Why Are There So Few Perovskite Ferroelectrics?

We use a combination of symmetry arguments and first principles calculations to explore the connection between structural distortions and ferroelectricity in the perovskite family of materials. We explain the role of octahedral rotations in suppressing ferroelectricity in these materials and show that, as the tolerance factor decreases, rotations alone cannot fully suppress ferroelectricity. Our results show that it is cation displacements (hidden in Glazer notation) that accompany the rotations, rather than the rotations themselves, that play the decisive role in suppressing ferroelectricity in these cases. We use the knowledge gained in our analysis of this problem to explain the origin of ferroelectricity in R3c materials such as FeTiO3 and ZnSnO3 and to suggest strategies for the design and synthesis of new perovskite ferroelectrics. Our results have implications not only for the fundamental crystal chemistry of the perovskites but also for the discovery of new functional materials.