Perovskite ABO3 oxides display an amazing variety of phenomena that can be altered by subtle changes in the chemistry and internal structure, making them a favorite class of materials to explore the rational design of novel properties. Here we highlight a recent advance in which rotations of the BO6 octahedra give rise to a novel form of ferroelectricity – hybrid improper ferroelectricity. Octahedral rotations also strongly influence other structural, magnetic, orbital, and electronic degrees of freedom in perovskites and related materials. Octahedral rotation-driven ferroelectricity consequently has the potential to robustly control emergent phenomena with an applied electric field. The concept of ‘functional’ octahedral rotations is introduced and the challenges for materials chemistry and the possibilities for new rotation-driven phenomena in multifunctional materials are explored.
A3B2O7 and (A/A′)B2O6 are two types of layered perovskites in which octahedral rotations induce ferroelectricity.