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

Nature Chemistry volume 11, pages 730–736 (2019)Cite this article

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Abstract

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.

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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.

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Acknowledgements

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).

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Author notes

  1. These authors contributed equally: Can Liu, Xiaozhi Xu, Lu Qiu, Muhong Wu.

Authors and Affiliations

  1. State Key Laboratory for Mesoscopic Physics, Academy for Advanced Interdisciplinary Studies, School of Physics, Peking University, Beijing, China

    Can Liu, Xiaozhi Xu, Muhong Wu, Ruixi Qiao, Li Wang, Jinhuan Wang, Jingjing Niu, Jing Liang, Xu Zhou, Zhihong Zhang, Xiaosong Wu & Kaihui Liu

  2. State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science and Technology of China, Chengdu, China

    Can Liu, Xu Zhou & Jie Xiong

  3. School of Physics and Telecommunication Engineering, South China Normal University, Guangzhou, China

    Xiaozhi Xu

  4. Centre for Multidimensional Carbon Materials, Institute for Basic Science, Ulsan, Republic of Korea

    Lu Qiu & Feng Ding

  5. School of Materials Science and Engineering, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea

    Lu Qiu & Feng Ding

  6. Songshan Lake Materials Laboratory, Dongguan, Guangdong, China

    Muhong Wu & Enge Wang

  7. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Li Wang, Wenlong Wang & Xuedong Bai

  8. Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering and College of Engineering, and BIC-ESAT, Peking University, Beijing, China

    Mi Peng & Ding Ma

  9. International Centre for Quantum Materials, Peking University, Beijing, China

    Peng Gao, Ying Jiang & Enge Wang

  10. Collaborative Innovation Centre of Quantum Matter, Beijing, China

    Peng Gao & Kaihui Liu

  11. Institute for Quantum Science and Engineering and Department of Physics, South University of Science and Technology of China, Shenzhen, China

    Dapeng Yu

  12. Shenzhen Key Laboratory of Quantum Science and Engineering, Shenzhen, China

    Dapeng Yu

Authors
  1. Can Liu
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Contributions

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, Feng Ding or Kaihui Liu.

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Supplementary Information

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

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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). https://doi.org/10.1038/s41557-019-0290-1

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