Latent Electronic (Anti-)Ferroelectricity in BiNiO_{3}.

Abstract

BiNiO_{3} exhibits an unusual metal-insulator transition from Pnma to P1[over ¯] that is related to charge ordering at the Bi sites, which is intriguingly distinct from the charge ordering at Ni sites usually observed in related rare-earth nickelates. Here, using first principles calculations, we first rationalize the phase transition from Pnma to P1[over ¯], revealing an overlooked intermediate P2_{1}/m bridging phase and a complex interplay between distinct degrees of freedom. Going further, we point out that the charge ordering at Bi sites in the P1[over ¯] phase is not unique. We highlight an alternative polar ordering giving rise to a ferroelectric Pmn2_{1} phase nearly degenerated in energy with P1[over ¯] and showing an in-plane electric polarization of 53 μC/cm^{2} directly resulting from the charge ordering. The close energy of Pmn2_{1} and P1[over ¯] phases, together with low energy barrier between them, make BiNiO_{3} a potential electronic antiferroelectric in which the field-induced transition from nonpolar to polar would relate to nonadiabatic intersite electron transfer. We also demonstrate the possibility to stabilize an electronic ferroelectric ground state from strain engineering in thin films, using an appropriate substrate.