Although graphene is well known for super-lubricity on its basal plane, friction at its step edge is not well understood and contradictory friction behaviors have been reported. In this study, friction of mono-layer thick graphene step edges was studied using atomic force microscopy (AFM) with a Si tip in dry nitrogen atmosphere. It is found that, when the tip slides over a 'buried’ graphene step edge, there is a resistive force during the step-up motion and an assistive force during the step-down motion due to the topographic height change. The magnitude of these two forces is small and the same in both step-up and step-down motions. As for the 'exposed’ graphene step edge, friction increases in magnitude and exhibits more complicated behaviors. During the step-down motion of the tip over the exposed step edge, both resistive and assistive components can be detected in the lateral force signal of AFM if the scan resolution is sufficiently high. The resistive component is attributed to chemical interactions between the functional groups at the tip and step-edge surfaces, and the assistive component is due to the topographic effect, same as the case of buried step edge. If a blunt tip is used, the distinct effects of these two components become more prominent. In the step-up scan direction, the blunt tip appears to have two separate topographic effects-elastic deformation of the contact region at the bottom of the tip due to the substrate height change at the step edge and tilting of the tip while the vertical position of the cantilever (the end of the tip) ascends from the lower terrace to the upper terrace. The high-resolution measurement of friction behaviors at graphene step edges will further enrich understanding of interfacial friction behaviors on graphene-covered surfaces.

Tribology involves not only two-body contacts of two solid materials—a substrate and a counter-surface; it often involves three-body contacts whether the third body is intentionally introduced or inevitably added during the sliding or rubbing. The intentionally added third body could be lubricant oil or engineered nano- material used to mitigate the friction and wear of the sliding contact. The inevitably added third body could be wear debris created from the substrate or the counter surface during sliding. Even in the absence of any solid third-body between the sliding surfaces, molecular adsorption of water or organic vapors from the surrounding environment can dramatically alter the friction and wear behavior of solid surfaces tested in the absence of lubricant oils. This review article covers the last case: the effects of molecular adsorption on sliding solid surfaces both inevitably occurring due to the ambient test and intentionally introduced as a solution for engineering problems. We will review how adsorbed molecules can change the course of wear and friction, as well as the mechanical and chemical behavior, of a wide range of materials under sliding conditions.