Synthesis and characterization of sulfur-incorporated microcrystalline diamond and nanocrystalline carbon thin films by hot filament chemical vapor deposition

The synthesis of microcrystalline and nanocrystalline carbon thin films using sulfur as an impurity addition to chemical vapor deposition (CVD) was investigated. Sulfur-incorporated microcrystalline diamond (μc-D:S) and nanocrystalline carbon (n-C:S) thin films were deposited on Mo substrates using methane (CH4), hydrogen (H2), and hydrogen sulfide (H2S) gas feedstocks by hot-filament CVD. These films were grown under systematically varied process parameters, while the methane concentration was fixed at 0.3% and 2% for μc-D:S and n-C:S, respectively, to study the corresponding variations of the films’ microstructure. Through these studies we obtained an integral understanding of the materials grown and learned how to control key material properties. The nanocrystalline nature of the material was proposed to be due to the change in the growth mechanisms in the gas phase (continuous secondary nucleation). The growth rate (G) was found to increase with increasing TS and [H2S] in gas phase, thus following the chemisorption model that describes the surface reactions. One of the propositions for the increase was that H2S increases the production rates of methane and consequent methyl radicals without much of its own consumption, which is almost negligible and increases the carbon-containing species. This is analogous to the increase of G with increasing methane concentration, but for the relatively high S/C ratio used here, there is a possibility of its incorporation in the material, however small. This particular conjecture was verified. In this context, the results are discussed in terms of the decomposition of reactant gases (CH4/H2/H2S) that yield ionized species. The inferences drawn are compared to those grown without sulfur to study the influence of sulfur addition to the CVD.