The Kinetics of Shear-Induced Boundary Film Formation from Dimethyl Disulfide on Copper

The kinetics of the shear-induced surface-to-bulk transport of methyl thiolate species formed from dimethyl disulfide (DMDS) on a copper surface are explored. It is found that the loss of surface species as a function of the number of rubbing cycles can be modeled by assuming that the adsorbed layer penetrates the subsurface a distance of ~0.7 nm per scan. Adding wear to this model does not improve the fit to the experimental data providing an upper limit for the wear rate of ~0.06 nm/scan. This model is applied to analyzing the depth distribution of sulfur within the subsurface region as a function of the number of rubbing cycles, measured by Auger depth profiling when continually dosing the copper sample with DMDS. It is found that the shape of the experimental depth profile is in agreement with the model developed to analyze the surface-to-bulk transport kinetics of the adsorbed layer. However, the profiles are almost identical for surfaces that have been rubbed 130 and 360 times, so that the surface-to-bulk transport kinetics are self limiting.