Deterministic Switching of Antipolar Variants in Antiferroelectric Membranes

Antiferroelectric (AFE) materials, characterized by their antiparallel dipole alignments, offer distinct ferroic functionalities desirable for high‐energy‐density storage and next‐generation low‐power electronic devices. However, the intrinsic degeneracy among antipolar domain variants poses a critical obstacle to their deterministic, nonvolatile control and practical integration into functional architectures. Here, selective and reversible manipulation of AFE domain configurations in freestanding PbZrO 3 membranes via electron beam irradiation are demonstrated. By tailoring the electron beam–induced built‐in electric field, controlled writing and erasure of both in‐plane and out‐of‐plane antipolar domain variants are enabled. Complementary phase‐field simulations uncover the underlying energetic landscape and domain evolution under varying irradiation conditions, offering mechanistic insight into the observed transformations. These findings demonstrate a promising strategy for domain‐level engineering of antiferroelectrics, establishing a generic and programmable approach to deterministically control antipolar ordering in perovskite systems—suggesting a pathway toward controlled, reversible switching of AFE domains in nanoscale oxide architectures.