Atomic layer deposition of hafnium oxide: A detailed reaction mechanism from first principles

Abstract

Atomic layer deposition (ALD) of hafnium oxide (HfO2) using HfCl4 and H2O as precursors is studied using density functional theory. The mechanism consists of two deposition half-reactions: (1) HfCl4 with Hf-OH sites, and (2) H2O with Hf-Cl sites. Both half-reactions exhibit stable intermediates with energies lower than those of the final products. We show that increasing the temperature reduces the stability of the complex. However, increasing temperature also increases the dissociation free-energy barrier, which in turn results in increased desorption of adsorbed precursors. Both half-reactions are qualitatively similar to the corresponding reactions of ZrO2 ALD using ZrCl4 and H2O.