Atomic scale symmetry and polar nanoclusters in the paraelectric phase of ferroelectric materials

Abstract

The nature of the “forbidden” local- and long-range polar order in nominally non-polar paraelectric phases of ferroelectric materials has been an open question since the discovery of ferroelectricity in oxide perovskites, ABO3. A currently considered model suggests locally correlated displacements of B-site atoms along a subset of <111> cubic directions. Such off-site displacements have been confirmed experimentally; however, being essentially dynamic in nature they cannot account for the static nature of the symmetry-forbidden polarization implied by the macroscopic experiments. Here, in an atomically resolved study by aberration-corrected scanning transmission electron microscopy complemented by Raman spectroscopy, we reveal, directly visualize and quantitatively describe static, 2–4 nm large polar nanoclusters in the nominally non-polar cubic phases of (Ba,Sr)TiO3 and BaTiO3. These results have implications on understanding of the atomic-scale structure of disordered materials, the origin of precursor states in ferroelectrics, and may help answering ambiguities on the dynamic-versus-static nature of nano-sized clusters.