Abstract
Graphene has a range of unique physical properties1,2 and could be of use in the development of a variety of electronic, photonic and photovoltaic devices3,4,5. For most applications, large-area high-quality graphene films are required and chemical vapour deposition (CVD) synthesis of graphene on copper surfaces has been of particular interest due to its simplicity and cost effectiveness6,7,8,9,10,11,12,13,14,15. However, the rates of growth for graphene by CVD on copper are less than 0.4 μm s–1, and therefore the synthesis of large, single-crystal graphene domains takes at least a few hours. Here, we show that single-crystal graphene can be grown on copper foils with a growth rate of 60 μm s–1. Our high growth rate is achieved by placing the copper foil above an oxide substrate with a gap of ∼15 μm between them. The oxide substrate provides a continuous supply of oxygen to the surface of the copper catalyst during the CVD growth, which significantly lowers the energy barrier to the decomposition of the carbon feedstock and increases the growth rate. With this approach, we are able to grow single-crystal graphene domains with a lateral size of 0.3 mm in just 5 s.
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References
Novoselov, K. S. et al. Two-dimensional gas of massless Dirac fermions in graphene. Nature 438, 197–200 (2005).
Castro Neto, A. H. et al. The electronic properties of graphene. Rev. Mod. Phys. 81, 109–162 (2009).
Zhang, Y. B. et al. Direct observation of a widely tunable bandgap in bilayer graphene. Nature 459, 820–823 (2009).
Kim, K. et al. A role for graphene in silicon-based semiconductor devices. Nature 479, 338–344 (2011).
Novoselov, K. S. et al. A roadmap for graphene. Nature 490, 192–200 (2012).
Wang, H. et al. Controllable synthesis of submillimeter single-crystal monolayer graphene domains on copper foils by suppressing nucleation. J. Am. Chem. Soc. 134, 3627–3630 (2012).
Yan, Z. et al. Toward the synthesis of wafer-scale single-crystal graphene on copper foils. ACS Nano 6, 9110–9117 (2012).
Gan, L. & Luo, Z. T. Turning off hydrogen to realize seeded growth of subcentimeter single-crystal graphene grains on copper. ACS Nano 7, 9480–9488 (2013).
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).
Zhou, H. L. et al. Chemical vapour deposition growth of large single crystals of monolayer and bilayer graphene. Nature Commun. 4, 2096 (2013).
Mohsin, A. et al. Synthesis of millimeter-size hexagon-shaped graphene single crystals on resolidified copper. ACS Nano 7, 8924–8931 (2013).
Wu, T. R. et al. Triggering the continuous growth of graphene toward millimeter-sized grains. Adv. Funct. Mater. 23, 198–203 (2013).
Wang, C. C. et al. Growth of millimeter-size single crystal graphene on Cu foils by circumfluence chemical vapor deposition. Sci. Rep. 4, 4537 (2014).
Miseikis, V. et al. Rapid CVD growth of millimetre-sized single crystal graphene using a cold-wall reactor. 2D Mater. 2, 014006 (2015).
Nguyen, V. L. et al. Seamless stitching of graphene domains on polished copper (111) foil. Adv. Mater. 27, 1376–1382 (2015).
Babenko, V. et al. Rapid epitaxy-free graphene synthesis on silicidated polycrystalline platinum. Nature Commun. 6, 7536 (2015).
Wu, T. R. et al. Fast growth of inch-sized single-crystalline graphene from a controlled single nucleus on Cu-Ni alloys. Nature Mater. 15, 43–47 (2016).
Zhang, R. F. et al. Growth of half-meter long carbon nanotubes based on schulz-flory distribution. ACS Nano 7, 6156–6161 (2013).
Yuan, Q. H., Hu, H. & Ding, F. Threshold barrier of carbon nanotube growth. Phys. Rev. Lett. 107, 156101 (2011).
Gao, J. et al. Graphene nucleation on transition metal surface: structure transformation and role of the metal step edge. J. Am. Chem. Soc. 133, 5009–5015 (2011).
Hata, K. et al. Water-assisted highly efficient synthesis of impurity-free single-walled carbon nanotubes. Science 229, 1362–1364 (2004).
Gottardi, S. et al. Comparing graphene growth on Cu(111) versus oxidized Cu(111). Nano Lett 15, 917–922 (2015).
Ishizaka, A. & Shiraki, Y. Low-temperature surface cleaning of silicon and its application to silicon Mbe. J. Electrochem. Soc. 133, 666–671 (1986).
Bignardi, L. et al. Microscopic characterisation of suspended graphene grown by chemical vapour deposition. Nanoscale 5, 9057–9061 (2013).
Banszerus, L. et al. Ultrahigh-mobility graphene devices from chemical vapor deposition on reusable copper. Sci. Adv. 1, e1500222 (2015).
Gao, L. B. et al. Face-to-face transfer of wafer-scale graphene films. Nature 505, 190–194 (2014).
Duong, D. L. et al. Probing graphene grain boundaries with optical microscopy. Nature 490, 235–239 (2012).
Zhao, P. et al. Self-limiting chemical vapor deposition growth of monolayer graphene from ethanol. J. Phys. Chem. C 117, 10755–10763 (2013).
Kim, H., Saiz, E., Chhowalla, M. & Mattevi, C. Modeling of the self-limited growth in catalytic chemical vapor deposition of graphene. New J. Phys. 15, 053012 (2013).
Gao, J. F. et al. Graphene nucleation on transition metal surface: structure transformation and role of the metal step edge. J. Am. Chem. Soc. 133, 5009–5015 (2011).
Chen, S. S. et al. Millimeter-size single-crystal graphene by suppressing evaporative loss of Cu during low pressure chemical vapor deposition. Adv. Mater. 25, 2062–2065 (2013).
Deng, B. et al. Roll-to-roll encapsulation of metal nanowires between graphene and plastic substrate for high-performance flexible transparent electrodes. Nano Lett. 15, 4206–4213 (2015).
Acknowledgements
We are grateful to Z. Liu for the helpful comments. We thank F. Wang and T. Cao for their help revising the manuscript. This work was supported by the NSFC (51522201, 11474006, 21525310, 11234001, 11327902, 91433102, 91021007 and 11074005), the National Basic Research Program of China (2016YFA0300903, 2013CBA01603, 2014CB932500, 2012CB921300) and the National Program for Thousand Young Talents of China.
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K.L. and X.X. conceived the project. K.L. supervised the project. X.X., Z.Z. and Z.H. conducted the growth experiment. X.X. performed STM, AES and LEED experiments. X.X., K.L., H.P., F.D., D.Y. and E.W. analysed the experimental data. Z.Z. and H.W. performed the transfer of the graphene. R.Q. and P.G. conducted the TEM experiments. Z.L., L.L., L.Z., H.S. and C.L. performed the electrical measurements. F.D., L.Q. and J.Z. performed theoretical calculations. All of the authors discussed the results and wrote the paper.
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Xu, X., Zhang, Z., Qiu, L. et al. Ultrafast growth of single-crystal graphene assisted by a continuous oxygen supply. Nature Nanotech 11, 930–935 (2016). https://doi.org/10.1038/nnano.2016.132
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DOI: https://doi.org/10.1038/nnano.2016.132
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