Raman and EPR spectroscopic studies of chromium-doped diamond-like carbon films

The diamond-like carbon (Cr-free DLC) and chromium-doped DLC (Cr doped-DLC) films prepared by a hybrid technology using a combination of pulsed laser deposition and magnetron sputtering were studied by Raman and electron paramagnetic resonance (EPR) spectroscopy. Raman spectra are dominated by the well-known carbon (D/G) band. The intensity ratio of the D/G bands was found to increase with the increase of the Cr content. Careful elimination of the substrate-related (SiO2) peaks enabled us to identify new weak features attributable to the presence of the C-Cr bonds. Two EPR signals were observed in Cr-free and Cr-doped DLC films. The EPR signal at g = 2.0025(3) was attributed to the sp(2) coordinated carbon-related defect (CRD) and the second EPR signal at g = 2.0064 was assigned to the P-b0 interface defect which may appear due to the formation of the oxidized Si on the interface of the DLC film and SiO2 substrate. The observed temperature behavior of the CRD EPR signal g-factor in Cr free DLC films was described by the model of exchange coupled two spin systems (localized defects and conduction electrons) in the bottleneck regime. From the temperature dependence of the linewidth and integral intensity of the CRD EPR signal it was concluded that ferromagnetic ordering occurs in the spin system with exchange constant of J = 0.069 meV. The spin density of the CRD was found to be significantly decreased in Cr-doped DLC films, possibly due to the formation of the C-Cr bonds. The observed change of the CRD lineshape from Lorentzian in Cr free DLC films to Gaussian in Cr-doped DLC films indicates that there is a superhyperfine coupling between unpaired spins of the CRD and surrounding Cr nuclei.