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Author Lemoine, Pierric ♦ Bourgès, Cédric ♦ Barbier, Tristan ♦ Nassif, Vivian ♦ Cordier, Stéphane ♦ Guilmeau, Emmanuel
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY ♦ INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ ANTIMONY COMPOUNDS ♦ COPPER COMPOUNDS ♦ CRYSTAL LATTICES ♦ EXPERIMENTAL DATA ♦ HEAT RATE ♦ HEATING RATE ♦ NEUTRON DIFFRACTION ♦ NEUTRON TEMPERATURE ♦ POWDERS ♦ SOLAR ENERGY ♦ SULFIDE MINERALS ♦ SULFIDES ♦ THERMOELECTRIC MATERIALS ♦ TIN COMPOUNDS
Abstract Ternary copper-containing sulfides Cu{sub 12}Sb{sub 4}S{sub 13} and Cu{sub 4}Sn{sub 7}S{sub 16} have attracted considerable interest since few years due to their high-efficiency conversion as absorbers for solar energy and promising thermoelectric materials. We report therein on the decomposition study of Cu{sub 12}Sb{sub 4}S{sub 13} and Cu{sub 4}Sn{sub 7}S{sub 16} phases using high temperature in situ neutron powder diffraction. Our results obtained at a heating rate of 2.5 K/min indicate that: (i) Cu{sub 12}Sb{sub 4}S{sub 13} decomposes above ≈792 K into Cu{sub 3}SbS{sub 3}, and (ii) Cu{sub 4}Sn{sub 7}S{sub 16} decomposes above ≈891 K into Sn{sub 2}S{sub 3} and a copper-rich sulfide phase of sphalerite ZnS-type structure with an assumed Cu{sub 3}SnS{sub 4} stoichiometry. Both phase decompositions are associated to a sulfur volatilization. While the results on Cu{sub 12}Sb{sub 4}S{sub 13} are in fair agreement with recent published data, the decomposition behavior of Cu{sub 4}Sn{sub 7}S{sub 16} differs from other studies in terms of decomposition temperature, thermal stability and products of reaction. Finally, the crystal structure refinements from neutron powder diffraction data are reported and discussed for the Cu{sub 4}Sn{sub 7}S{sub 16} and tetrahedrite Cu{sub 12}Sb{sub 4}S{sub 13} phases at 300 K, and for the high temperature form of skinnerite Cu{sub 3}SbS{sub 3} at 843 K. - Graphical abstract: In situ neutron powder diffraction data (heating rate of 2.5 K/min) indicates that (i) the ternary Cu{sub 12}Sb{sub 4}S{sub 13} phase is stable up to 792 K and decomposes at higher temperature into Cu{sub 3}SbS{sub 3} and Cu{sub 1.5}Sb{sub 0.5}S{sub 2}, and (ii) the Cu{sub 4}Sn{sub 7}S{sub 16} phase is stable up to 891 K and decomposes at higher temperature into Sn{sub 2}S{sub 3} and a cubic phase of sphalerite ZnS-type structure. Sulfur volatilization likely occurs in order to balance the overall stoichiometry.
ISSN 00224596
Educational Use Research
Learning Resource Type Article
Publisher Date 2017-03-15
Publisher Place United States
Journal Journal of Solid State Chemistry
Volume Number 247


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