Ferroelectricity at the extreme thickness limit in the archetypal antiferroelectric PbZrO$_3$

Abstract: Size-driven transition of an antiferroelectric into a polar ferroelectric or ferrielectric state is a strongly debated issue from both experimental and theoretical perspectives. While critical thickness limits for such transitions have been explored, a bottom-up approach in the ultrathin limit considering few atomic layers could provide insight into the mechanism of stabilization of the polar phases over the antipolar phase seen in bulk PbZrO$_3$. Here, we use first-principles density functional theory to predict the stability of polar phases in Pt/PbZrO$_3$/Pt nanocapacitors. In a few atomic layer thick slabs of PbZrO$_3$ sandwiched between Pt electrodes, we find that the polar phase originating from the well established R3c phase of bulk PbZrO$_3$ is energetically favorable over the antipolar phase originating from the Pbam phase of bulk PbZrO$_3$. The famous triple-well potential of antiferroelectric PbZrO$_3$ is modified in the nanocapacitor limit in such a way as to swap the positions of the global and local minima, stabilizing the polar phase relative to the antipolar one. The size effect is decomposed into the contributions from dimensionality reduction, surface charge screening, and interfacial relaxation, which reveals that it is the creation of well-compensated interfaces that stabilizes the polar phases over the antipolar ones in nanoscale PbZrO$_3$.