The fate of graphene on copper: Intercalation / de-intercalation processes and the role of silicon

Intercalation and de-intercalation processes below graphene (g) grown by chemical vapor deposition (CVD) on Cu foils (g/Cu) were investigated in a combined low-energy electron microscopy and X-ray photoemission electron microscopy study. Exposure of g/Cu to air induces oxygen and water intercalation which can be removed by annealing in vacuum leading to clean and well-ordered graphene on Cu. However, prolonged air exposure leads to intercalation of large amounts of oxygen, most likely inducing the formation of copper oxides. If sufficient intercalated oxygen remains at the interface when exceeding 320 °C, graphene is oxidized and burned off. Cu foils can be loaded with silicon on purpose during foil pre-treatment or accidently during long growth time when applying high temperatures at elevated H2 pressure inducing the reactive removal of Si species from the quartz reactor wall. Due to the dissolution of Si in the Cu bulk, the Si surface concentration remains below detection limit and graphene of equal crystalline quality is grown as if the Cu foil was silicon-free. However, oxygen intercalation underneath graphene on Si-containing Cu foils can induce Si segregation towards the surface and formation of intercalated silica without attacking the covering graphene. Even at high temperatures, segregating Si acts as oxygen scavenger so that graphene resists oxidation. The observed effect explains the usefulness of certain synthesis protocols and paves the way towards large-scale fabrication of electronically decoupled graphene. The effect can be used to immobilize adsorbing oxygen at the interface and image the initial steps of intercalation below graphene in-situ.