Metal–Semiconductor Transition Concomitant with a Structural Transformation in Tetrahedrite Cu<sub>12</sub>Sb<sub>4</sub>S<sub>13</sub>

DOI Web Site 被引用文献8件 参考文献30件
  • Hiromi I. Tanaka
    Department of Quantum Matter, Graduate School of Advanced Sciences of Matter, Hiroshima University, Higashihiroshima, Hiroshima 739-8530, Japan
  • Koichiro Suekuni
    Department of Quantum Matter, Graduate School of Advanced Sciences of Matter, Hiroshima University, Higashihiroshima, Hiroshima 739-8530, Japan
  • Kazunori Umeo
    Natural Science Center for Basic Research and Development, Hiroshima University, Higashihiroshima, Hiroshima 739-8526, Japan
  • Toshiki Nagasaki
    Department of Physical Science, Graduate School of Science, Hiroshima University, Higashihiroshima, Hiroshima 739-8526, Japan
  • Hitoshi Sato
    Hiroshima Synchrotron Radiation Center, Hiroshima University, Higashihiroshima, Hiroshima 739-0046, Japan
  • Galif Kutluk
    Hiroshima Synchrotron Radiation Center, Hiroshima University, Higashihiroshima, Hiroshima 739-0046, Japan
  • Eiji Nishibori
    Faculty of Pure and Applied Sciences, Center for Integrated Research in Fundamental Science and Engineering (CiRfSE), and Tsukuba Research Center for Interdisciplinary Materials Science (TIMS), University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
  • Hidetaka Kasai
    Faculty of Pure and Applied Sciences, Center for Integrated Research in Fundamental Science and Engineering (CiRfSE), and Tsukuba Research Center for Interdisciplinary Materials Science (TIMS), University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan
  • Toshiro Takabatake
    Department of Quantum Matter, Graduate School of Advanced Sciences of Matter, Hiroshima University, Higashihiroshima, Hiroshima 739-8530, Japan

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説明

The tetrahedrite Cu12Sb4S13 undergoes a metal–semiconductor transition (MST) at TMST = 85 K, whose mechanism remains elusive. Our Cu 2p X-ray photoemission spectroscopy study revealed the monovalent state of Cu ions occupying the two sites in this compound. This fact excludes the possibilities of previously proposed antiferromagnetic order and Jahn–Teller instability inherent in a divalent Cu system. A synchrotron X-ray diffraction study has revealed that the body-centered cubic cell of Cu12Sb4S13 transforms into a body-centered 2a × 2a × 2c tetragonal supercell below TMST, where the cell volume per formula unit expands by 0.25%. We have further studied pressure effects on the MST as well as the effects of the substitution of As for Sb. The application of pressure above 1 GPa completely inhibits the MST and leads to a metallic state, suggesting that the low-temperature structure with a larger volume becomes unstable under pressure. The As substitution also reduces the volume and suppresses the MST but the...

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