Structure refinement of large domain relaxors in the Pb(Mg1/3Ta2/3)O3–PbZrO3 system Original Research Article

The relaxor ferroelectric compound Pb(Mg0.3Ta0.6Zr0.1)O3 (PMT–PZ) was studied by X-ray, neutron and electron diffraction and transmission electron microscopy in the as-sintered and annealed states. The as-sintered sample was comprised of nanometer-sized 1:1 chemically ordered domains dispersed in a disordered matrix. After annealing at 1325°C the domain size increased to ∼30 nm and the degree of order exceeded 95% in terms of the volume fraction of the ordered domains, yet the sample retained its diffuse, frequency dependent relaxor characteristics. Refinements of the chemically ordered structure using the Rietveld analysis revealed that the octahedral (B) site occupancies were in excellent agreement with a “random site” model for the chemical ordering. In this charge-balanced model for the 1:1 ordered Pb(β′1/2β″1/2)O3 structure the Ta cations predominantly occupy the β″ site, while the β′ site is populated by a random distribution of the Mg, Zr and remaining Ta cations. Large temperature factors for Pb and O atoms are observed in both as-sintered and annealed samples, indicating localized displacements of the Pb and O atoms. The mixed occupancy of the β′ position appears to be responsible for the relaxor characteristics in the dielectric response in spite of the growth of the chemical domains.