Origin of High Friction at Graphene Step Edges on Graphite

On graphite, friction is known to be more than an order of magnitude larger at step edge defects as compared to on the basal plane, especially when the counter surface slides from the lower terrace of the step to the upper terrace. Very different mechanisms have been proposed to explain this phenomenon, including atomic interactions between the counter surface and step edge (without physical deformation) and buckling or peeling deformation of the upper graphene terrace. Here, we use atomic force microscopy (AFM) and reactive molecular dynamic (MD) simulations to capture and differentiate the mechanisms proposed to cause high friction at step edges. AFM experiments reveal the difference between cases of no deformation and buckling deformation, and the latter case is attributed to the physical stress exerted by the sliding tip. Reactive MD simulations explore the process of peeling deformation due to tribochemical bond formation between the tip and the step edge. Combining the results of AFM experiments and MD simulations, it is found that each mechanism has identifiable and characteristic features in the lateral force and vertical height profiles recorded during the step-up process. The results demonstrate that buckling and peeling deformation of the graphene edge rarely occur under typical AFM experimental conditions and thus are unlikely to be the origin of high friction at step edges in most measurements. Instead, the high step-up friction is due to stick-slip behavior facilitated by the topographical change and atomic interactions between the tip and step edge without deformation of the graphene itself.