Theory of prospective tetrahedral perovskite ferroelectrics

Abstract

Using first-principles methods, we predict the energy landscape and ferroelectric states of double perovskites of the form AA${}^{\prime }$BB${}^{\prime }$O${}_6$ in which the atoms on both the A and B sites are arranged in rock-salt order. While we are not aware of compounds that occur naturally in this structure, we argue that they might be realizable by directed synthesis. The high-symmetry structure formed by this arrangement belongs to the tetrahedral $F\bar{4}3m$ space group. If a ferroelectric instability occurs, the energy landscape will tend to have minima with the polarization along tetrahedral directions, leading to a rhombohedral phase, or along Cartesian directions, leading to an orthorhombic phase. We find that the latter scenario applies to CaBaTiZrO${}_6$ and KCaZrNbO${}_6$, which are weakly ferroelectric, and the former one applies to PbSnTiZrO${}_6$, which is strongly ferroelectric. The results are modeled with a fourth- or fifth-order Landau-Devonshire expansion, providing good agreement with the first-principles calculations. Computations of zone-center soft modes are also carried out in order to characterize the polar and octahedral-rotation instabilities in more detail. Prospects for synthesis of ferroelectric materials belonging to this class are discussed.

arXiv comment8 pages, 3 figures

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• First principle study of structural, elastic, electronic and optical properties of Pb0.5Sn0.5TiO3 and Pb0.5Sn0.5Ti0.5(Zr0.5)O3