Direct observation ofB-site cation displacements in Pb-based complex perovskite relaxor oxides

Abstract

Electron diffraction patterns recorded using a scanning transmission electron microscope (STEM) from PbMg1/3Nb2/3O3(PMN) crystallites and PbZn1/3Nb2/3O3(PZN) crystals show weak and systematic continuous diffuse streaking along the 〈110〉 directions. Detailed high-angle annular dark-field (HAADF) images recordedviaan aberration-corrected STEM show that theB-site cations in PMN and PZN undergo correlated and long-range displacements towards the Pb2+ions on the (110) planes. The planarB-site displacement measured from the centres of the octahedra is about 0.3–0.5 Å in PMN and about 0.20–0.4 Å in PZN. In the HAADF images of the PMN crystallites and PZN crystals studied, there is insufficient evidence for systematic long-range planar displacements of the Pb2+ions. The observed Pb2+ion displacements in PMN and PZN appear randomly distributed, mostly displaced along 〈110〉 towards theB-site columns. There is also evidence of possible stress-related distortion in certain unit cells of PMN. In the relaxors studied, two distinct types of displacements were observed: one is the long-range planarB-site spatial displacement on the (110) planes, correlated with the Pb2+ions, possibly resulting in the observed diffuse streaking; the other is short-range Pb2+ion displacement on the (110) planes. The observed displacement status indicates a mutual attraction between the Pb ions and theB-site cations in which theBsites undergo the largest spatial displacements towards the Pb ions along 〈110〉.