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Nanoscale polar heterogeneities and branching Bi-displacement directions in K0.5Bi0.5TiO3

DOI: 10.1021/acs.chemmater.8b05187 DOI Help

Authors: Igor Levin (National Institute of Standards and Technology) , Dean S. Keeble (Diamond Light Source) , Giannantonio Cibin (Diamond Light Source) , Helen Y. Playford (ISIS Facility) , Maksim Eremenko (National Institute of Standards and Technology) , Victor Krayzman (National Institute of Standards and Technology) , William J. Laws (National Institute of Standards and Technology) , Ian M. Reaney (University of Sheffield)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry Of Materials

State: Published (Approved)
Published: March 2019
Diamond Proposal Number(s): 16168 , 19240 , 16460

Abstract: K0.5Bi0.5TiO3 (KBT) – one of the few perovskite-like ferroelectric compounds with room-temperature tetragonal symmetry – differs from other members of this family (BaTiO3 and PbTiO3) by the presence of a disordered mixture of K and Bi on cuboctahedral sites. This disorder is expected to affect local atomic displacements and their response to an applied electric field. We have derived nanoscale atomistic models of KBT by refining atomic coordinates to simultaneously fit neutron/X-ray total-scattering and extended X-ray absorption fine-structure data. Both Bi and Ti ions were found to be offset relative to their respective oxygen cages in the high-temperature cubic phase; in contrast, the coordination environment of K remained relatively undistorted. In the cubic structure, Bi displacements prefer the <100> directions and the probability-density distribution of Bi features six well-separated sites; a similar preference exists for the much smaller Ti displacements although the split sites for Ti could not be resolved. The cation displacements are correlated, yielding polar nanoregions, while on average the structure appears as cubic. The cubic<->tetragonal phase transition involves both order-disorder and displacive mechanisms. A qualitative change in the form of the Bi probability-density distribution occurs in the tetragonal phase on cooling to room temperature because Bi displacements “branch off” to <111> directions. This change, which preserves the average symmetry, is accompanied by the development of nanoscale polar heterogeneities that exhibit significant deviations of their polarization vectors from the average polar axis.

Journal Keywords: X-rays; Chemical structure; Mathematical methods; Phase transitions; Polarization

Diamond Keywords: Ferroelectricity

Subject Areas: Materials, Chemistry

Instruments: B18-Core EXAFS , I15-1-X-ray Pair Distribution Function (XPDF)

Other Facilities: Polaris at ISIS

Added On: 11/03/2019 11:40

Discipline Tags:

Inorganic Chemistry Materials Science Metallurgy Perovskites Quantum Materials Chemistry

Technical Tags:

Scattering Spectroscopy Total Scattering X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS)