2012/05/31 by Andrew T. Mulder, Nicole A. Benedek, James M. Rondinelli +1 · 2 citations
Chemistry · Materials Science · Physics and Astronomy · #Advanced Condensed Matter Physics #Antiferroelectricity #Chemical physics #Chemistry #Condensed matter physics #Crystal structure #Crystallography #Density functional theory #Dielectric #Electric field #Ferroelectric and Piezoelectric Materials #Ferroelectricity #Materials science #Multiferroics and related materials #Octahedron #Optoelectronics #Perovskite (structure) #Phase transition #Physics #Polarization (electrochemistry) #Quantum mechanics #cond-mat.mtrl-sci
paper · pdf · doi:10.1002/adfm.201300210
published as Advanced Functional Materials, 23, 4810-4820 (2013) · 13 pages, 11 figures
openalex publication_date 2013/05/06 · arxiv created 2014/12/02 · arxiv updated 2015/03/19 · openalex created_date 2016/06/24 · openalex updated_date 2026/08/06
Abstract Ferroic transition metal oxides, which exhibit spontaneous elastic, electrical, magnetic, or toroidal order, exhibit functional properties that find use in ultrastable solid‐state memories, sensors, and medical imaging technologies. To realize multifunctional behavior, where one order parameter can be coupled to the conjugate field of another order parameter, however, requires a common microscopic origin for the long‐range order. Here, a complete theory is formulated for a novel form of ferroelectricity, whereby a spontaneous and switchable polarization emerges from the destruction of an antiferroelectric state due to octahedral rotations and ordered cation sublattices. A materials design framework is then constructed based on crystal‐chemistry descriptors rooted in group theory, which enables the facile design of artificial oxides with large electric polarizations, P , simultaneous with small energetic switching barriers between + P and ‐ P . The theory is validated with first principles density functional calculations on more than 16 perovskite‐structured oxides, illustrating it could be operative in any materials classes exhibiting two‐ or three‐dimensional corner‐connected octahedral frameworks. The principles governing materials selection of the “layered” systems are shown to originate in the lattice dynamics of the A cation displacements stabilized by the pervasive BO 6 rotations of single phase ABO 3 materials, whereby the latter distortions govern the optical band gaps, magnetic order, and critical transition temperatures. This approach provides the elusive route to the practical control of octahedral rotations, and hence, a wide range of functional properties, with an applied electric field.