Tuning graphene doping by carbon monoxide intercalation at the Ni(111) interface

Under near-ambient pressure conditions, carbon monoxide molecules intercalate underneath an epitaxial graphene monolayer grown on Ni(111), getting trapped into the confined region at the interface. On the basis of ab-initio density functional theory calculations, we provide here a full investigation of the intercalated CO pattern, highlighting the modifications induced on the graphene electronic structure. For a CO coverage as low as 0.14 monolayer (ML), the graphene layer is spatially decoupled from the metallic substrate, with a significant C 1s core level shift towards lower binding energies. The most relevant signature of the CO intercalation is a clear switching of the graphene doping state, which changes from n-type, when strongly interacting with the metal surface, to p-type. The shift of the Dirac cone linearly depends on the CO coverage, reaching about 0.9 eV for the saturation value of 0.57 ML. Theoretical predictions are compared with the results of scanning tunnelling microscopy, low-energy electron diffraction and photoemission spectroscopy experiments, which confirm the proposed scenario for the nearly saturated intercalated CO system. This result opens the way to the application of the graphene/Ni(111) interface as gas sensor to easily detect and quantify the presence of carbon monoxide. (C) 2021 Elsevier Ltd. All rights reserved.

Automated summary

Through ab-initio density functional theory calculations, this study reveals the impact of CO intercalation on the graphene/Ni(111) interface, showing a spatial separation of the graphene layer from the metal substrate leading to a significant change in the doping state of graphene. Experimental results confirm the influence of CO intercalation on the electronic structure of graphene, providing new insights for the application of graphene in gas sensing.