Stabilization of the epitaxial rhombohedral ferroelectric phase in ZrO2 by surface energy

Doped HfO2 and HfO2-ZrO2 compounds are gaining significant interest thanks to their ferroelectric properties in ultrathin films. Here, we show that ZrO2 could be a playground for doping and strain engineering to increase the thickness in epitaxial thin films. Based on surface energy considerations supported by ab initio calculations, we show that a pure ZrO2 epitaxial thin film exhibits a ferroelectric rhombohedral phase (r-phase, with R3m space group) more stable than for the Hf0.5Zr0.5O2 (HZO) and pure HfO2 cases. In particular, for a thickness up to 37 nm we experimentally evidence a single (111)-oriented r-phase in ZrO2 films deposited on La2/3Sr1/3MnO3-buffered DyScO3(110) substrate, while a tetragonal phase is observed alongside the rhombohedral one on SrTiO3(001). The formation of this r-phase is discussed and compared between HfO2, ZrO2 and HZO, highlighting the role of surface energy.
Comment: 21 pages, 14 figures, 2 tables, including supplemental information