A new approach to the analysis of carbon-containing materials by the method of secondary ion mass spectrometry is studied, which allows one to determine the concentration of carbon atoms in the states of sp2 and sp3 hybridization. It is proposed to use the ratio of the intensities of cluster secondary ions C8/C7 as the main parameter of the mass spectra of secondary ions characterizing the concentration of N(sp3). From measurements of several test structures, a calibration dependence of N (sp3) on the C8/C7 ratio was obtained. The N(sp3) profiles of diamond-like carbon samples grown on diamond and silicon substrates were measured, showing an N(sp3) concentration of 0.3 to 0.6 for different growth modes and an inhomogeneous distribution of the N(sp3) concentration over the thickness of the samples.