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Insight into the rapid growth of graphene single crystals on liquid metal via chemical vapor deposition

化学气相沉积法在液态金属上快速生长石墨烯单晶

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Abstract

Previous reports about the growth of large graphene single crystals on polycrystalline metal substrates usually adopted the strategy of suppressing the nucleation by lowering the concentration of the feedstock, which greatly limited the rate of the nucleation and the sequent growth. The emerging liquid metal catalyst possesses the characteristic of quasi-atomically smooth surface with high diffusion rate. In principle, it should be a naturally ideal platform for the lowdensity nucleation and the fast growth of graphene. However, the rapid growth of large graphene single crystals on liquid metals has not received the due attention. In this paper, we firstly purposed the insight into the rapid growth of large graphene single crystals on liquid metals. We obtained the millimeter-size graphene single crystals on liquid Cu. The rich free-electrons in liquid Cu accelerate the nucleation, and the isotropic smooth surface greatly suppresses the nucleation. Moreover, the fast mass-transfer of carbon atoms due to the excellent fluidity of liquid Cu promotes the fast growth with a rate up to 79 μm s–1. We hope the research on the growth speed of graphene on liquid Cu can enrich the recognition of the growth behavior of two-dimensional (2D) materials on the liquid metal. We also believe that the liquid metal strategy for the rapid growth of graphene can be extended to various 2D materials and thus promote their future applications in the photonics and electronics.

摘要

实现石墨烯大单晶的快速生长对于其未来在光电及电学器件领域的应用十分必要. 目前已报道的在多晶金属衬底上生长石墨烯单晶的工作通常是通过降低前驱体供应量从而抑制成核来实现的, 而这会显著降低成核以及后续生长的速度. 新兴的液态金属催化剂具有准原子级平滑的表面和高扩散速率. 理论上, 液态金属是一个天然理想的基底可同时实现低密度成核和快速生长. 但截至目前, 尚无工作探讨液态金属上石墨烯单晶的快速生长. 在本研究中, 我们成功地在液态铜表面实现了毫米级高质量石墨烯单晶的生长. 液态铜中丰富的自由电子能加速石墨烯的成核, 且其各向同性的平滑表面能显著抑制成核, 使得成核密度较低. 更重要的是, 由于液态铜优异的可流动性, 前驱体碳原子能实现快速扩散, 这极大促进了石墨烯的生长, 最高速率可达79 μm s−1. 我们希望这一关于液态铜体系中石墨烯生长速率的研究能丰富研究者们对液态金属上二维材料生长行为的认知. 我们也相信利用液态金属来实现石墨烯快速生长的策略能被拓展至其他二维材料, 由此来促进它 们在未来光电以及电学器件领域的应用.

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References

  1. Novoselov KS, Geim AK, Morozov SV, et al. Two-dimensional gas of massless Dirac fermions in graphene. Nature, 2005, 438: 197–200

    Article  Google Scholar 

  2. Novoselov KS, Fal'ko VI, Colombo L, et al. A roadmap for graphene. Nature, 2012, 490: 192–200

    Article  Google Scholar 

  3. Zeng M, Xiao Y, Liu J, et al. Exploring two-dimensional materials toward the next-generation circuits: from monomer design to assembly control. Chem Rev, 2018, 118: 6236–6296

    Article  Google Scholar 

  4. Li K, Zhang J. Recent advances in flexible supercapacitors based on carbon nanotubes and graphene. Sci China Mater, 2017, 61: 210–232

    Article  Google Scholar 

  5. Lin L, Deng B, Sun J, et al. Bridging the gap between reality and ideal in chemical vapor deposition growth of graphene. Chem Rev, 2018, 118: 9281–9343

    Article  Google Scholar 

  6. Vlassiouk I, Smirnov S, Regmi M, et al. Graphene nucleation density on copper: fundamental role of background pressure. J Phys Chem C, 2013, 117: 18919–18926

    Article  Google Scholar 

  7. Safron NS, Kim M, Gopalan P, et al. Barrier-guided growth of micro- and nano-structured graphene. Adv Mater, 2012, 24: 1041–1045

    Article  Google Scholar 

  8. Kim HK, Mattevi C, Calvo MR, et al. Activation energy paths for graphene nucleation and growth on Cu. ACS Nano, 2012, 6: 3614–3623

    Article  Google Scholar 

  9. Wang L, Gao J, Ding F. Application of crystal growth theory in graphene CVD nucleation and growth. Acta Chim Sin, 2014, 72: 345–358

    Article  Google Scholar 

  10. Gao J, Yip J, Zhao J, et al. Graphene nucleation on transition metal surface: structure transformation and role of the metal step edge. J Am Chem Soc, 2011, 133: 5009–5015

