Kinetic modulation of graphene growth by fluorine through spatially confined decomposition of metal fluorides


Two-dimensional materials show a variety of promising properties, and controlling their growth is an important aspect for practical applications. To this end, active species such as hydrogen and oxygen are commonly introduced into reactors to promote the synthesis of two-dimensional materials with specific characteristics. Here, we demonstrate that fluorine can play a crucial role in tuning the growth kinetics of three representative two-dimensional materials (graphene, hexagonal boron nitride and WS2). When growing graphene by chemical vapour deposition on a copper foil, fluorine released from the decomposition of a metal fluoride placed near the copper foil greatly accelerates the growth of the graphene (up to a rate of ~200 μm s−1). Theoretical calculations show that it does so by promoting decomposition of the methane feedstock, which converts the endothermic growth process to an exothermic one. We further show that the presence of fluorine also accelerates the growth of two-dimensional hexagonal boron nitride and WS2.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Fig. 1: Graphene growth modulated by local fluorine.
Fig. 2: Crystallinity and quality characterizations of graphene domains.
Fig. 3: Proposed mechanism for local fluorine-modulated graphene growth.
Fig. 4: Modulated growth of 2D h-BN and WS2 by a local fluorine supply.

Data availability

The data supporting the findings of this study are available within the paper and its Supplementary Information, and also from the authors upon request.


  1. 1.

    Xu, X. Z. et al. Ultrafast growth of single-crystal graphene assisted by a continuous oxygen supply. Nat. Nanotechnol. 11, 930–935 (2016).

    CAS  Article  Google Scholar 

  2. 2.

    Hao, Y. F. et al. The role of surface oxygen in the growth of large single-crystal graphene on copper. Science 342, 720–723 (2013).

    CAS  Article  Google Scholar 

  3. 3.

    Hao, Y. F. et al. Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene. Nat. Nanotechnol. 11, 426–431 (2016).

    CAS  Article  Google Scholar 

  4. 4.

    Kiplinger, J. L., Richmond, T. G. & Osterberg, C. E. Activation of carbon fluorine bonds by metal-complexes. Chem. Rev. 94, 373–431 (1994).

    CAS  Article  Google Scholar 

  5. 5.

    Reichenbacher, K., Suss, H. I. & Hulliger, J. Fluorine in crystal engineering—‘the little atom that could’. Chem. Soc. Rev. 34, 22–30 (2005).

    Article  Google Scholar 

  6. 6.

    Muller, K., Faeh, C. & Diederich, F. Fluorine in pharmaceuticals: looking beyond intuition. Science 317, 1881–1886 (2007).

    Article  Google Scholar 

  7. 7.

    Purser, S., Moore, P. R., Swallow, S. & Gouverneur, V. Fluorine in medicinal chemistry. Chem. Soc. Rev. 37, 320–330 (2008).

    CAS  Article  Google Scholar 

  8. 8.

    Price, S. C. et al. Fluorine substituted conjugated polymer of medium band gap yields 7% efficiency in polymer–fullerene solar cells. J. Am. Chem. Soc. 133, 4625–4631 (2011).

    CAS  Article  Google Scholar 

  9. 9.

    Furuya, T., Kamlet, A. S. & Ritter, T. Catalysis for fluorination and trifluoromethylation. Nature 473, 470–477 (2011).

    CAS  Article  Google Scholar 

  10. 10.

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

    CAS  Article  Google Scholar 

  11. 11.

    Zboril, R. et al. Graphene fluoride: a stable stoichiometric graphene derivative and its chemical conversion to graphene. Small 6, 2885–2891 (2010).

    CAS  Article  Google Scholar 

  12. 12.

    Romero-Aburto, R. et al. Fluorinated graphene oxide; a new multimodal material for biological applications. Adv. Mater. 25, 5632–5637 (2013).

    CAS  Article  Google Scholar 

  13. 13.

    Castro Neto, A. H. et al. The electronic properties of graphene. Rev. Mod. Phys. 81, 109–162 (2009).

    CAS  Article  Google Scholar 

  14. 14.

    Chhowalla, M. et al. The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat. Chem. 5, 263–275 (2013).

    Article  Google Scholar 

  15. 15.

    Giles, A. J. et al. Ultralow-loss polaritons in isotopically pure boron nitride. Nat. Mater. 17, 134–139 (2018).

    CAS  Article  Google Scholar 

  16. 16.

    Kubota, Y., Watanabe, K., Tsuda, O. & Taniguchi, T. Deep ultraviolet light-emitting hexagonal boron nitride synthesized at atmospheric pressure. Science 317, 932–934 (2007).

    CAS  Article  Google Scholar 

  17. 17.

    Novoselov, K. S. et al. A roadmap for graphene. Nature 490, 192–200 (2012).

    CAS  Article  Google Scholar 

  18. 18.

    Wang, Q. H. et al. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides. Nat. Nanotechnol. 7, 699–712 (2012).

    CAS  Article  Google Scholar 

  19. 19.

