Graphitization effects of CH4 addition on NCD growth by first and second Raman spectra and by X-ray diffraction measurements

Nanocrystalline diamond (NCD) films were grown on silicon substrates by hot filament chemical vapour deposition in Ar/H₂/CH₄ gas mixtures. In the current study, the methane volume concentration varied from 0.5 to 3.5 vol.% in order to estimate its effect on nanodiamond morphology and structure. Film micrograph obtained from scanning electron microscopy showed diamond grain agglomerate, also called ballas diamond, which presented the grain size variation as a function of methane concentration increase. The transition from diamond agglomerate to graphite structure was also observed when CH₄ concentration is higher than 2.0 vol.%, confirmed from second order Raman measurements. The film local stress was estimated from the G-peak shift analyses and showed critical values necessary for the graphite/diamond phase formation. Structural investigations carried out by X-ray diffraction measurements for films deposited from 0.5 up to 2.0 vol.% CH₄ presented characteristic diamond diffraction peaks corresponding to 〈111〉, 〈220〉 and 〈311〉. A preferential orientation, changed from 〈110〉 to 〈111〉, was observed during NCD film deposition as a function of the methane concentration.