Stoichiometry-related Auger lineshapes in titanium oxides: Influence of valence-band profile and of Coster-Kronig processes

The ability to determine the nature and the occurrence of defects is a central need of ceramic surface chemistry. In titanium oxides, the Ti-LMV Auger decays line shape is very sensitive to the titanium degree of oxidation, and has long been empirically used as a qualitative probe of the stoichiometry. In the present work, resonant Auger and resonant valence-band measurements at the Ti-L2,3 edges in TiO2, TiO2-x and metallic titanium provide a clear evidence that the evolutions of the Ti-LMV Auger line shape are due to drastic changes in the valence-band profile and in the probability of L2L3V Coster-Kronig decay processes when a fraction of titanium ions is reduced. Both are shown to be consequences of the filling of Ti-3d states near the Fermi level on defects sites. These conclusions are confirmed by Auger-photoelectron coincidence experiments.