Oxidation kinetics of transition metals exposed to molecular and atomic oxygen

In this work we analyze the oxidation of 30 nm polycrystalline transition metals films (Hf, Ta, Mo and Ru) at low temperatures (298 K to 473 K) upon the exposure to two different species: molecular oxygen and atomic oxygen. Using in-situ spectroscopic ellipsometry and in-vacuum X-ray photoelectron spectroscopy, we verify the oxide growth kinetics and the final stoichiometry after each exposure condition for the four metals, and explore the particularities present in each oxide growth mechanics. The temperature-dependent analysis enabled to experimentally obtain the dissociation energy of molecular oxygen at polycrystalline O covered surfaces. By applying the principles of coupled currents and the Cabrera-Mott oxide growth mechanism, we extract values of the energy barrier for oxidation and the field formed in both oxygen molecule-metal and atom-metal interaction, exploring the differences between both exposure conditions. We demonstrate that in oxide growth at low temperatures two key points should be highlighted: (i) the strong dependence of surface potential on reactive oxygen coverage; (ii) the interrelation between exposure conditions and crystalline oxide formation. The obtained results and analysis contribute to the understanding of oxidation processes at low temperatures, advancing the knowledge required for the design and synthesis of thin metal and oxide films.