Structural Polymorphism Kinetics Promoted by Charged Oxygen Vacancies in HfO$_2$

Defects such as oxygen vacancy are widely considered to be critical for the performance of HfO2-based devices, and yet atomistic mechanisms underlying various exotic effects such as wake-up and fluid imprint remain elusive. Here, guided by a lattice-mode-matching criterion, we systematically study the phase transitions between different polymorphs of hafnia under the influences of neutral and positively charged oxygen vacancies by mapping out the minimum energy pathways using a first-principles-based variable-cell nudged elastic band technique. We find that the positively charged oxygen vacancy can substantially promote the transition of various nonpolar phases to the polar phase kinetically, enabled by a transient high-energy tetragonal phase and extreme charge-carrier-inert ferroelectricity of the polar $Pca2_1$ phase. The intricate coupling between structural polymorphism kinetics and the charge state of the oxygen vacancy has important implications for the origin of ferroelectricity in HfO$_2$-based thin films as well as wake-up, fluid imprint, and inertial switching.

Liyang Ma, Shi Liu · 2022