Electron-Injection-Assisted Generation of Oxygen Vacancies in Monoclinic HfO2

Understanding the mechanisms of generation of oxygen vacancies in monoclinic (m)-HfO2 is important for improving and controlling its performance as an oxide layer in transistor gate stacks and in resistive random-access memory (RRAM) devices. We use ab initio calculations to investigate the mechanism of formation of Frenkel pairs of oxygen vacancies and interstitial ions in m-HfO2 under electron-injection conditions. The results demonstrate that the formation of stable pairs of neutral oxygen vacancies and interstitial oxygen ions assisted by extra electrons is thermodynamically feasible and requires overcoming activation barriers of less than 1.3 eV at preexisting O vacancies. A preexisting oxygen vacancy can act as an electron trap and facilitate the formation of an O vacancy and O interstitial ion pair nearby. The resulting O divacancy is stabilized by weak attraction between neutral vacancies, further lowering the formation energy of the defect pair. The binding energy per vacancy in larger oxygen-vacancy aggregates increases as the aggregate grows, facilitating the formation of defect pairs next to larger vacancy aggregates. These results are useful for understanding the mechanisms of oxide degradation and electroforming in RRAM cells, which can proceed through creation of new O vacancies in the vicinity of preexisting vacancies complementing vacancy aggregation via diffusion processes.