Determination of sp2 and sp3 phase fractions on the surface of diamond films from C1s, valence band X-ray photoelectron spectra and CKVV X-ray-excited Auger spectra

The practice of applying the methods for determining the relative contents of carbon atoms in sp2 and sp3 hybridization states from the profiles of C1s X-ray photoelectron and carbon KVV (CKVV) Auger spectra is analyzed. Difficulties in using C1s and CKVV spectra for determining the sp2/sp3 ratios are discussed. A method is proposed for evaluating the fractions of sp2 and sp3 phases based on the fitting of the valence band X-ray photoelectron spectra by superposition of valence band spectra of samples with carbon atoms in pure sp2 and sp3 states. Relative fractions of sp2 and sp3 phases on the virgin surfaces of two ultrananocrystalline diamond films, and on their surfaces subjected to friction, were determined using C1s spectra, CKVV Auger spectra, and valence band spectra. All three methods gave the results that are consistent for virgin film surfaces with accuracy of 2%, and for the surfaces of films subjected to friction, 15%. In contrast to the ultrananocrystalline films, three XPS-based methods applied to a microcrystalline diamond film yielded significantly different sp2/sp3 ratios. The reasons for this discrepancy are shown to lie in different analysis depths of these methods, and in different morphology of the film surfaces.