Enhanced Reversibility of Antiferroelectric–Ferroelectric Transition in PbZr1−xTixO3 Through a Compatible Pathway

Abstract

Abstract. Enhancing the reversibility and reducing the hysteresis of antiferroelectric (AFE)-to-ferroelectric (FE) transformations is essential for improving the functionality of energy-storage devices by using antiferroelectric ceramics. In this work, we show that, in PbZr1−xTixO3 (PZT), the AFE–FE transformation occurs as a rhombohedral-to-orthorhombic transition—a symmetry-breaking process that is not conventionally expected to be reversible. Through thermal and structural analysis, we find that this transformation can become reversible when a stable rhombohedral phase mediates the transition, satisfying geometric compatibility conditions. We theorize transformation pathways, derive lattice correspondence and compatibility criteria, and identify that the Ti0.005 composition closely satisfies the conditions of compatibility and exhibits the lowest thermal hysteresis and reduced bias field for AFE–FE switching. Micropillar compression experiments confirm mechanical reversibility is enhanced at this composition, validating the theoretical predictions. These results establish phase compatibility as a design principle for achieving reversible AFE–FE switching in functional oxides.