Abstract
The interfacial reaction between deposited molybdenum and three different TiO 2(1 1 0) substrates (a bulk and surface stoichiometric TiO 2; a bulk stoichiometric and surface reduced crystal; a bulk and surface slightly reduced crystal) was investigated by means of X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). While the interfacial reaction is not a function of the substrate at room temperature (in any case, molybdenum layers grow with oxygen dissolved in), this study clearly reveals a strong effect of the substrate bulk stoichiometry on the chemical state of the deposit after annealing up to 750 °C whereas the substrate surface stoichiometry plays a minor role. Indeed, annealing carried out on deposits performed on bulk stoichiometric TiO 2 (whatever the initial surface stoichiometry is) leads to MoO 3 formation whereas annealing carried out on layers which grew on bulk non-stoichiometric TiO 2 involves metallic molybdenum overlayers. These results, as well as others previously published on the same system, are discussed from a new model based on thermodynamical considerations including entropic effect.
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