Computational discovery of Bi-based perovskite oxide polymorphs*

In this paper we present our recent study[1] of the energy surface of BiScO₃, BiCrO₃, BiMnO₃, BiFeO₃, and BiCoO₃. In normal conditions, the bulk crystals of these materials show three very different variations of the perovskite structure: an antipolar phase, a rhombohedral phase with a large polarization along the space diagonal of the pseudocubic unit cell, and a supertetragonal phase with even larger polarization. With the aim of understanding the causes for this variety, we have used a genetic algorithm to search for minima in the energy surface of these materials. Our results show that the number of these minima is very large when compared to that of typical ferroelectric perovskites like BaTiO₃ and PbTiO₃, and that a fine energy balance between them results in the large structural differences seen. As byproducts of our search we have identified charge-ordering structures with low energy in BiMnO₃, and several phases with energies that are similar to that of the ground state of BiCrO₃. We have also found that a inverse supertetragonal phase exists in bulk, likely to be favored in films epitaxially grown at large values of tensile misfit strain.

[1] A. Singh, V.N. Singh, E. Canadell, J. Íñiguez, and O. Diéguez: Phys Rev Materials (in press, 2018).