Antiferroelectric switching inside ferroelastic domain walls

Abstract: Ferroelastic materials (materials with switchable spontaneous strain) often are centrosymmetric, but their domain walls are always polar, as their internal strain gradients cause polarization via flexoelectricity. This polarization is generally not switchable by an external electric field, because reversing the domain wall polarity would require reversing the strain gradient, which in turn would require switching the spontaneous strain of the adjacent domains, destroying the domain wall in the process. However, domain wall polarization can also arise from biquadratic coupling between polar and non-polar order parameters (e.g. octahedral tilts in perovskites). Such coupling is independent of the sign of the polarization and thus allows switching between +P and -P. In this work, we seek to answer the question of whether the polarization of domain walls in ferroelastic perovskites is switchable, as per the symmetric biquadratic term, or non-switchable due to the unipolar flexoelectric bias. Using perovskite calcium titanate (CaTiO3) as a paradigm, molecular dynamics calculations indicate that high electric fields broaden the ferroelastic domain walls, thereby reducing flexoelectricity (as the domain wall strain gradient is inversely proportional to the wall width), eventually enabling switching. The polarization switching, however, is not ferroelectric-like with a simple hysteresis loop, but antiferroelectric-like with a double hysteresis loop. Ferroelastic domain walls thus behave as functional antiferroelectric elements, and also as nucleation points for a bulk phase transition to a polar state.