Indium chalcogenides

The indium chalcogenides include all compounds of indium with the chalcogen elements, oxygen, sulfur, selenium and tellurium. (Polonium is excluded as little is known about its compounds with indium). The best characterised compounds are the In(III) and In(II) chalcogenides e.g. the sulfides In₂S₃ and InS.
This group of compounds has attracted a lot of research attention because they include semiconductors, photovoltaics and phase-change materials. In many applications indium chalcogenides are used as the basis of ternary and quaternary compounds such as indium tin oxide, ITO and copper indium gallium selenide, CIGS.
Some compounds that were reported and have found their way into text books have not been substantiated by later researchers. The list of compounds below shows compounds that have been reported, and those compounds that have not had their structure determined, or whose existence has not been confirmed by the latest structural investigations, are in italics.

There are a lot of compounds, the reason for this being that indium can be present as

• In³⁺ ,oxidation state +3
• In⁺, oxidation state +1
• In₂⁴⁺ units, oxidation state of +2, also found in some indium halides, e.g. In₂Br₃.
• non linear In₃⁵⁺ units isoelectronic with Hg₃²⁺.

The compound In₂Te₅ is a polytelluride containing the Te₃²⁻ unit.
None of the indium chalcogenides can be described simply as ionic in nature, they all involve a degree of covalent bonding. However in spite of this it is useful to formulate the compounds in ionic terms to get an insight into how the structures are built up. Compounds almost invariably have multiple polymorphs, that is they can crystallise in slightly different forms depending on either the method of production, or the substrate upon which they are deposited. Many of the compounds are made up of layers, and it is the different ways that the layers are stacked that is a cause of polymorphism.

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In₂O, In₂Se

In₂O is well documented. It exists in the gaseous phase and there are numerous reports of small amounts detected in the solid phase but no definitive structure has been published. It is now believed that the compound described as In₂Se was actually a sample of In₄Se₃.^[1]

In₄S₃, In₄Se₃, In₄Te₃

In₄S₃ had been reported but has more recently been re-investigated and is now believed not to exist. Both In₄Se₃ and In₄Te₃ are similar black crystalline solids and have been formulated to contain a non linear In₃⁵⁺ unit that is isoelectronic with Hg₃²⁺. For example the selenide is formulated as In⁺ In₃⁵⁺ 3Se²⁻.^[2]

In₅S₄

A reinvestigation showed that the original sample was actually SnIn₄S₄. ^[3]

InS, InSe, InTe

InS, InSe

InS and InSe are similar, both contain In₂⁴⁺ and have a layer structure. InS for instance can be formulated In₂⁴⁺ 2S²⁻. InSe has two crystal forms β-InSe and γ-InSe that differ only in the way that the layers are stacked. InSe is a semiconductor and a phase change material and has potential as an optical recording medium^[4].

InTe

InTe in contrast to InS and InSe is a mixed valence indium compound containing In⁺ and In³⁺ and can be formulated as In⁺ In³⁺ 2Te²⁻. It is similar to TlSe and has tetrahedral InTe₄ units that share edges. It has potential for use in photovoltaic devices. ^[5]

In₆S₇, In₆Se₇

These compounds are isostructural, and have been formulated with indium in 3 different oxidation states, +1, +2 and +3. They have been formulated as e.g. In⁺ In₂⁴⁺ 3In³⁺ 7S²⁻. The indium – indium bond length in the In₂ units are 2.741 A (sulfide), 2.760 (selenide).

^{[6] [7]} In₆S₇ is an n-type semiconductor.^[8]

In₃Te₄

This compound has been reported as a superconductor ^[9]. An unusual structure has been proposed ^[10] that is effectively In₄Te₄ but with one quarter of the indium positions vacant. There seems to be no short indium-indium distance that would indicate an In-In unit.

In₇Te₁₀

This is formulated as In₂⁴⁺ 12In³⁺ 20Te^2-. The In-In distance is 276.3pm. It has a similar structure to Ga₇Te₁₀ and Al₇Te₁₀

^[11]

In₂S₃, In₂Se₃, In₂Te₃

In₂S₃

Indium(III) sulfide is a yellow or red high melting solid. It is an n-type semiconductor.

