Special quasirandom structures description of the local structure of disordered Bi0.5K0.5TiO3

Abstract

Polar nanoregions (PNRs) are believed to play a decisive role in the local and macroscopic polarization in relaxor ferroelectrics. The limited microscopic understanding of the structure and dynamics of PNRs hampers the rational design of new lead-free materials. Here, the local structure of A-site disordered Bi0.5K0.5TiO3 (BKT) is investigated using synchrotron x-ray and neutron pair distribution function (PDF) analysis and density functional theory (DFT) optimized special quasirandom structures (SQSs). DFT-relaxed SQS with a 4 × 4 × 4 supercell size can reproduce the experimental PDFs of disordered BKT, as well as the partial PDFs and total polarization, with comparable results to those reported from a combined analysis of x-ray and neutron PDF data with large-box reverse Monte Carlo methods. We find that small Bi3+-rich polar clusters are likely to be the microscopic origin of relaxor behavior in disordered BKT, and that the existence of large polar nanoregions (PNRs) is not necessary to explain the relaxor properties. Our results also highlight the great potential of the SQS approach to gain a nanoscale-to-microscopic understanding of other relaxor solid solutions.