Defect structure in δ-Bi₅PbY₂O_11.5

Abstract

A detailed study of the defect structure in a di-substituted δ-Bi₂O₃ type phase, δ-Bi₅PbY₂O_11.5, is presented. Using a combination of conventional Rietveld analysis of neutron diffraction data, reverse Monte Carlo (RMC) analysis of total neutron scattering data and <i>ab initio</i> molecular dynamics (MD) simulations, both average and local structures have been characterized. δ-Bi₅PbY₂O_11.5 represents a model system for the highly conducting δ-Bi₂O₃ type phases, in which there is a higher nominal vacancy concentration than in the unsubstituted parent compound. Uniquely, the methodology developed in this study has afforded the opportunity to study both oxide-ion vacancy ordering as well as specific cation-cation interactions. Oxide-ion vacancies in this system have been found to show a preference for association with Pb²⁺ cations, with some evidence for clustering of these cations. The system shows a non-random distribution of vacancy pair alignments, with a preference for 〈100〉 ordering, the extent of which shows thermal variation. MD simulations indicate a predominance of oxide-ion jumps in the 〈100〉 direction.