Polymorphism in Bi-based perovskite oxides: A first-principles study

Under normal conditions, bulk crystals of BiScO3, BiCrO3, BiMnO3, BiFeO3, and BiCoO3 present 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 an inverse supertetragonal phase exists in bulk, likely to be favored in films epitaxially grown at large values of tensile misfit strain.