Mimicking Antiferroelectrics with Ferroelectric Superlattices

Antiferroelectric oxides are promising materials for applications in high‐density energy storage, solid‐state cooling, and negative capacitance devices. However, the range of oxide antiferroelectrics available today is rather limited. In this work, it is demonstrated that antiferroelectric properties can be electrostatically engineered in artificially layered ferroelectric superlattices. Using a combination of synchrotron X‐ray nanodiffraction, scanning transmission electron microscopy, macroscopic electrical measurements, and lateral and vertical piezoresponse force microscopy in parallel‐plate capacitor geometry, a highly reversible field‐induced transition is observed from a stable in‐plane polarized state to a state with in‐plane and out‐of‐plane polarized nanodomains that mimics, at the domain level, the nonpolar to polar transition of traditional antiferroelectrics, with corresponding polarization‐voltage double hysteresis and comparable energy storage capacity. Furthermore, it is found that such superlattices exhibit large out‐of‐plane dielectric responses without involving flux‐closure domain dynamics. These results demonstrate that electrostatic and strain engineering in artificially layered materials offers a promising route for the creation of synthetic antiferroelectrics. Antiferroelectrics are promising materials for applications in energy storage, solid‐state cooling, and negative‐capacitance devices. This study demonstrates that antiferroelectric‐like behavior can be electrostatically engineered in ferroelectric superlattices. An electric field induces a reversible transition from a stable in‐plane polarized state to a state with in‐plane and out‐of‐plane polarized nanodomains that mimics, at the domain level, the nonpolar‐to‐polar transition of traditional antiferroelectrics.