The initial interactions of oxygen with polycrystalline titanium surfaces

The interactions of gaseous oxygen and different types of polycrystalline titanium surfaces were studied at room temperature within the exposure range of 0-1000 L. Combined measurements utilizing direct recoils spectrometry (DRS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and work function variations enabled the distinction between processes occurring on the topmost atomic layer and those associated with subsurface incorporation of oxygen. Also, the different chemical forms (oxidation states) developing during the exposure course were identified. The results were compared for three types of surfaces, each prepared by a different cleaning procedure. It has been concluded that: (i) Oxygen initially accumulates on the topmost atomic layer, regardless of the type of the studied surface. No preferred subsurface occupation has been observed. (ii) The kinetics of initial accumulation (up to a complete surface coverage) are similar for all the different types of surfaces. (iii) Mixtures of different oxidation states of titanium (0, +2, +3, +4) are present during the whole course of exposure. Qualitatively, increasing proportions of the higher valence states are displayed for higher oxygen exposures. However, the quantitative estimates of their relative amounts indicate a strong dependence on the type of surface, with preferred high oxidation (+4) states obtained for high temperature annealed samples (as compared with room temperature sputtered surfaces). (iv) Topmost oxygen atoms which terminate the oxides surfaces are less negatively charged than the underlying (i.e., subsurface) "oxidic" atoms. These results may account for some of the controversies presented in the literature.