Preferential self-healing at grain boundaries in plasma-treated graphene

Abstract

Engineering of defects located in grains or at grain boundaries is central to the development of functional materials. Although there is a surge of interest in the formation, migration and annihilation of defects during ion and plasma irradiation of bulk materials, these processes are rarely assessed in low-dimensional materials and remain mostly unexplored spectroscopically at the micrometre scale due to experimental limitations. Here, we use a hyperspectral Raman imaging scheme providing high selectivity and diffraction-limited spatial resolution to examine plasma-induced damage in a polycrystalline graphene film. Measurements conducted before and after very low-energy (11–13 eV) ion bombardment show defect generation in graphene grains following a zero-dimensional defect curve, whereas domain boundaries tend to develop as one-dimensional defects. Damage generation is slower at grain boundaries than within the grains, a behaviour ascribed to preferential self-healing. This evidence of local defect migration and structural recovery in graphene sheds light on the complexity of chemical and physical processes at the grain boundaries of two-dimensional materials.

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Fig. 1: Evolution of AD/AG × \({\boldsymbol{E}}_{\boldsymbol{L}}^4\) versus ΓG for consecutive graphene plasma treatments.
Fig. 2: Evolution of 130 × 130-µm2 mappings of selected Raman band parameters.
Fig. 3: Analysis of plasma-induced damage in graphene.
Fig. 4: Imaging and probing of graphene boundaries.
Fig. 5: Relevant Raman parameters highlighting the discrepancies between GRs and GBs.
Fig. 6: Schematics of preferential self-healing at GBs in plasma-treated graphene.

Data availability

The data sets generated and analysed during the current study are available from the corresponding author upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was financially supported by the National Science and Engineering Research Council (NSERC), PRIMA-Québec, Plasmionique Inc., Photon etc., the Fonds de Recherche du Québec—Nature et Technologies (FRQNT) and the Canada Research Chair programme (L.S. and R.M.). We thank C. Charpin for providing the CVD-grown graphene samples and C. Allard for technical support with RIMA measurements.

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P.V. performed all experimental measurements. X.G. and P.V. participated in the initial writing of the manuscript. G.R.B. developed the code used for the analysis of RIMA data. All authors were involved in the design of experiments, data interpretation and manuscript revision. L.S. and R.M. contributed to funding acquisition, project administration and supervision.

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Correspondence to L. Stafford.

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Supplementary Discussion Sections I–VII, Figs. 1–6 and refs. 1–63.

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Data from Fig. 4b.

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Vinchon, P., Glad, X., Robert Bigras, G. et al. Preferential self-healing at grain boundaries in plasma-treated graphene. Nat. Mater. (2020). https://doi.org/10.1038/s41563-020-0738-0

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