Theoretical Analysis of Oxygen Diffusion in monoclinic HfO₂

In this report, we present the detailed analysis of the interstitial oxygen (O2+, O0, O2-) diffusion in monoclinic HfO2 (hafnia) using the first principles calculations. The interstitial oxygen atom kicks out the oxygen atom at the 3-fold-site and occupies the 3-fold-site. And then the newly kicked-out interstitial oxygen atom jumps to the nearest neighbor site and couples again with the atoms at the crystal sites. This kick-out- mechanism is valid for all charge states of the interstitial oxygen in monoclinic HfO2. In hafnia, the interstitial oxygen atom can take 3 charge states (+2, 0, -2) depending on the chemical potential (Ef), whereas the oxygen-vacancy in hafnia can get +2 or 0 charge state being dependent on Ef. In the lower range of Ef, O2+ and O0 might contribute. In the middle range of Ef, the O2- does not contribute to the diffusion process in hafnia because of the pair annihilation process between O2- and oxygen vacancy (V2+) defect pair. We can simulate such a pair annihilation process in hafnia. In the higher range, O2- might contribute the diffusion process.