Mechanism of Antiferroelectricity in Polycrystalline ZrO2

The size and electric field dependent induction of polarization in antiferroelectric ZrO2 is the key to several technological applications that are unimaginable a decade ago. However, the lack of a deeper understanding of the mechanism hinders progress. Molecular dynamics simulations of polycrystalline ZrO2, based on machine‐learned interatomic forces with near ab initio quality, shed light on the fundamental mechanism of the size effect on the transition fields. Stress in the oxygen sublattice is the most important factor. The so constructed interatomic forces allow the calculation of the transition fields as a function of the ZrO2 film thickness and predict the ferroelectricity at large thickness. The simulation results are validated with electrical and piezo response force microscopy measurements. The results allow a clear interpretation of the properties of the double‐hysteresis loops as well as the construction of the free energy landscape of ZrO2 grains. Using molecular dynamics with machine‐learned force fields, it is now possible to simulate whole polycrystalline ZrO2 grains. By fixing an experimentally observed dielectric interphase to the polar orthorhombic phase, the temperature‐dependent ferro‐ to antiferroelectric transition and its hysteresis loops can be studied for different film thicknesses and grain sizes.