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

Abstract

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 suchmore » as the Bi{sub 2}O{sub 2}S oxysulfide.« less

Authors:
; ;  [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)
Publication Date:
OSTI Identifier:
22584083
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 237; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BISMUTH; COPPER; COPPER OXIDES; DEFECTS; DISLOCATIONS; ELECTRONS; EPITAXY; INTERFACES; OXYSELENIDES; OXYSULFIDES; SUPERCONDUCTIVITY; TRANSMISSION ELECTRON MICROSCOPY

Citation Formats

Berthebaud, D., Guilmeau, E., Lebedev, O. I., Maignan, A., E-mail: antoine.maignan@ensicaen.fr, Gamon, J., and Barboux, P. The BiCu{sub 1−x}OS oxysulfide: Copper deficiency and electronic properties. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.02.033.
Berthebaud, D., Guilmeau, E., Lebedev, O. I., Maignan, A., E-mail: antoine.maignan@ensicaen.fr, Gamon, J., & Barboux, P. The BiCu{sub 1−x}OS oxysulfide: Copper deficiency and electronic properties. United States. https://doi.org/10.1016/J.JSSC.2016.02.033
Berthebaud, D., Guilmeau, E., Lebedev, O. I., Maignan, A., E-mail: antoine.maignan@ensicaen.fr, Gamon, J., and Barboux, P. 2016. "The BiCu{sub 1−x}OS oxysulfide: Copper deficiency and electronic properties". United States. https://doi.org/10.1016/J.JSSC.2016.02.033.
@article{osti_22584083,
title = {The BiCu{sub 1−x}OS oxysulfide: Copper deficiency and electronic properties},
author = {Berthebaud, D. and Guilmeau, E. and Lebedev, O. I. and Maignan, A., E-mail: antoine.maignan@ensicaen.fr and Gamon, J. and Barboux, P.},
abstractNote = {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.},
doi = {10.1016/J.JSSC.2016.02.033},
url = {https://www.osti.gov/biblio/22584083}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 237,
place = {United States},
year = {Sun May 15 00:00:00 EDT 2016},
month = {Sun May 15 00:00:00 EDT 2016}
}