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Chemically induced transformation of chemical vapour deposition grown bilayer graphene into fluorinated single-layer diamond

Abstract

Notwithstanding the numerous density functional studies on the chemically induced transformation of multilayer graphene into a diamond-like film carried out to date, a comprehensive convincing experimental proof of such a conversion is still lacking. We show that the fluorination of graphene sheets in Bernal (AB)-stacked bilayer graphene grown by chemical vapour deposition on a single-crystal CuNi(111) surface triggers the formation of interlayer carbon–carbon bonds, resulting in a fluorinated diamond monolayer (‘F-diamane’). Induced by fluorine chemisorption, the phase transition from (AB)-stacked bilayer graphene to single-layer diamond was studied and verified by X-ray photoelectron, UV photoelectron, Raman, UV-Vis and electron energy loss spectroscopies, transmission electron microscopy and density functional theory calculations.

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Fig. 1: AR-XPS characterization of fluorinated BLG.
Fig. 2: Raman characterization of fluorinated BLG on the CuNi(111) surface.
Fig. 3: TEM study of fluorinated BLG on the CuNi(111) surface.
Fig. 4: Spectroscopic analyses of fluorinated CVD BLG “suspended” on TEM grid.
Fig. 5: TEM and EELS studies of fluorinated BLG membranes.

Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

We acknowledge support from the Institute for Basic Science (IBS-R019-D1).

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Authors

Contributions

R.S.R. and P.V.B. conceived of the experiment. P.V.B. wrote the manuscript; designed and constructed the experimental setup; and performed experiments, characterizations and data analyses. P.V.B. and R.S.R. revised the manuscript. M.H. prepared CuNi(111) alloys by electroplating and annealing synthesized and characterized graphene films on CuNi(111) alloys and performed the graphene transfer onto TEM grids and SiO2/Si wafers; M.B. participated in making the metal alloy foils and synthesizing the graphene films. M.S. conducted the experiments and characterizations (transfer of the samples, assisting with building experimental setups and assisting with XPS and Raman characterizations). S.J. and Y.K. converted polycrystalline commercial Cu foils into single-crystal Cu(111). S.W.L. and Z.L. performed the TEM/STEM/EELS characterizations and TEM image simulations. S.H.J., S.O.P. and S.K.K. performed the DFT optimization and calculated formation energies as well as electronic and optical band gaps for various C2F configurations (Supplementary Figs. 4, 13 and 18). J.D. and F.D. performed the DFT calculations to simulate the transformation of BLG into F-diamane (Supplementary Fig. 7), as well as performing EELS simulations. D.C.M. performed DFT calculations, electronic band structure calculations and the TEM/diffraction pattern image simulations.

Corresponding authors

Correspondence to Pavel V. Bakharev or Rodney S. Ruoff.

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Peer review information Nature Nanotechnology thanks Rolf Erni and Anirudha Sumant for their contribution to the peer review of this work.

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Supplementary information

Supplementary information

Supplementary Figs. 1–22, Tables 1 and 2, DFT calculations and XPS quantitative analysis.

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Bakharev, P.V., Huang, M., Saxena, M. et al. Chemically induced transformation of chemical vapour deposition grown bilayer graphene into fluorinated single-layer diamond. Nat. Nanotechnol. 15, 59–66 (2020). https://doi.org/10.1038/s41565-019-0582-z

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