Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

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

Nature Nanotechnology volume 15, pages59–66(2020)Cite this article

Subjects

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.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

Rent or Buy

All prices are NET prices.

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.

References

  1. 1.

    Chernozatonskii, L. A., Sorokin, P. B., Kvashnin, A. G. & Kvashnin, D. G. Diamond-like C2H nanolayer, diamane: simulation of the structure and properties. JETP Lett 90, 134–138 (2009).

    CAS  Article  Google Scholar 

  2. 2.

    Ribas, M. A., Singh, A. K., Sorokin, P. B. & Yakobson, B. I. Patterning nanoroads and quantum dots on fluorinated graphene. Nano. Res 4, 143–152 (2011).

    CAS  Article  Google Scholar 

  3. 3.

    Barboza, A. P. et al. Room-temperature compression-induced diamondization of few-layer graphene. Adv. Mater. 23, 3014–3017 (2011).

    CAS  Article  Google Scholar 

  4. 4.

    Odkhuu, D., Shin, D., Ruoff, R. S. & Park, N. Conversion of multilayer graphene into continuous ultrathin sp3-bonded carbon films on metal surfaces. Sci. Rep 3, 3276 (2013).

    Article  Google Scholar 

  5. 5.

    Kvashnin, A. G., Chernozatonskii, L. A., Yakobson, B. I. & Sorokin, P. B. Phase diagram of quasi-two-dimensional carbon, from graphene to diamond. Nano Lett. 14, 676–681 (2014).

    CAS  Article  Google Scholar 

  6. 6.

    Martins, L. G. P. et al. Raman evidence for pressure-induced formation of diamondene. Nat. Commun. 8, 96 (2017).

    Article  Google Scholar 

  7. 7.

    Gao, Y. et al. Ultrahard carbon film from epitaxial two-layer graphene. Nat. Nanotechnol. 13, 133–138 (2018).

    CAS  Article  Google Scholar 

  8. 8.

    Rajasekaran, S., Abild-Pedersen, F., Ogasawara, H., Nilsson, A. & Kaya, S. Interlayer carbon bond formation induced by hydrogen adsorption in few-layer supported graphene. Phys. Rev. Lett. 111, 085503 (2013).

    Article  Google Scholar 

  9. 9.

    Rajasekaran, S. et al. Reversible graphene-metal contact through hydrogenation. Phys. Rev. B 86, 075417 (2012).

    Article  Google Scholar 

  10. 10.

    Pumera, M. & Wong, C. Graphane and hydrogenated graphene. Chem. Soc. Rev. 42, 5987–5995 (2013).

    CAS  Article  Google Scholar 

  11. 11.

    Piazza, F. et al. Low temperature, pressureless sp2 to sp3 transformation of ultrathin, crystalline carbon films. Carbon 145, 10–20 (2019).

    CAS  Article  Google Scholar 

  12. 12.

    Smith, D. et al. Hydrogenation of graphene by reaction at high pressure and high temperature. ACS Nano 9, 8279–8283 (2015).

    CAS  Article  Google Scholar 

  13. 13.

    Elias, D. C. et al. Control of graphene’s properties by reversible hydrogenation: evidence of graphane. Science 323, 610–613 (2009).

    CAS  Article  Google Scholar 

  14. 14.

    Burgess, J. S. et al. Tuning the electronic properties of graphene by hydrogenation in a plasma enhanced chemical vapor deposition reactor. Carbon 49, 4420–4426 (2011).

    CAS  Article  Google Scholar 

  15. 15.

    Nair, R. R. et al. Fluorographene: a two-dimensional counterpart of teflon. Small 6, 2877–2884 (2010).

    CAS  Article  Google Scholar 

  16. 16.

    Robinson, J. T. et al. Properties of fluorinated graphene films. Nano Lett. 10, 3001–3005 (2010).

    CAS  Article  Google Scholar 

  17. 17.

    Jeon, K.-J. et al. Fluorographene: a wide bandgap semiconductor with ultraviolet luminescence. ACS Nano 5, 1042–1046 (2011).

    CAS  Article  Google Scholar 

  18. 18.

    Fleisch, T. H. & Mains, G. J. Reduction of copper oxides by UV radiation and atomic hydrogen studied by XPS. Appl. Surf. Sci. 10, 51–62 (1982).

    CAS  Article  Google Scholar 

  19. 19.

    Grosvenor, A. P., Biesinger, M. C., Smart, R. St. C. & McIntyre, N. S. New interpretations of XPS spectra of nickel metal and oxides. Surf. Sci 600, 1771–1779 (2006).

    CAS  Article  Google Scholar 

  20. 20.

    Hoffman, S. in Practical Surface Analysis, Vol. 2 (eds Briggs, D. & Seah, M. P.) Ch. 4 (Wiley, 1990).

  21. 21.

    Watanabe, N. Characteristics and applications of graphite fluoride. Physica B & C 105, 17–21 (1981).

    CAS  Article  Google Scholar 

  22. 22.

    Asanov, I. P., Paasonen, V. M., Mazalov, L. N. & Nazarov, A. S. X-ray photoelectron study of fluorinated graphite intercalation compounds. J. Struct. Chem 39, 1127–1133 (1998).

    Article  Google Scholar 

  23. 23.

    An, K. H. et al. X-ray photoemission spectroscopy study of fluorinated single-walled carbon nanotubes. Appl. Phys. Lett. 80, 4235–4237 (2002).

    CAS  Article  Google Scholar 

  24. 24.

