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Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene

Nature Nanotechnology volume 11, pages 426–431 (2016)Cite this article

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Abstract

Bernal (AB)-stacked bilayer graphene (BLG) is a semiconductor whose bandgap can be tuned by a transverse electric field, making it a unique material for a number of electronic and photonic devices1,2,3. A scalable approach to synthesize high-quality BLG is therefore critical, which requires minimal crystalline defects in both graphene layers4,5 and maximal area of Bernal stacking, which is necessary for bandgap tunability6. Here we demonstrate that in an oxygen-activated chemical vapour deposition (CVD) process, half-millimetre size, Bernal-stacked BLG single crystals can be synthesized on Cu. Besides the traditional ‘surface-limited’ growth mechanism for SLG (1st layer), we discovered new microscopic steps governing the growth of the 2nd graphene layer below the 1st layer as the diffusion of carbon atoms through the Cu bulk after complete dehydrogenation of hydrocarbon molecules on the Cu surface, which does not occur in the absence of oxygen. Moreover, we found that the efficient diffusion of the carbon atoms present at the interface between Cu and the 1st graphene layer further facilitates growth of large domains of the 2nd layer. The CVD BLG has superior electrical quality, with a device on/off ratio greater than 104, and a tunable bandgap up to ∼100 meV at a displacement field of 0.9 V nm−1.

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Figure 1: Growth of large BLG domains on the exterior surface of an OR-Cu pocket.
Figure 2: BLG domain size and stacking order control.
Figure 3: O-activated growth mechanism and DFT calculations.
Figure 4: Electrical transport in Bernal-stacked BLG.

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Change history

  • 26 February 2016

    In the version of this Letter originally published online, in Fig. 2d, the values on the y axis were incorrect. This error has been corrected in all versions of the Letter.

References

  1. Geim, A. K. & Novoselov, K. S. The rise of graphene. Nature Mater. 6, 183–191 (2007).

    Article  CAS  Google Scholar 

  2. Zhang, Y. et al. Direct observation of a widely tunable bandgap in bilayer graphene. Nature 459, 820–823 (2009).

    Article  CAS  Google Scholar 

  3. Yan, J. et al. Dual-gated bilayer graphene hot-electron bolometer. Nature Nanotechnol. 7, 472–478 (2012).

    Article  CAS  Google Scholar 

  4. Yu, Q. et al. Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition. Nature Mater. 10, 443–449 (2011).

    Article  CAS  Google Scholar 

  5. Yazyev, O. V. & Louie, S. G. Electronic transport in polycrystalline graphene. Nature Mater. 9, 806–809 (2010).

    Article  CAS  Google Scholar 

  6. Kim, K. et al. Raman spectroscopy study of rotated double-layer graphene: misorientation angle dependence of electronic structure. Phys. Rev. Lett. 108, 246103 (2012).

    Article  Google Scholar 

  7. Batzill, M. The surface science of graphene: metal interfaces, CVD synthesis, nanoribbons, chemical modifications, and defects. Surf. Sci. Rep. 67, 83–115 (2012).

    Article  CAS  Google Scholar 

  8. Kim, K. S. et al. Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 457, 706–710 (2010).

    Article  Google Scholar 

  9. Weatherup, R. S. et al. Interdependency of subsurface carbon distribution and graphene-catalyst interactions. J. Am. Chem. Soc. 136, 13698–13708 (2014).

    Article  CAS  Google Scholar 

  10. Mattevi, C., Kim, H. & Chhowalla, M. A review of chemical vapour deposition of graphene on copper. J. Mater. Chem. 21, 3324–3334 (2011).

    Article  CAS  Google Scholar 

  11. Lee, S., Lee, K. & Zhong, Z. Wafer scale homogeneous bilayer graphene films by chemical vapor deposition. Nano Lett. 10, 4702–4707 (2010).

    Article  CAS  Google Scholar 

  12. Liu, W. et al. Controllable and rapid synthesis of high-quality and large-area Bernal stacked bilayer graphene using chemical vapor deposition. Chem. Mater. 26, 907–915 (2014).

    Article  Google Scholar 

  13. Zhou, H. et al. Chemical vapor deposition growth of large single crystals of monolayer and bilayer graphene. Nature Commun. 4, 2096 (2013).

    Article  Google Scholar 

  14. Yan, K., Peng, H., Zhou, Y., Li, H. & Liu, Z. Formation of bilayer Bernal graphene: layer-by-layer epitaxy via chemical vapor deposition. Nano Lett. 11, 1106–1110 (2011).

    Article  CAS  Google Scholar 

  15. Fang, W. et al. Asymmetric growth of bilayer graphene on copper enclosures using low pressure chemical vapor deposition. ACS Nano 8, 6491–6499 (2014).

    Article  CAS  Google Scholar 

  16. Sun, Z. et al. Large-area Bernal-stacked bi-, tri-, and tetralayer graphene. ACS Nano 6, 9790–9796 (2012).

    Article  CAS  Google Scholar 

  17. Liu, L. et al. High-yield chemical vapor deposition growth of high-quality large-area AB-stacked bilayer graphene. ACS Nano 6, 8241–8249 (2012).

