Asymmetric Character of the Ferroelectric Phase Transition and Charged Domain Walls in a Hybrid Improper Ferroelectric

In improper ferroelectrics, the spontaneous ordering is typically driven by a structural distortion or a magnetic spin alignment. The induced electric polarization is only a secondary effect. This dependence is a rich source for unusual phenomena and ferroelectric domain configurations for proper, polarization‐driven ferroelectrics. This study focuses on the polar domain structure and the hysteretic behavior at the ferroelectric phase transition in Ca3Mn1.9Ti0.1O7 as a representative of the recently discovered hybrid improper ferroelectric class of multiferroics. Combining optical second harmonic generation and Raman spectroscopy gives access to the spontaneous structural distortion and the resulting improper electric polarization. This study shows that hybrid improper ferroelectrics contrast proper and improper ferroelectrics in several ways. Most intriguingly, adjacent ferroelectric domains favor head‐to‐head and tail‐to‐tail domain walls over charge‐neutral configurations. Furthermore, the phase transition occurs in an asymmetric fashion. The regime of phase coexistence of the nonpolar and polar phases shows a clear and abrupt upper temperature limit. In contrast, the coexistence toward low temperatures is best described as a fade‐out process, where 100‐nm‐sized islands of the nonpolar phase expand deep into the polar phase. The behavior of hybrid improper ferroelectrics contrasts that of proper and improper ferroelectrics in several ways. Adjacent ferroelectric domains favor head‐to‐head and tail‐to‐tail domain walls over charge‐neutral configurations. Furthermore, the ferroelectric phase transition occurs in an asymmetric fashion—into the nonpolar phase as a clear and abrupt phase change opposed to a fade‐out‐like transition into the polar phase.