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Continuous epitaxy of single-crystal graphite films by isothermal carbon diffusion through nickel

Nature Nanotechnology volume 17, pages 1258–1264 (2022)Cite this article

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Abstract

Multilayer van der Waals (vdW) film materials have attracted extensive interest from the perspective of both fundamental research1,2,3 and technology4,5,6,7. However, the synthesis of large, thick, single-crystal vdW materials remains a great challenge because the lack of out-of-plane chemical bonds weakens the epitaxial relationship between neighbouring layers8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31. Here we report the continuous epitaxial growth of single-crystal graphite films with thickness up to 100,000 layers on high-index, single-crystal nickel (Ni) foils. Our epitaxial graphite films demonstrate high single crystallinity, including an ultra-flat surface, centimetre-size single-crystal domains and a perfect AB-stacking structure. The exfoliated graphene shows excellent physical properties, such as a high thermal conductivity of ~2,880 W m−1 K−1, intrinsic Young’s modulus of ~1.0 TPa and low doping density of ~2.2 × 1010 cm−2. The growth of each single-crystal graphene layer is realized by step edge-guided epitaxy on a high-index Ni surface, and continuous growth is enabled by the isothermal dissolution–diffusion–precipitation of carbon atoms driven by a chemical potential gradient between the two Ni surfaces. The isothermal growth enables the layers to grow at optimal conditions, without stacking disorders or stress gradients in the final graphite. Our findings provide a facile and scalable avenue for the synthesis of high-quality, thick vdW films for various applications.

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Fig. 1: Continuous growth of the large epitaxial graphite film.
Fig. 2: Structural characterization of the epitaxial graphite film.
Fig. 3: Thermal, mechanical and electronic properties of the exfoliated graphene monolayer and few layers.
Fig. 4: Mechanism for the continuous epitaxial growth of the graphite film.

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Data availability

Source data are provided with this paper. The data that support the findings of this study are available within the paper and Supplementary Information. Additional data are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by Guangdong Major Project of Basic and Applied Basic Research (2021B0301030002 (Enge Wang and Kaihui Liu)), the National Natural Science Foundation of China (52025023 (Kaihui Liu), 51991342 (Kaihui Liu), 52021006 (Kaihui Liu), 11888101 (Enge Wang), 92163206 (M.W.), 52172035 (M.W.), 52125307 (P.G.) and T2188101 (Kaihui Liu)), the Key R&D Programme of Guangdong Province (2019B010931001 (Kaihui Liu) and 2018B030327001 (D.Y.)), the National Key R&D Programme of China (2021YFB3200303 (Kaihui Liu), 2021YFA1400502 (M.W.)), the Strategic Priority Research Programme of Chinese Academy of Sciences (XDB33000000 (Kaihui Liu)), Beijing Natural Science Foundation (JQ19004 (Kaihui Liu)), the Tencent Foundation through the XPLORER PRIZE (Kaihui Liu) and the Institute for Basic Science of South Korea (IBS-R019-D1 (F.D.)). We acknowledge the use of the IBS-CMCM high-performance computing system simulator.

Author information

Author notes

  1. These authors contributed equally: Zhibin Zhang, Mingchao Ding, Ting Cheng.

Authors and Affiliations

  1. State Key Laboratory for Mesoscopic Physics, Frontiers Science Centre for Nano-optoelectronics, School of Physics, Peking University, Beijing, China

    Zhibin Zhang, Mengze Zhao, Xingguang Li, Zhihong Zhang, Fang Liu, Can Liu, Xinqiang Wang & Kaihui Liu

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

    Mingchao Ding & Xuedong Bai

  3. School of Physical Sciences, University of Chinese Academy of Sciences, Beijing, China

    Mingchao Ding & Xuedong Bai

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

    Ting Cheng & Feng Ding

  5. College of Chemistry and Molecular Engineering, Academy for Advanced Interdisciplinary Studies, Peking University, Beijing, China

    Ting Cheng

  6. International Centre for Quantum Materials, Collaborative Innovation Centre of Quantum Matter, Peking University, Beijing, China

    Ruixi Qiao, Muhong Wu, Peng Gao, Enge Wang & Kaihui Liu

  7. State Key Laboratory of Surface Physics and Department of Physics, Fudan University, Shanghai, China

    Mingyan Luo & Yuanbo Zhang

  8. State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, China

    Enze Wang, Yufei Sun & Kai Liu

  9. State Key Laboratory of Tribology in Advanced Equipment, Applied Mechanics Laboratory, Tsinghua University, Beijing, China

    Shuai Zhang & Qunyang Li

  10. State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

    Hancheng Mao, Chuanlin Fan & Qingshan Zhu

  11. Songshan Lake Materials Laboratory, Dongguan, China

    Ying Fu, Kehai Liu, Muhong Wu, Xuedong Bai, Enge Wang & Kaihui Liu

  12. Shenzhen Institute for Quantum Science and Engineering, Southern University of Science and Technology, Shenzhen, China

    Dingxin Zou & Dapeng Yu

  13. Interdisciplinary Institute of Light-Element Quantum Materials and Research Centre for Light-Element Advanced Materials, Peking University, Beijing, China

    Muhong Wu

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

    Feng Ding

  15. School of Physics, Liaoning University, Shenyang, China

    Enge Wang

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  1. Zhibin Zhang
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Contributions

Kaihui Liu and Enge Wang supervised the project. Kaihui Liu conceived the experiments. F.D., Enge Wang and Kaihui Liu developed the growth mechanism. D.Y. organized the structural characterization. Zhibin Zhang and M.D. synthesized the epitaxial graphite film. T.C. and F.D. performed the theoretical analysis. X.B., Zhibin Zhang, R.Q., M.Z., X.L., F.L., Zhihong Zhang, D.Z., C.L., M.W., X.W. and P.G. performed the SEM, TEM, EBSD and X-ray diffraction experiments. Zhibin Zhang, M.D., Y.F. and Kehai Liu performed the thermal conductivity measurements. Kai Liu, Q.L., Enze Wang, Y.S. and S.Z. performed the mechanical experiments. Y.Z. and M.L. performed the electronic transport experiment. Q.Z., Zhibin Zhang, H.M. and C.F. performed the chlorination experiment. All authors discussed the results and contributed to writing the paper.

Corresponding authors

Correspondence to Dapeng Yu, Feng Ding, Enge Wang or Kaihui Liu.

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Nature Nanotechnology thanks Maria Losurdo and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Zhang, Z., Ding, M., Cheng, T. et al. Continuous epitaxy of single-crystal graphite films by isothermal carbon diffusion through nickel. Nat. Nanotechnol. 17, 1258–1264 (2022). https://doi.org/10.1038/s41565-022-01230-0

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