Oxidation mechanisms of copper under graphene: the role of oxygen encapsulation

The oxidation and corrosion of copper are fundamental issues studied for many decades due to their ubiquitous and transversal impact. However, the oxidation of copper used as catalyst for graphene synthesis has opened a singular problem not yet solved. Contradictory results are reported about the protecting or enhancing role of graphene in copper oxidation. We study short- and long-term oxidation of copper with different characteristics, such as oxygen content and morphology, with and without graphene, and in polycrystalline copper foils and almost totally textured (100) and (111) copper films on MgO and sapphire substrates, respectively. We propose a mechanism to explain the enhanced oxidation of polycrystalline copper originated by oxygen encapsulated by the graphene impermeable layer during graphene growth. The initial oxygen content and the existence of grain boundaries are the main factors that determine the relevance of this process. Graphene is shown to prevent oxidation from the atmosphere for any of the copper substrates but also promotes slow oxidation derived by the release of out-of-equilibrium encapsulated oxygen. The formation of bubbles after several months evidence this slow release. The occluded oxygen in graphene covered copper is demonstrated by comparing the oxygen to copper ratio at different depths using hard X-ray photoelectron spectroscopy for samples with and without graphene.
Funding by the Spanish Ministerio de Economía y Competitividad (MINECO) under Projects MAT2015-65356-C3-1-R and MAT2012-37276-C03-01 and Comunidad de Madrid Excellence Network under Project S2013/MIT-2740 is acknowledged. We also acknowledge the MINECO for financial support and provision of synchrotron radiation facilities at BM25 SpLine The Spanish CRG Beamline at the ESRF. L.A-F. acknowledges a FPI grant (BES-2013-062759) from MINECO.