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Diamond-like carbon (DLC) films were prepared by a pulsed laser deposition under Ar ion beam assisted growth. In-depth resolved carbon atom coordination was determined nondestructively and quantitatively from angular-resolved C 1s spectra by the Maximum entropy method. The results show that the sp2 coordination dominated at the surface, while the sp3 one is prevailing beneath the surface. The in-depth profiles were validated independently by the analysis of Auger C KVV spectra and by the measurement of the volume density of the layers.