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

Abstract

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 CH 3 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.