The initial, thermal oxidation of zirconium at room temperature

Angle-resolved x-ray photoelectron spectroscopy (ARXPS) and in situ spectroscopic ellipsometry have been used to investigate the initial oxidation of polycrystalline zirconium at room temperature in the partial oxygen pressure range of 1.3x10(-7)-1.3x10(-4) Pa. Detailed quantitative analysis of the measured Zr 3d ARXPS spectra of the oxidized metal allowed separation of the intrinsic and extrinsic metallic and oxidic contributions to the spectra. It was shown that, in addition to the metallic contribution from the substrate and the oxidic contribution from stoichiometric ZrO2, two additional suboxidic components are contained in the measured Zr 3d spectra of the oxidized Zr metal. As evidenced by angle-resolved XPS and in situ ellipsometry, both of these components can be attributed to a gradient of Zr enrichment in the region of the oxide film adjacent to the metal/oxide interface (with the highest Zr enrichment at the metal/oxide interface). Investigation of the oxide-film growth kinetics at various pO(2), as determined independently using both techniques, showed the occurrence of an initial regime of very fast, electric-field-controlled growth, followed by a much slower oxidation stage. As a result, an, on average, nonstoichiometric oxide film develops. The observed effect of the pO(2) on the low-temperature oxidation of Zr has been discussed in terms of the relationship between the fraction of coverage of the surface with physi- and chemisorbed oxygen and the applied pO(2). (C) 2004 American Institute of Physics.