Unveiling the ferrielectric nature of PbZrO₃-based antiferroelectric materials

Benefitting from the reversible phase transition between antiferroelectric and ferroelectric states, antiferroelectric materials have recently received widespread attentions for energy storage applications. Antiferroelectric configuration with specific antiparallel dipoles has been used to establish antiferroelectric theories and understand its characteristic behaviors. Here, we report that the so-called antiferroelectric (Pb,La)(Zr,Sn,Ti)O₃ system is actually ferrielectric in nature. We demonstrate different ferrielectric configurations, which consists of ferroelectric ordering segments with either magnitude or angle modulation of dipoles. The ferrielectric configurations are mainly contributed from the coupling between A-cations and O-anions, and their displacement behavior is dependent largely on the chemical doping. Of particular significance is that the width and net polarization of ferroelectric ordering segments can be tailored by composition, which is linearly related to the key electrical characteristics, including switching field, remanent polarization and dielectric constant. These findings provide opportunities for comprehending structure-property correlation, developing antiferroelectric/ferrielectric theories and designing novel ferroic materials.