    Sato, Y., Itoh, K., Hagiwara, R., Fukunaga, T. & Ito, Y. On the so-called “semi-ionic” C-F bond character in fluorine-GIC. Carbon 42, 3243–3249 (2004).

    CAS  Article  Google Scholar 

  25. 25.

    Okotrub, A. V., Yudanov, N. F., Asanov, I. P., Vyalikh, D. V. & Bulusheva, L. G. Anisotropy of chemical bonding in semifluorinated graphite C2F revealed with angle-resolved X-ray absorption spectroscopy. ACS Nano 7, 65–74 (2013).

    CAS  Article  Google Scholar 

  26. 26.

    Grayfer, E. D. et al. Synthesis, properties, and dispersion of few-layer graphene fluoride. Chem.-Asian J. 8, 2015–2022 (2013).

    CAS  Article  Google Scholar 

  27. 27.

    Claves, D. Spectroscopic study of fluorinated carbon nanostructures. New J. Chem. 35, 2477–2482 (2011).

    CAS  Article  Google Scholar 

  28. 28.

    Yun, S.-M. et al. An XPS study of oxyfluorinated multiwalled carbon nano tubes. Carbon Lett 8, 292–298 (2007).

    Article  Google Scholar 

  29. 29.

    Wu, Y. et al. Growth mechanism and controlled synthesis of AB-stacked bilayer graphene on CuNi alloy foils. ACS Nano 6, 77311–77738 (2012).

    Google Scholar 

  30. 30.

    Liu, L. et al. High-yield chemical vapor deposition growth of high-quality large-area AB-stacked bilayer graphene. ACS Nano 6, 8241–8249 (2012).

    CAS  Article  Google Scholar 

  31. 31.

    Luo, Z. et al. Large-scale synthesis of Bi-layer graphene in strongly coupled stacking order. Adv. Funct. Mater. 21, 911–917 (2011).

    CAS  Article  Google Scholar 

  32. 32.

    Bianconi, A., Hagström, S. B. M. & Bachrach, R. Z. Photoemission studies of graphite high-energy conduction-band and valence-band states using soft X-ray synchrotron radiation excitation. Phys. Rev. B 16, 5543–5548 (1977).

    CAS  Article  Google Scholar 

  33. 33.

    Ono, M. et al. UPS study of VUV-photodegradation of polytetrafluoroethylene (PTFE) ultrathin film by using synchrotron radiation. Nucl. Instrum. Meth. B 236, 377–382 (2005).

    CAS  Article  Google Scholar 

  34. 34.

    Pate, B. B. The diamond surface: atomic and electronic structure. Surf. Sci 165, 83–142 (1986).

    CAS  Article  Google Scholar 

  35. 35.

    Rietwyk, K. J. et al. Work function and electron affinity of the fluorine-terminated (100) diamond surface. Appl. Phys. Lett. 102, 091604 (2013).

    Article  Google Scholar 

  36. 36.

    Kravets, V. G. et al. Spectroscopic ellipsometry of graphene and an exciton-shifted van Hove peak in absorption. Phys. Rev. B 81, 155413 (2010).

    Article  Google Scholar 

  37. 37.

    Warner, J. H. et al. Structural transformations in graphene studied with high spatial and temporal resolution. Nat. Nanotechnol 4, 500–504 (2009).

    CAS  Article  Google Scholar 

  38. 38.

    Withers, F., Bointon, T. H., Dubois, M., Russo, S. & Craciun, M. F. Nanopatterning of fluorinated graphene by electron beam irradiation. Nano Lett. 11, 3912–3916 (2011).

    CAS  Article  Google Scholar 

  39. 39.

    Martins, S. E., Withers, F., Dubois, M., Craciun, M. F. & Russo, S. Tuning the transport gap of functionalized graphene via electron beam irradiation. New J. Phys. 15, 033024 (2013).

    Article  Google Scholar 

  40. 40.

    Hayashi, T. et al. NanoTeflons: structure and EELS characterization of fluorinated carbon nanotubes and nanofibers. Nano Lett. 2, 491–496 (2002).

    CAS  Article  Google Scholar 

Download references

Acknowledgements

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

Author information

Author notes

  1. Manav Saxena

    Present address: Centre for Nano Material Sciences, Jain University, Karnataka, India

  2. These authors contributed equally: Pavel V. Bakharev and Ming Huang.

Affiliations

  1. Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), Ulsan, Republic of Korea

    Pavel V. Bakharev, Ming Huang, Manav Saxena, Jichen Dong, Dulce C. Camacho-Mojica, Sunghwan Jin, Youngwoo Kwon, Mandakini Biswal, Feng Ding, Sang Kyu Kwak, Zonghoon Lee & Rodney S. Ruoff

  2. School of Materials Science and Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Ming Huang, Suk Woo Lee, Feng Ding, Zonghoon Lee & Rodney S. Ruoff

  3. School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Se Hun Joo, Sung O Park, Sang Kyu Kwak & Rodney S. Ruoff

  4. Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Rodney S. Ruoff

Authors
  1. Pavel V. Bakharev
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ming Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Manav Saxena
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Suk Woo Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Se Hun Joo
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Sung O Park
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jichen Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Dulce C. Camacho-Mojica
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Sunghwan Jin
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Youngwoo Kwon
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Mandakini Biswal
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Feng Ding
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Sang Kyu Kwak
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Zonghoon Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Rodney S. Ruoff
    View author publications

    You can also search for this author in PubMed Google Scholar

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.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary information

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

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

Further reading

Search

Quick links

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research