Atomic layer deposition of TiO2 from TiI4 and H2O onto SiO2 surfaces: ab initio calculations of the initial reaction mechanisms

The initial surface reactions involved in the atomic layer deposition (ALD) of TiO2 from TiI4 and H2O onto a SiO2 substrate have been investigated using electronic structure calculations based on cluster models. The detailed atomic growth mechanisms on different types of functionalities on the SiO2 substrate have been proposed. The effects of quantum tunneling and hindered rotations of adsorbates on the rate of surface reactions have been investigated. The effects of tunneling were found to be negligible for all reactions, because typical ALD temperatures range from 150 to 450 degrees C. However, the rotational contributions to the rate constants must be taken into account in certain cases. All of the three surface functionalities investigated exhibit high chemical reactivity toward TiI4 precursors at typical ALD temperatures. The rate constants of the second half-reactions between Ti intermediates and H2O are 5-8 orders of magnitude smaller than the first half-reactions between TiI4 and the surface functionalities. Although the iodine release reaction has been used to explain previous experimental measurements, it is predicted to be unfavorable (kinetically and thermodynamically) and is unlikely to occur at typical ALD temperatures. Substitution of TiI4 with TiCl4 as the metal precursor can increase the binding energies of the absorbates onto the surface due to the high electronegativity of the Cl ligands. However, the activation barriers are not significantly different between these two metal precursors. More importantly, our calculations predict that TiI4 precursors tend to produce TiO2 films with fewer impurities than the TiCl4 precursors.