期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 136, 期 43, 页码 15386-15393出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja508564s
关键词
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资金
- NSF of China [11190023, 90922002]
- National Basic Research Program of China [2010CB923003, 2011CBA00103]
- Fundamental Research Funds for the Central Universities of China [2013FZA3003]
We have synthesized a novel europium bismuth sulfofluoride, Eu3Bi2S4F4, by solid-state reactions in sealed evacuated quartz ampules. The compound crystallizes in a tetragonal lattice (space group I4/mmm, a = 4.0771(1) angstrom, c = 32.4330(6) angstrom, and Z = 2), in which CaF2-type Eu3F4 layers and NaCl-like BiS2 bilayers stack alternately along the crystallographic c axis. There are two crystallographically distinct Eu sites, Eu(1) and Eu(2) at the Wyckoff positions 4e and 2a, respectively. Our bond valence sum calculation, based on the refined structural data, indicates that Eu(1) is essentially divalent, while Eu(2) has an average valence of +2.64(5). This anomalous Eu valence state is further confirmed and supported, respectively, by Mossbauer and magnetization measurements. The Eu3+ components donate electrons into the conduction bands that are mainly composed of Bi 6px and 6py states. Consequently, the material itself shows metallic conduction and superconducts at 1.5 K without extrinsic chemical doping.
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