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Structural Difference in Superconductive and Nonsuperconductive Bi–S Planes within Bi4O4Bi2S4Blocks

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Title: Structural Difference in Superconductive and Nonsuperconductive Bi–S Planes within Bi4O4Bi2S4Blocks
Authors: Miura, Akira Browse this author →KAKEN DB
Mizuguchi, Yoshikazu Browse this author
Sugawara, Tsuyoshi Browse this author
Wang, Yongming Browse this author
Takei, Takahiro Browse this author
Kumada, Nobuhiro Browse this author
Magome, Eisuke Browse this author
Moriyoshi, Chikako Browse this author
Kuroiwa, Yoshihiro Browse this author
Miura, Osuke Browse this author
Tadanaga, Kiyoharu Browse this author →KAKEN DB
Issue Date: 19-Oct-2015
Publisher: American Chemical Society
Journal Title: Inorganic Chemistry
Volume: 54
Issue: 21
Start Page: 10462
End Page: 10467
Publisher DOI: 10.1021/acs.inorgchem.5b01919
PMID: 26479778
Abstract: The relationship between the structure and superconductivity of Bi4O4S3 powders synthesized by heating under ambient and high pressures was investigated using synchrotron X-ray diffraction, Raman spectroscopy, and transmission electron microscopy (TEM) observation. The Bi4O4S3 powders synthesized under ambient pressure exhibited a strong superconductivity (diamagnetic) signal and zero resistivity below ∼4.5 K, while the Bi4O4S3 powder synthesized by the high-pressure method exhibited a low-intensity signal down to 2 K. Further annealing of the latter Bi4O4S3 powder under ambient pressure led to the development of a strong signal and zero resistivity. The crystal structures of all Bi4O4S3 phases consisted of Bi4O4Bi2S4 blocks including a Bi–S layer and anion(s) sandwiched between Bi4O4Bi2S4 blocks, but minor structural differences were detected. A comparison of the structures of the superconductive and nonsuperconductive Bi4O4S3 samples suggested that the superconductive Bi4O4S3 phases had slightly smaller lattice parameters. The average structures of the superconductive Bi4O4S3 phases were characterized by a slightly shorter and less bent Bi–S plane. Raman spectroscopy detected vibration of the S–O bonds, which can be attributed to sandwiched anion(s) such as SO42–. TEM observation showed stacking faults in the superconductive Bi4O4S3 phases, which indicated local fluctuation of the average structures. The observed superconductivity of Bi4O4S3 was discussed based on impurity phases, enhanced hybridization of the px and py orbitals of the Bi–S plane within Bi4O4Bi2S4 blocks, local fluctuation of the average structures, compositional deviation related to suspicious anion(s) sandwiched between Bi4O4Bi2S4 blocks, and the possibility of suppression of the charge-density-wave state by enriched carrier concentrations.
Rights: This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in Inorganic Chemistry, copyright © American Chemical Society after peer review. To access the final edited and published work, see
Type: article (author version)
Appears in Collections:工学院・工学研究院 (Graduate School of Engineering / Faculty of Engineering) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 三浦 章

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