Quantum chemical study of the elementary reactions in zirconium oxide atomic layer deposition

Elementary reactions in atomic layer deposition of zirconia using zirconium tetrachloride and water are investigated using the density functional theory. The atomistic mechanisms of the two deposition half cycles on the Zr-OH and Zr-Cl surface sites are investigated. Both half reactions proceed through the formation of stable intermediates, resulting in high barriers for HCl formation. We find that the intermediate stability is lowered as the surface temperature is raised. However, increasing temperature also increases the dissociation free-energy barrier, which in turn results in increased desorption of adsorbed precursors. (C) 2002 American Institute of Physics.