Adsorption of Carbon on Partially Oxidized Low-Index Cu Surfaces.

We use first-principles calculations to study the carbon adsorption on copper slabs of (100) and (111) surfaces predosed by oxygen atoms. Our results show that on both surfaces, an incoming carbon atom has the ability to replace and completely desorb a previously surface-adsorbed oxygen atom producing CO and CO2 molecules in the gas phase. By comparison, the (111) surface is better suited for oxygen desorption, and an incoming carbon atom can more easily bond to and desorb oxygen atoms even at low oxygen coverages. We examine this mechanism at two different temperatures for both surfaces at 0.5 ML oxygen coverage. An implication of this process is the experimentally proven cleaning effect of predosing copper surfaces with oxygen before graphene growth in the chemical vapor deposition process. Conversely, adsorption and diffusion of carbon atoms, both of which are necessary for the nucleation and growth of carbon nanotubes, may be hindered by the presence of the oxidized or partially oxidized surfaces.