  7. Semiconducting Chalcogenide Glass III: Applications of Chalcogenide Glasses, Robert Fairman, Boris Ushkov, Elsevier, 2004, (ebook), ISBN   9780080541068