Argon plasma treatment techniques on steel and effects on diamond-like carbon structure and delamination

We demonstrate alteration in diamond-like carbon (DLC) film structure, chemistry and adhesion on steel, related to variation in the argon plasma pretreatment stage of plasma enhanced chemical vapour deposition. We relate these changes to the alteration in substrate structure, crystallinity and chemistry due to application of an argon plasma process with negative self bias up to 600 V. Adhesion of the DLC film to the substrate was assessed by examination of the spallated fraction of the film following controlled deformation. Films with no pretreatment step immediately delaminated. At 300 V pretreatment, the spallated fraction is 8.2%, reducing to 1.2% at 450 V and 0.02% at 600V. For bias voltages below 450V the adhesion enhancement is explained by a reduction in carbon contamination on the substrate surface, from 59at.% with no treatment to 26at.% at 450V, concurrently with a decrease in the surface roughness, Rq, from 31.5nm to 18.9nm. With a pretreatment bias voltage of 600V a nanocrystalline, nanostructured surface is formed, related to removal of chromium and relaxation of stress; X-ray diffraction indicates this phase is incipient at 450V. In addition to improving film adhesion, the nanotexturing of the substrate prior to film deposition results in a DLC film that shows an increase in sp/sp ratio from 1.2 to 1.5, a reduction in surface roughness from 31nm to 21nm, and DLC nodular asperities with reduced diameter and increased uniformity of size and arrangement. These findings are consistent with the substrate alterations due to the plasma pretreatment resulting in limitation of surface diffusion in the growth process. This suggests that in addition to deposition phase processes, the parameters of the pretreatment process need to be considered when designing diamond-like carbon coatings. Prime Novelty: We elucidate the mechanisms behind the enhancement of diamond-like carbon film adhesion with increase in pretreatment bias voltage, and demonstrate the effect on the final film structure of alterations in the pretreatment process.