Abstract : An oxysulfide series of nominal compositions BiCu1−xOS with xandlt;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 (xandgt;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. © 2016 Elsevier Inc.
