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Title: Synthesis, crystal structure, and properties of the rhombohedral modification of the thiospinel CuZr{sub 1.86(1)}S{sub 4}

The rhombohedral modification of the thiospinel, CuZr{sub 1.86(1)}S{sub 4}, has been synthesized by the reaction of the constituent elements in an alkali metal halide flux and structurally characterized by single crystal X-ray diffraction techniques. The title compound crystallizes in the rhombohedral space group D{sub 3d}{sup 5}-R3-barm (no. 166, a=7.3552(2) A, c=35.832(2) A, V=1678.76(13) A{sup 3}, Z=12, and R/wR=0.0239/0.0624). The structure is composed of close packed S layers, with a stacking order of ...ABCBCABABCACAB....along the c axis. The Zr and Cu atoms occupy the octahedral and tetrahedral holes between S layers, respectively. Three different kinds of S-M-S layers exist in the structure: layer I has fully occupied Zr and Cu sites, layer II has fully occupied Zr sites but no Cu, and layer III has partially occupied Zr and fully occupied Cu sites. Transport and optical properties indicate that the title compound is a small band gap (1.26 eV) n-type semiconductor. - Graphical abstract: The projected view of the rhombohedral modification, CuZr{sub 1.86(1)}S{sub 4}, down the [100] direction. Large letters denote the packing sequence of the S atoms (yellow circles) along the c axis. Zr (black circles) and Cu (red circles) atoms occupy the octahedral and tetrahedral holes, respectively, between closemore » packed S layers.« less
Authors:
 [1] ;  [2] ;  [3] ;  [1]
  1. Baker Laboratory, Department of Chemistry, Cornell University, Ithaca, NY 14853-1301 (United States)
  2. Department of Physics, Cornell University, Ithaca, NY 14853-1301 (United States)
  3. Division of Energy Research System and Department of Chemistry, Ajou University, Suwon 442-749 (Korea, Republic of)
Publication Date:
OSTI Identifier:
21372527
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 183; Journal Issue: 3; Other Information: DOI: 10.1016/j.jssc.2009.12.012; PII: S0022-4596(09)00575-1; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CHARGED-PARTICLE TRANSPORT; COPPER COMPOUNDS; EV RANGE 01-10; HALIDES; LAYERS; MONOCRYSTALS; OPTICAL PROPERTIES; SEMICONDUCTOR MATERIALS; SPACE GROUPS; SULFIDES; SYNTHESIS; TRIGONAL LATTICES; X-RAY DIFFRACTION; ZIRCONIUM COMPOUNDS CHALCOGENIDES; COHERENT SCATTERING; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CRYSTALS; DIFFRACTION; ENERGY RANGE; EV RANGE; HALOGEN COMPOUNDS; MATERIALS; PHYSICAL PROPERTIES; RADIATION TRANSPORT; SCATTERING; SULFUR COMPOUNDS; SYMMETRY GROUPS; TRANSITION ELEMENT COMPOUNDS