    Young, R. J. Two-dimensional nanocrystals: structure, properties and applications. Arab. J. Sci. Eng. 38, 1289–1304 (2013).

    Article  Google Scholar 

  20. 20.

    Fiori, G. et al. Electronics based on two-dimensional materials. Nat. Nanotechnol. 9, 768–779 (2014).

    CAS  Article  Google Scholar 

  21. 21.

    Cho, S. et al. Phase patterning for ohmic homojunction contact in MoTe2. Science 349, 625–628 (2015).

    CAS  Article  Google Scholar 

  22. 22.

    Keum, D. H. et al. Bandgap opening in few-layered monoclinic MoTe2. Nat. Phys. 11, 482–486 (2015).

    CAS  Article  Google Scholar 

  23. 23.

    Yang, H., Kim, S. W., Chhowalla, M. & Lee, Y. H. Structural and quantum-state phase transitions in van der Waals layered materials. Nat. Phys. 13, 1232–1232 (2017).

    Article  Google Scholar 

  24. 24.

    Dai, B. Y. et al. Rational design of a binary metal alloy for chemical vapour deposition growth of uniform single-layer graphene. Nat. Commun. 2, 522 (2011).

    Article  Google Scholar 

  25. 25.

    Gao, L. et al. Repeated growth and bubbling transfer of graphene with millimetre-size single-crystal grains using platinum. Nat. Commun. 3, 699 (2012).

    Article  Google Scholar 

  26. 26.

    Geng, D. C. et al. Uniform hexagonal graphene flakes and films grown on liquid copper surface. Proc. Natl Acad. Sci. USA 109, 7992–7996 (2012).

    CAS  Article  Google Scholar 

  27. 27.

    Yan, Z. et al. Toward the synthesis of wafer-scale single-crystal graphene on copper foils. ACS Nano 6, 9110–9117 (2012).

    CAS  Article  Google Scholar 

  28. 28.

    Zhou, H. L. et al. Chemical vapour deposition growth of large single crystals of monolayer and bilayer graphene. Nat. Commun. 4, 2096 (2013).

    Article  Google Scholar 

  29. 29.

    Lee, J. H. et al. Wafer-scale growth of single-crystal monolayer graphene on reusable hydrogen-terminated germanium. Science 344, 286–289 (2014).

    CAS  Article  Google Scholar 

  30. 30.

    Gao, L. B. et al. Face-to-face transfer of wafer-scale graphene films. Nature 505, 190–194 (2014).

    CAS  Article  Google Scholar 

  31. 31.

    Babenko, V. et al. Rapid epitaxy-free graphene synthesis on silicidated polycrystalline platinum. Nat. Commun. 6, 7536 (2015).

    CAS  Article  Google Scholar 

  32. 32.

    Nguyen, V. L. et al. Seamless stitching of graphene domains on polished copper (111) foil. Adv. Mater. 27, 1376–1382 (2015).

    CAS  Article  Google Scholar 

  33. 33.

    Wu, T. R. et al. Fast growth of inch-sized single-crystalline graphene from a controlled single nucleus on Cu–Ni alloys. Nat. Mater. 15, 43–47 (2016).

    CAS  Article  Google Scholar 

  34. 34.

    Wang, Z. J. et al. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging. Nat. Commun. 7, 13256 (2016).

    CAS  Article  Google Scholar 

  35. 35.

    Wang, H. et al. Surface monocrystallization of copper foil for fast growth of large single-crystal graphene under free molecular flow. Adv. Mater. 28, 8968–8974 (2016).

    CAS  Article  Google Scholar 

  36. 36.

    Zhang, Z. H. et al. The way towards ultrafast growth of single-crystal graphene on copper. Adv. Sci. 4, 1700087 (2017).

    Article  Google Scholar 

  37. 37.

    Xu, X. Z. et al. Ultrafast epitaxial growth of metre-sized single-crystal graphene on industrial Cu foil. Sci. Bull. 62, 1074–1080 (2017).

    CAS  Article  Google Scholar 

  38. 38.

    Vlassiouk, I. V. et al. Evolutionary selection growth of two-dimensional materials on polycrystalline substrates. Nat. Mater. 17, 318–322 (2018).

    CAS  Article  Google Scholar 

  39. 39.

    Liu, Z. et al. In-plane heterostructures of graphene and hexagonal boron nitride with controlled domain sizes. Nat. Nanotechnol. 8, 119–124 (2013).

    CAS  Article  Google Scholar 

  40. 40.

    Liu, L. et al. Heteroepitaxial growth of two-dimensional hexagonal boron nitride templated by graphene edges. Science 343, 163–167 (2014).

    CAS  Article  Google Scholar 

  41. 41.

    Duan, X. D. et al. Lateral epitaxial growth of two-dimensional layered semiconductor heterojunctions. Nat. Nanotechnol. 9, 1024–1030 (2014).

    CAS  Article  Google Scholar 

  42. 42.

    Yin, J. et al. Large single-crystal hexagonal boron nitride monolayer domains with controlled morphology and straight merging boundaries. Small 11, 4497–4502 (2015).

