Local structure and the phase transitions of BaTiO3

Abstract

We have measured and analyzed the Extended X-ray Absorption Fine Structure (EXAFS) of BaTiO₃ at the barium k edge and the X-ray Absorption Near Edge Structure (XANES) at the titanium K edge. Our structural data show that the sequence of phase transitions in this material as the temperature increases is explained by a disordering of domains wherein the local structural environment remains approximately rhombohedrally distorted at all temperatures around both metal sites. As the temperature is raised, the long range correlations between these local distortions change, resulting in the observed sequence of phase transitions. Our measurements confirm the model of eight-site disorder used to explain the phase diagram of BaTiO₃. We show that EXAFS and XANES are sensitive probes of both the magnitude and direction of the local structural distortions which accompany ferroelectricity and therefore are sensitive probes of the microscopic mechanism of ferroelectricity.