Stabilization of metastable phases in hafnia owing to surface energy effects

摘要

The recent empirical observation of ferroelectricity in hafnia is rather surprising since all of its known ground-state phases are nonpolar. In this letter, we show that finite size effects, relevant under experimental conditions, may themselves lead to this unexpected phenomenon due to stabilization of metastable polar phase(s). Using surface energies computed from first principles, we determine the thermodynamic stability of a parallelepiped shaped particle constructed from various low energy nonpolar and polar phases of hafnia. We find that at small dimensions, surface effects may stabilize either one of the polar phases or the nonpolar tetragonal phase (the parent phase of the polar phases), suggesting a possible explanation of the ferroelectric behavior observed in pure hafnia films. These results also explain the stabilization of the metastable tetragonal phase in nanoparticles of zirconia, the twin oxide of hafnia. While a comprehensive understanding of the origins of ferroelectricity in hafnia will require inclusion of other relevant factors (such as strain and dopants), this work highlights the importance of finite size effects as a possible key factor.