    Article  Google Scholar 

  11. Geng D, Wang H, Yu G. Graphene single crystals: size and morphology engineering. Adv Mater, 2015, 27: 2821–2837

    Article  Google Scholar 

  12. Wang H, Xu X, Li J, et al. Surface monocrystallization of copper foil for fast growth of large single-crystal graphene under free molecular flow. Adv Mater, 2016, 28: 8968–8974

    Article  Google Scholar 

  13. Hao Y, Bharathi MS, Wang L, et al. The role of surface oxygen in the growth of large single-crystal graphene on copper. Science, 2013, 342: 720–723

    Article  Google Scholar 

  14. Xu X, Zhang Z, Qiu L, et al. Ultrafast growth of single-crystal graphene assisted by a continuous oxygen supply. Nat Nanotech, 2016, 11: 930–935

    Article  Google Scholar 

  15. Xu X, Zhang Z, Dong J, et al. Ultrafast epitaxial growth of metresized single-crystal graphene on industrial Cu foil. Sci Bull, 2017, 62: 1074–1080

    Article  Google Scholar 

  16. Wu T, Zhang X, Yuan Q, et al. Fast growth of inch-sized singlecrystalline graphene from a controlled single nucleus on Cu–Ni alloys. Nat Mater, 2015, 15: 43–47

    Article  Google Scholar 

  17. Zeng M, Wang L, Liu J, et al. Self-assembly of graphene single crystals with uniform size and orientation: the first 2D superordered structure. J Am Chem Soc, 2016, 138: 7812–7815

    Article  Google Scholar 

  18. Liu J, Fu L. Controllable growth of graphene on liquid surfaces. Adv Mater, 2018, 8: 1800690

    Article  Google Scholar 

  19. Zeng M, Fu L. Controllable fabrication of graphene and related two-dimensional materials on liquid metals via chemical vapor deposition. Acc Chem Res, 2018, 51: 2839–2847

    Article  Google Scholar 

  20. Gao L, Ren W, Xu H, et al. Repeated growth and bubbling transfer of graphene with millimetre-size single-crystal grains using platinum. Nat Commun, 2012, 3: 699

    Article  Google Scholar 

  21. Hedayat SM, Karimi-Sabet J, Shariaty-Niassar M. Evolution effects of the copper surface morphology on the nucleation density and growth of graphene domains at different growth pressures. Appl Surf Sci, 2017, 399: 542–550

    Article  Google Scholar 

  22. Liu L, Zhou H, Cheng R, et al. A systematic study of atmospheric pressure chemical vapor deposition growth of large-area monolayer graphene. J Mater Chem, 2012, 22: 1498–1503

    Article  Google Scholar 

  23. Zhou H, Yu WJ, Liu L, et al. Chemical vapour deposition growth of large single crystals of monolayer and bilayer graphene. Nat Commun, 2013, 4: 2096

    Article  Google Scholar 

  24. Lin L, Li J, Ren H, et al. Surface engineering of copper foils for growing centimeter-sized single-crystalline graphene. ACS Nano, 2016, 10: 2922–2929

    Article  Google Scholar 

  25. Wood JD, Schmucker SW, Lyons AS, et al. Effects of polycrystalline Cu substrate on graphene growth by chemical vapor deposition. Nano Lett, 2011, 11: 4547–4554

    Article  Google Scholar 

  26. Ross M, Boehler R, Errandonea D. Melting of transition metals at high pressure and the influence of liquid frustration: the late metals Cu, Ni, and Fe. Phys Rev B, 2007, 76: 184117

    Article  Google Scholar 

  27. Shabanova IN, Kholzakov AV, Kraposhin VS. XPS study of transition metal electronic structure in crystalline and liquid states. J Electron Spectr Related Phenomena, 1998, 88-91: 453–455

    Article  Google Scholar 

  28. Shabanova IN, Mitrokhin YS. The study of the atomic and electronic structures of liquid copper. J Electron Spectr Related Phenomena, 2004, 137-140: 569–571

    Article  Google Scholar 

  29. Laidler KJ, Meiser JH. Physical Chemistry. Boston: Houghton Mifflin, 1999

    Google Scholar 

  30. Lin L, Sun L, Zhang J, et al. Rapid growth of large single-crystalline graphene via second passivation and multistage carbon supply. Adv Mater, 2016, 28: 4671–4677

    Article  Google Scholar 

  31. Sun L, Lin L, Zhang J, et al. Visualizing fast growth of large singlecrystalline graphene by tunable isotopic carbon source. Nano Res, 2017, 10: 355–363

