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

Journal Article · Mon Mar 15 00:00:00 EDT 2010 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2009.12.012· OSTI ID:21372527

Dong, Yongkwan ^[1]; McGuire, Michael A ^[2]; Yun, Hoseop ^[3]

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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)

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 close packed S layers.

• OSTI ID: 21372527
• Journal Information: Journal of Solid State Chemistry, Vol. 183, 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.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

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