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Title: The BiCu{sub 1−x}OS oxysulfide: Copper deficiency and electronic properties

Journal Article · · Journal of Solid State Chemistry
; ;  [1]; ;  [2]
  1. Laboratoire CRISMAT, UMR 6508 CNRS/ENSICAEN/UCBN, 6 bd du Maréchal Juin, F-14050 CAEN Cedex 4 (France)
  2. Institut de Recherche de Chimie de Paris, Ecole Nationale Supérieure de Chimie de Paris, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 09 France (France)

An oxysulfide series of nominal compositions BiCu{sub 1−x}OS with x<0.20 has been prepared and its structural properties characterized by combining powder X-ray diffraction and transmission electron microscopy techniques. It is found that this oxysulfide, crystallizing in the P4/nmm space group, tends to adopt a constant amount of copper vacancy corresponding to x=0.05 in the BiCu{sub 1−x}OS formula. The presence of Cu vacancies is confirmed by HAADF-STEM analysis showing, in the Cu atomic columns, alternating peaks of different intensities in some very localized regions. For larger Cu deficiencies (x>0.05 in the nominal composition), other types of structural nanodefects are evidenced such as bismuth oxysulfides of the “BiOS” ternary system which might explain the report of superconductivity for the BiCu{sub 1−x}OS oxysulfide. Local epitaxial growth of the BiCuOS oxysulfide on top of CuO is also observed. In marked contrast to the BiCu{sub 1−x}OSe oxyselenide, these results give an explanation to the limited impact of Cu deficiency on the Seebeck coefficient in BiCu{sub 1−x}OS compounds. - Graphical abstract: High resolution TEM image showing a Bi(Cu)OS/Bi{sub 2}O{sub 2}S interface and corresponding dislocation region. The Bi(Cu)OS structure adopts a rather constant Cu content (near 0.95); starting from BiCuOS leads to the formation of defects such as the Bi{sub 2}O{sub 2}S oxysulfide.

OSTI ID:
22584083
Journal Information:
Journal of Solid State Chemistry, Vol. 237; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
Country of Publication:
United States
Language:
English