High temperature study of yttrium--barium--copper oxides near the YBa2Cu3Ox composition by 111In/Cd time differential \gamma--\gamma perturbed angular correlation spectroscopy

Abstract

The local atomic order around very dilute indium impurities in c-axis-oriented YBa2Cu3O7 and YBa2Cu3O6.25 films at room temperature and in YBa2Cu3Ox bulk powders held in air or oxygen over a wide temperature range were investigated using 111In/Cd \gamma--\gamma perturbed angular correlation (PAC) spectroscopy. The probe atoms occupy a single substitutional lattice position in YBa2Cu3Ox, and evidence reported here strongly supports previous claims that this is the yttrium position. In YBa2Cu3Ox powders, the local atomic order changes continuously with temperature. At room temperature the electric field gradient measured by PAC in bulk YBa2Cu3Ox powder is indistinguishable from that in the fully oxygenated YBa2Cu3O7 film. Near the decomposition temperature, the bulk YBa2Cu3Ox powder data are semiquantitatively similar to data in the room temperature YBa2Cu3O6.25 film, with quantitative differences that we attribute to temperature averaging in the former. Other sites usually found in PAC spectra of YBa2Cu3Ox bulk samples arise from 111In dissolved in Y2BaCuO5 and Y2Cu2O5 impurity phases. The latter phase apparently arises because of significant barium loss during processing; the barium deficiency is clearly demonstrated by comparison of PAC data with the alloy phase diagram above the decomposition temperature. PAC data on pure Y2Cu2O5 are reported here also.