Evolution of carbon film structure during its catalyst-free growth in the plasma of direct current glow discharge

Catalyst-free growth of nanocrystalline carbon films on silicon substrates under direct current glow discharge in a mixture of hydrogen and methane was studied by scanning and transmission electron microscopy, Raman spectroscopy, as well as X-ray photoelectron and near edge X-ray absorption fine structure spectroscopy (BESSY II, Berlin). The in-time development of the film structure on a carbided silicon substrate includes the formation of diamond-like particles, ultra-thin graphite flakes parallel to the surface, carbon nanowalls nucleated on the stacked flakes and their growth accompanied by a permanent decrease of the structural defect density, and finally nanotube nucleation at the nanowall edges. Based on the observation of the carbon nanotube/nanowall linear size variation in time and using the calculated binding energies and the diffusion thresholds obtained from the literature, we propose that direct attachment of the CH3 radicals to the carbon nanowall edge is the predominant mechanism and the rate-limiting step of its growth, whereas carbon nanotube growth is controlled by radicals diffusing along its outer surface.