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Phase relations and structural properties of the ternary narrow gap semiconductors Zn5Sb4In2-δ (δ = 0.15) and Zn9Sb6In2
Department of Chemistry and Biochemistry, Arizona State University.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Materials Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Materials Chemistry.
School of Materials, Arizona State University.
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2010 (English)In: Journal of Solid State Chemistry, ISSN 0022-4596, E-ISSN 1095-726X, Vol. 183, no 7, 1574-1581 p.Article in journal (Refereed) Published
Abstract [en]

A systematic study of the Zn-rich corner of the ternary system Zn-Sb-In revealed the presence of two ternary compounds, stable Zn5Sb4In2-δ(δ = 0.15) and metastable Zn9Sb6In2, with closely related crystal structures. Their common motif is a tetragonal basic structure of 32434 nets formed by the Sb atoms that are stacked in antiposition to yield layers of square antiprisms sharing edges plus intervening tetracapped tetrahedra (tetreadersterns). The majority of Zn atoms occupy peripheral tetrahedra of such tetraedersterns which produces frameworks with a composition “ZnSb”. These frameworks represent orthorhombic superstructures, (2×1×1) for Zn5Sb4In2-δ (Z = 4) and (2×3×1) for Zn9Sb6In2 (Z = 8), with respect to the tetragonal arrangement of Sb atoms. The In and remaining Zn atoms are distributed in the channels formed by the square antiprisms. Phase relations in the Zn-Sb-In system are complex. Crystals of metastable Zn9Sb6In2 are regularly intergrown with various amounts of Zn5Sb4In2-δ. Additionally, a monoclinic variant to orthorhombic Zn9Sb6In2 could be identified. Zn9Sb6In2 decomposes exothermically into a mixture of Zn5Sb4In2-δ, Zn4Sb3 and elemental Zn at around 480 K. Both Zn5Sb4In2-δ and Zn9Sb6In2 are poor metals with resistivity values that are characteristic of heavily doped or degenerate semiconductors (0.2 to 3 mW cm at room temperature).

Place, publisher, year, edition, pages
Elsevier , 2010. Vol. 183, no 7, 1574-1581 p.
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-42957DOI: 10.1016/j.jssc.2010.05.001ISI: 000279711200015OAI: oai:DiVA.org:su-42957DiVA: diva2:352460
Available from: 2010-09-21 Created: 2010-09-21 Last updated: 2017-12-12Bibliographically approved
In thesis
1. Thermoelectric Properties of Antimony Based Networks
Open this publication in new window or tab >>Thermoelectric Properties of Antimony Based Networks
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

With the retreating sources of carbon based fuels, thermoelectric materials can play an important role in the future of environmentally friendly power generators. Sb based framework have in some cases shown some promising properties as thermoelectric materials. The physical properties may be modified with doping or incorporation of new elements. Zn4Sb3 and Cd4Sb3 are structurally related with a Sb-based network and Zn/Cd occupying the rest of the positions. Both structures undergo order-disorder αβ transition of the Zn/Cd positions, at 254 K and ~355 K respectively. The previously ordered interstitial atoms become distributed in the structure and the two high temperature phases are isostructural (R-3c). Cd4Sb3 was synthesized from melt-quench, flux synthesis with Sn, Bi and In. The syntheses made with In resulted in interstitial-free β-Cd4Sb3 with the composition Cd11.7In1.5Sb10. This compound exhibits no phase transitions until decomposition. ZnSnSb2 and InSb both exhibit the cubic sphalerite structure. ZnSnSb2 is metallic and InSb narrow band-gap semiconductor. Attempts were made to fine-tune the electrical properties by probing the mutual solid solubility range. The formula [ZnSnSb2]x[2(InSb)]1-xSn4 and 0<X<1 with 0.1 increments for the whole composition range was used. Resistivity changes from semiconducting to metallic conduction between x=0.9 and x=0.8. In the attempt to dope Zn4Sb3 by In a novel metastable compound with the composition Zn9Sb6In2 was found. Another novel phase was discovered with the composition Zn5Sb4In2-δ (δ=0.15).  The two phases have the same Sb-framework with a CuAl2 structure. Zn and In arrangements fill the square antiprisms formed by the stacking of 32434 nets in anti configuration. The filling of the antiprisms in the two phases are different, in Zn9Sb6In2 the antiprisms have two filling arrangements, an In or Zn3 triangles. In Zn5Sb4In2-δ the antiprisms are filled with an In and a Zn that occupies a split position to form a hetero-atomic dimers.

Place, publisher, year, edition, pages
Stockholm: Department of Materials and Environmental Chemistry, Stockholm University, 2010. 65 p.
Keyword
thermoelectric, narrow gap semiconductors, zinc antimonides, cadmium antimonides, chalcopyrites, sphalerites
National Category
Inorganic Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-42981 (URN)978-91-7447-143-4 (ISBN)
Public defence
2010-10-22, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
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Available from: 2010-09-30 Created: 2010-09-22 Last updated: 2010-10-04Bibliographically approved

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