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Depth profiling analysis of the surface oxide layer of TiAIN film was conducted using synchrotron radiation excited x-ray photoelectron spectroscopy. The results indicated that the oxidation of nitride and segregation into titanium oxide and aluminum oxide take place simultaneously. Topmost surface layer was found to be aluminum oxide. The depth profiling also suggests that molecular nitrogen, which is formed by the oxidation of the nitride, occurs only in the titanium oxide layer. Thus, the topmost alumina layer is dense and functions as a protective layer for the inward diffusion of oxygen and the outward diffusion of nitrogen.