| Hard carbon thin films are important candidate materials to improve the tribological performance of mechanical components ranging from the macro- to the nanoscale. Extensive study at the macroscale has established their excellent tribomechanical properties, but little is known about their nanoscale properties. We investigated three carbon-based films: ultrananocrystalline diamond (UNCD), tetrahedral amorphous carbon (ta-C), and diamond-like carbon (DLC). We used near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to determine the chemical composition and the nature of the surface bonds. We used atomic force microscopy (AFM) to measure the work of adhesion and frictional forces between diamond tips (microcrystalline and UNCD) and both UNCD and ta-C surfaces, and between fluorinated DLC (F-DLC) tips and both F-DLC and silicon-containing DLC (Si-DLC).;For UNCD, we were able to reach van der Waals's limit of adhesion for hydrocarbons (∼30 mJ/m2) and reduce nanoscale friction forces by terminating defective surfaces with hydrogen. This is particularly important for the underside of UNCD films, which we studied by etching away their underlying substrates. We found that this underside had a higher percentage of sp2 bonding and oxygen than the upper surface, but exposure to hydrogen plasma restored the sp3 character and improved the nanotribological properties.;We studied ta-C films annealed from 200°C - 1000°C, and found that thermal annealing increased the sp2 bonding percentage. Above 600°C, the conversion from sp3→sp2 bonding increased dramatically. When the as-deposited films were oxygen-free, we observed no change in the work of adhesion (which is low at ∼40 mJ/m 2) as a function of thermal annealing, but we did see a reduction in nano scale friction.;F-DLC and Si-DLC films were investigated before and after thermally annealing them at 300°C in air. The NEXAFS and AFM results demonstrated that Si-DLC is stable, both chemically and nanotribologically. The F-DLC film, however, showed an increase in C-F bonding, O=C-OH bonding, and friction. No significant change in the work of adhesion for either film was observed.;Overall, these results demonstrate that the composition and bonding state of the surface atoms of carbon-based films can have a significant impact on the tribological properties at the nanometer scale. |
