Superlow friction of a-C:H coatings in vacuum: Passivation regimes and structural characterization of the sliding interfaces

A combination of atomistic simulations and vacuum tribometry allows atomic-scale insights into the chemical structure of superlubricious hydrogenated diamond-like carbon (a-C:H) interfaces in vacuum. Quantum molecular dynamics shearing simulations provide a structure-property map of the friction regimes that characterize the dry sliding of a-C:H. Shear stresses and structural properties at the sliding interfaces are crucially determined by the hydrogen content CH in the shear zone of the a-C:H coating. Extremely small CH (below 3 at.%) cause cold welding, mechanical mixing and high friction. At intermediate CH (ranging approximately from 3 to 20 at.%), cold welding in combination with mechanical mixing remains the dominant sliding mode, but some a-C:H samples undergo aromatization, resulting in a superlubricious sliding interface. A further increase in CH (above 20 at.%) prevents cold welding completely and changes the superlubricity mechanism from aromatic to hydrogen passivation. The hydrogen-passivated surfaces are composed of short hydrocarbon chains hinting at a tribo-induced oligomerization reaction. In the absence of cold welding, friction strongly correlates with nanoscale roughness, measured by the overlap of colliding protrusions at the sliding interface. Finally, the atomistic friction map is related to reciprocating friction experiments in ultrahigh vacuum. Accompanying X-ray photoelectron and Auger electron spectroscopy (XPS, XAES) analyses elucidate structural changes during vacuum sliding of a hydrogen-rich a-C:H with 36 at.% hydrogen. Initially, the a-C:H is covered by a nanometer-thick hydrogen-depleted surface layer. After a short running-in phase that results in hydrogen accumulation, superlubricity is established. XPS and XAES indicate a non-aromatic 1-2-nm-thick surface layer with polyethylene-like composition in agreement with our simulations.