    Article  Google Scholar 

  32. Chen CC, Kuo CJ, Liao CD, et al. Growth of large-area graphene single crystals in confined reaction space with diffusion-driven chemical vapor deposition. Chem Mater, 2015, 27: 6249–6258

    Article  Google Scholar 

  33. Babenko V, Murdock AT, Koós AA, et al. Rapid epitaxy-free graphene synthesis on silicidated polycrystalline platinum. Nat Commun, 2015, 6: 7536

    Article  Google Scholar 

  34. Guo W, Jing F, Xiao J, et al. Oxidative-etching-assisted synthesis of centimeter-sized single-crystalline graphene. Adv Mater, 2016, 28: 3152–3158

    Article  Google Scholar 

  35. Vlassiouk IV, Stehle Y, Pudasaini PR, et al. Evolutionary selection growth of two-dimensional materials on polycrystalline substrates. Nat Mater, 2018, 17: 318–322

    Article  Google Scholar 

  36. Geng D, Wu B, Guo Y, et al. Uniform hexagonal graphene flakes and films grown on liquid copper surface. Proc Natl Acad Sci USA, 2012, 109: 7992–7996

    Article  Google Scholar 

  37. Guo W, Xu C, Xu K, et al. Rapid chemical vapor deposition of graphene on liquid copper. Synth Met, 2016, 216: 93–97

    Article  Google Scholar 

  38. Zeng M, Tan L, Wang J, et al. Liquid metal: an innovative solution to uniform graphene films. Chem Mater, 2014, 26: 3637–3643

    Article  Google Scholar 

  39. Li X, Cai W, Colombo L, et al. Evolution of graphene growth on Ni and Cu by carbon isotope labeling. Nano Lett, 2009, 9: 4268–4272

    Article  Google Scholar 

  40. Zeng M, Tan L, Wang L, et al. Isotropic growth of graphene toward smoothing stitching. ACS Nano, 2016, 10: 7189–7196

    Article  Google Scholar 

  41. Ferrari AC, Meyer JC, Scardaci V, et al. Raman spectrum of graphene and graphene layers. Phys Rev Lett, 2006, 97: 187401

    Article  Google Scholar 

Download references

Acknowledgements

The research was supported by the National Natural Science Foundation of China (21673161) and the Sino-German Center for Research Promotion (1400).

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Authors and Affiliations

  1. College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China

    Shuting Zheng  (郑舒婷), Mengqi Zeng  (曾梦琪), Hui Cao  (曹慧), Tao Zhang  (张涛), Xiaowen Gao  (高晓雯) & Lei Fu  (付磊)

  2. Institute for Advanced Studies (IAS), Wuhan University, Wuhan, 430072, China

    Yao Xiao  (肖遥) & Lei Fu  (付磊)

Authors
  1. Shuting Zheng  (郑舒婷)
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  2. Mengqi Zeng  (曾梦琪)
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  3. Hui Cao  (曹慧)
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  4. Tao Zhang  (张涛)
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  5. Xiaowen Gao  (高晓雯)
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  6. Yao Xiao  (肖遥)
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  7. Lei Fu  (付磊)
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Corresponding authors

Correspondence to Mengqi Zeng  (曾梦琪) or Lei Fu  (付磊).

Additional information

Shuting Zheng received her BSc from the Northwest University in 2016 and is now a master’s degree candidate under the supervision of Prof. Lei Fu at the College of Chemistry and Molecular Sciences at Wuhan University. Her current research interest is the controllable growth of 2D material

Mengqi Zeng received her BSc from Wuhan University in 2013. She obtained her PhD degree under the supervision of Prof. Lei Fu in 2018 from Wuhan University. In 2018, she joined Wuhan University as an Associate Professor. Her current research interest is the catalyst design for the controllable growth and self-assembly of 2D materials.

Lei Fu received his BSc degree in chemistry from Wuhan University in 2001. He obtained his PhD degree from the Institute of Chemistry, Chinese Academy of Sciences in 2006. After obtaining his PhD, he worked as a Director’s Postdoctoral Fellow at the Los Alamos National Laboratory, Los Alamos, NM (2006−2007). Thereafter, he became an Associate Professor at Peking University. In 2012, he joined Wuhan University as a Full Professor. His current interest of research focuses on the controlled growth and novel property exploration of 2D atomic layer thin crystals.

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Zheng, S., Zeng, M., Cao, H. et al. Insight into the rapid growth of graphene single crystals on liquid metal via chemical vapor deposition. Sci. China Mater. 62, 1087–1095 (2019). https://doi.org/10.1007/s40843-019-9406-7

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