    CAS  Article  Google Scholar 

  43. 43.

    Kang, K. et al. High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity. Nature 520, 656–660 (2015).

    CAS  Article  Google Scholar 

  44. 44.

    Lu, G. Y. et al. Synthesis of large single-crystal hexagonal boron nitride grains on Cu–Ni alloy. Nat. Commun. 6, 6160 (2015).

    CAS  Article  Google Scholar 

  45. 45.

    Gao, Y. et al. Ultrafast growth of high-quality monolayer WSe2 on Au. Adv. Mater. 29, 1700990 (2017).

    Article  Google Scholar 

  46. 46.

    Zhang, Z. W. et al. Robust epitaxial growth of two-dimensional heterostructures, multiheterostructures and superlattices. Science 357, 788–792 (2017).

    CAS  Article  Google Scholar 

  47. 47.

    Wang, H. et al. High-quality monolayer superconductor NbSe2 grown by chemical vapour deposition. Nat. Commun. 8, 394 (2017).

    Article  Google Scholar 

  48. 48.

    Dong, J., Zhang, L. & Ding, F. Kinetics of graphene and 2D materials growth. Adv. Mater. 31, 1801583 (2019).

    Article  Google Scholar 

  49. 49.

    Li, X. S., Cai, W. W., Colombo, L. & Ruoff, R. S. Evolution of graphene growth on Ni and Cu by carbon isotope labeling. Nano Lett. 9, 4268–4272 (2009).

    CAS  Article  Google Scholar 

  50. 50.

    Moss, J. H., Ottie, R. & Wilford, J. B. The fluorination of methane and related compounds by copper(ii) fluoride and other metal fluorides. J. Fluor. Chem. 6, 393–416 (1975).

    CAS  Article  Google Scholar 

  51. 51.

    Kaneko, C. et al. Reaction of methane with molecular fluorine: an ab initio MO study. Chem. Pharm. Bull. 42, 745–747 (1994).

    CAS  Article  Google Scholar 

  52. 52.

    Zhou, J. D. et al. A library of atomically thin metal chalcogenides. Nature 556, 355–359 (2018).

    CAS  Article  Google Scholar 

  53. 53.

    Kresse, G. & Furthmuller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 6, 15–50 (1996).

    CAS  Article  Google Scholar 

  54. 54.

    Kresse, G. & Hafner, J. Ab-initio molecular-dynamics for open-shell transition-metals. Phys. Rev. B. 48, 13115–13118 (1993).

    CAS  Article  Google Scholar 

  55. 55.

    Wu, P. et al. Carbon dimers as the dominant feeding species in epitaxial growth and morphological phase transition of graphene on different Cu substrates. Phys. Rev. Lett. 114, 216102 (2015).

    Article  Google Scholar 

  56. 56.

    Henkelman, G., Uberuaga, B. P. & Jonsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).

    CAS  Article  Google Scholar 

  57. 57.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    CAS  Article  Google Scholar 

  58. 58.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B. 59, 1758–1775 (1999).

    CAS  Article  Google Scholar 

Download references


This work was supported by the National Key R&D Program of China (2016YFA0300903, 2016YFA0300804 and 2015CB358600), the NSFC (51522201, 11474006 and 51722204), the National Equipment Program of China (ZDYZ2015-1), Beijing Municipal Science & Technology Commission (Z181100004218006), Beijing Graphene Innovation Program (Z181100004818003 and Z161100002116028), the Bureau of Industry and Information Technology of Shenzhen (Graphene Platform contract no. 201901161512), the Science–Technology and Innovation Commission of Shenzhen Municipality (ZDSYS20170303165926217 and JCYJ20170412152620376), the Economic–Trade and Information Commission of Shenzhen Municipality, Guangdong Innovative and Entrepreneurial Research Team Program (2016ZT06D348), the National Postdoctoral Program for Innovative Talents (BX201700014 and BX20190016), the Fundamental Research Funds for the Central Universities (ZYGX2016Z004), the Institute for Basic Science (IBS-R019-D1) of South Korea and the Outstanding Research Fund (1.180066.01) of UNIST (Ulsan National Institute of Science & Technology).

Author information




K.L., E.W., D.Y. and C.L. conceived the experiment. K.L., F.D. and J.X. supervised the project. C.L., X.X. and M.W. conducted the growth experiment. C.L. performed Raman and XPS experiments. X.X. and Y.J. performed LEED and STM experiments. R.Q. and P.G. conducted the TEM experiments. J.N. and X.W. performed the electrical measurements. F.D. and L.Q. performed theoretical calculations. All of the authors discussed the results and wrote the paper.

Corresponding authors

Correspondence to Jie Xiong or Feng Ding or Kaihui Liu.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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

Supplementary information

Supplementary Information

Supplementary Figs. 1–18; Supplementary Tables 1–2; Supplementary Note

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Liu, C., Xu, X., Qiu, L. et al. Kinetic modulation of graphene growth by fluorine through spatially confined decomposition of metal fluorides. Nat. Chem. 11, 730–736 (2019).

Download citation

Further reading


Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing