After decades of searching for robust nanoscale ferroelectricity that could enable integration into the next generation memory and logic devices, hafnia-based thin films have appeared as the ultimate candidate because their ferroelectric (FE) polarization becomes more robust as the size is reduced. This exposes a new kind of ferroelectricity, whose mechanism still needs to be understood. Towards this end, thin films with increased crystal quality are needed. We report the epitaxial growth of Hf0.5Zr0.5O2 (HZO) thin films on (001)-oriented La0.7Sr0.3MnO3/SrTiO3 (STO) substrates. The films, which are under epitaxial compressive strain and are predominantly (111)-oriented, display large FE polarization values up to 34 μC/cm 2 and do not need wake-up cycling. Structural characterization reveals a rhombohedral phase, different from the commonly reported polar orthorhombic phase. This unexpected finding allows us to propose a compelling model for the formation of the FE phase. In addition, these results point towards nanoparticles of simple oxides as a vastly unexplored class of nanoscale ferroelectrics.

Unconventional ferroelectricity exhibited by hafnia-based thin films, robust at nanoscale sizes, presents tremendous opportunities in nanoelectronics. However, the exact nature of polarization switching remains controversial. We investigated La0.67Sr0.33MnO3/Hf0.5Zr0.5O2 capacitor interfaced with various top electrodes while in situ electrical biasing using atomic resolution microscopy with direct oxygen imaging, as well as synchrotron nanobeam diffraction. When the top electrode is oxygen reactive, we clearly show reversible oxygen vacancy migration with electrodes being the source and sink of oxygen, and the dielectric layer acting as a fast conduit at millisecond timescales. With non-reactive top electrodes and at longer time scales (seconds), the dielectric layer also acts as an oxygen source/sink. Our results show that ferroelectricity in hafnia-based thin films is unmistakably intertwined to oxygen voltammetry.