In₂Se₃

Indium(III) selenide is a black compound with potential photo-optic applications.

In₂Te₃

Indium(III) telluride is a black high melting solid with applications as a semiconductor and in photo-optic applications. It has two crystalline forms, α- and β-.

In₃Te₅

This was reported in phase studies in 1964 but its structure has not been confirmed.

In₂Te₅

This is a polytelluride compound and the structure is made up of layers that in turn are made up of chains of linked InTe₄ tetrahedra where three of the Te atoms are bridging. There are Te atoms separate from the chains. The compound has been formulated as (2In³⁺ Te²⁻Te₃²⁻)_n counterbalanced with separate Te²⁻ ions. The structure is similar to Al₂Te₅.^[12]

General references

• WebElements
• Greenwood, N. N.; Earnshaw, A. (1997). Chemistry of the Elements, 2nd Edition, Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4. 

Footnotes

1. ^ The crystal structure of tetraindium triselenide J. H. C. Hogg, H. H. Sutherland and D. J. Williams Acta Cryst. (1973). B29, 1590-1593 DOI: doi:10.1107/S0567740873005108
2. ^ In₄Te₃ und In₄Se₃: Neubestimmung der Kristallstrukturen, druckabhängiges Verhalten und eine Bemerkung zur Nichtexistenz von In₄S₃. U. Schwarz, H. Hillebrecht, H.J. Deiseroth, R. Walther Z. Krist. 210, 342-347 (1995)
3. ^ In₅S₄ = SnIn₄S₄ : Eine Korrektur! H.J. Deiseroth, H. Pfeifer Z. Krist. 196, 197-205 (1991)
4. ^ Phase-change recording medium that enables ultra high-density electron-beam data storage G. A. Gibson, A. Chaiken, K. Nauka, C. C. Yang, R. Davidson, A. Holden R. Bicknell, B. S Yeh, J. Chen, H. Liao, S. Subramanian, D. Schut J. Jasinski and Z. Liliental-Weber Appl. Phys. Lett. 86, 051902 (2005)doi:10.1063/1.1856690
5. ^ Grown of InTe films by close spaced vapor transport M. Zapata-Torres, J.L. Peña, Y. P. Mascarenhas, R. Castro-Rodríguez, M. Meléndez-Lira, O. Calzadilla Superficies y Vacío 13, 69-71, Diciembre 2001
6. ^ The crystal structure of In₆Se₇ J.H.C. Hogg Acta Cryst. (1971). B27, 1630 doi:10.1107/S056774087100445X
7. ^ The crystal structure of In₆S₇ J. H. C. Hogg and W. J. Duffin Acta Cryst. (1967). 23, 111-118 doi:10.1107/S0365110X6700221X
8. ^ On the conduction mechanism and thermoelectric phenomena in In₆S₇ layer crystals G. A. Gamal Crystal Research and Technology 32, 5 , 723 – 731 doi: 10.1002/crat.2170320517
9. ^ Superconductivity of Intermetallic Compounds with NaCl-Type and Related Structures S. Geller and G. W. Hull, Jr. Phys. Rev. Lett. 13, 127 – 29 (1964) DOI: 10.1103/PhysRevLett.13.127
10. ^ The ordered state of In₃Te₄ T. Karakostas, N. F. Flevaris, N. Vlachavas, G. L. Bleris and N. A. Economou Acta Cryst. (1978). A34, 123-126 doi:10.1107/S0567739478000224
11. ^ The Crystal Structures of Heptagallium- and Heptaindiumdecatellurides: Ga₇Te₁₀ and In₇Te₁₀ H.J. Deiseroth, H.D. Müller Z. Krist. (1995) 210, 57-58
12. ^ Die Pentatelluride M₂Te₅ (M=Al, Ga, In) Polymorphie, Strukturbeziehungen und Homogenitätsbereiche Deiseroth H. J., Amann P., Thurn H. Z für anorg und allgem Chemie 622, 6 , 985