The BiCu1-xOS oxysulfide: Copper deficiency and electronic properties

An oxysulfide series of nominal compositions BiCu1-xOS 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 BiCu1-xOS 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 BiCu1-xOS oxysulfide. Local epitaxial growth of the BiCuOS oxysulfide on top of CuO is also observed. In marked contrast to the BiCu1-xOSe oxyselenide, these results give an explanation to the limited impact of Cu deficiency on the Seebeck coefficient in BiCu1-xOS compounds. (C) 2016 Elsevier Inc. All rights reserved.