One-phonon Raman spectra of carbon in composite films prepared by modification of amorphous hydrogenated carbon by copper and cobalt

One-phonon visible-range Raman spectra of a-C: H〈Cu〉 and a-C: H〈Co〉 composite films with comparable metal and carbon contents were studied in the frequency region 1200–1700 cm^?1 including the carbon sp²-bond vibrations. Broad bands G and D characteristic of unmodified a-C: H films, as well as some additional features, are observed experimentally in the spectra. By unfolding the spectra into Gaussian components, it was possible to follow the variation of Raman shifts and of contributions of individual components to the spectrum as a function of metal content and thermal annealing. The data obtained, complemented by available information on carbon sp²-coordinated systems, show that incorporation of Cu or Co favors growth and ordering of graphite-like nanoclusters in a-C: H, the effect being substantially stronger in the case of Co. It is shown that the process of metal-stimulated graphitization includes carbon bond breaking with the formation of short chainlike fragments and their linkage with the formation of aromatic-ring nanoclusters. A qualitatively similar sp²-structure rearrangement takes place under thermal annealing. For the Cu and Co concentrations studied, the linear dimensions L _a of graphite-like clusters are estimated to vary from ～0.8 nm in unannealed a-C: H to ～1.0 and ～1.2 nm in annealed a-C: H〈Cu〉 and a-C: H〈Co〉, respectively. The number of aromatic rings in these clusters is approximately estimated to increase from 12 to 16 (for Cu) and 20 (for Co).