    Article  CAS  Google Scholar 

  18. Zhao, P. et al. Equilibrium chemical vapor deposition growth of Bernal-stacked bilayer graphene. ACS Nano, 8, 11631–11638 (2014).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  20. Hao, Y. et al. Probing layer number and stacking order of few-layer graphene by Raman spectroscopy. Small 6, 195–200 (2010).

    Article  CAS  Google Scholar 

  21. Vlassiouk, I. et al. Graphene nucleation density on copper: fundamental role of background pressure. J. Phys. Chem. C 117, 18919–18926 (2013).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  24. Kim, H. et al. Activation energy paths for graphene nucleation and growth on Cu. ACS Nano, 6, 3614–3623 (2012).

    Article  CAS  Google Scholar 

  25. López, G. A. & Mittemeijer, E. J. The solubility of C in solid Cu. Scr. Mater. 51, 1–5 (2004).

    Article  Google Scholar 

  26. Kidambi, P. R. et al. Observing graphene grow: catalyst-graphene interactions during scalable graphene growth on polycrystalline copper. Nano Lett. 13, 4769–4778 (2013).

    Article  CAS  Google Scholar 

  27. Riikonen, S., Krasheninnikov, A. V., Halonen, L. & Nieminen, R. M. The role of stable and mobile carbon adspecies in copper-promoted graphene growth. J. Phys. Chem. C 116, 5802–5809 (2012).

    Article  CAS  Google Scholar 

  28. Zhang, W., Wu, P., Li, Z. & Yang, J. First-principles thermodynamics of graphene growth on Cu surfaces. J. Phys. Chem. C, 115, 17782–17787 (2011).

    Article  CAS  Google Scholar 

  29. Taychatanapat, T. & Jarillo-Herrero, P. Electronic transport in dual-gated bilayer graphene at large displacement fields. Phys. Rev. Lett. 105, 166601 (2010).

    Article  Google Scholar 

  30. Fang, W. et al. Rapid identification of stacking orientation in isotopically labeled chemical-vapor grown bilayer graphene by Raman spectroscopy. Nano Lett. 13, 1541–1548 (2013).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank J. B. Goodenough, Z. Zhang, N. C. Bartelt, F. Wang, D. Su, E. Stach, G. A. López, E. J. Mittemeijer, L. Ju, and J. Yin for valuable discussions and/or technical assistance. We thank K. Watanabe and T. Taniguchi for providing h-BN crystals. Work at Columbia University was supported by Office of Naval Research (ONR) -N000141310662 and the Nanoelectronics Research Initiative (NRI) through the Institute for Nanoelectronics Discovery and Exploration (INDEX). Work at Austin was supported by the NRI through the South West Academy of Nanoelectronics (SWAN). Work at Sandia was supported by the Office of Basic Energy Sciences, Division of Materials and Engineering Sciences, US Department of Energy (DOE) under Contract No. DE-AC04-94AL85000. Work at Rice University was supported by the ONR and NSF's Chemical, Bioengineering, Environmental, and Transport Systems Division. Work at NREL was supported by DOE under Contract No. DE-AC36-08GO28308, and used the NREL Peregrine Supercomputer and NERSC clusters (supported by DOE DE-AC02-05CH11231). Work at Hong Kong was supported by Hong Kong University of Science and Technology under award RPC11EG39. Work at Harvard University was supported by the Air Force Office of Scientific Research under contract no. FA9550-13-1-0211. Work at Sungkyunkwan University was supported by the convergence technology development program for bionic arm (no. 2014M3C1B2048175) and the Basic Science Research Program (NRF-2014R1A1A1004818) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning. H. C. was supported by NSF DMR-1122603 and by ONR-N00014-14-1-0330. C. T. was supported by a National Defense Science and Engineering Graduate (NDSEG) Fellowship - FA9550-11-C-0028. R.S.R. was supported by IBS-R019-D1.

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Authors and Affiliations

  1. Department of Mechanical Engineering, Columbia University, New York, 10027, New York, USA

    Yufeng Hao, Lei Wang, Cheng Tan, Junfeng Xiao & James Hone

  2. Department of Materials Science and NanoEngineering, Rice University, Houston, 77005, Texas, USA

    Yuanyue Liu & Boris I. Yakobson

  3. National Renewable Energy Laboratory, Golden, 80401, Colorado, USA

    Yuanyue Liu

  4. Department of Physics, The University of Texas at Austin, Austin, 78712, Texas, USA

    Hua Chen

  5. Department of Mechanical Engineering and the Materials Science and Engineering Program, The University of Texas at Austin, Austin, 78712, Texas, USA

    Xiaohan Wang & Rodney S. Ruoff

  6. Sandia National Laboratories, Livermore, 94550, California, USA

    Shu Nie & Kevin F. McCarty

  7. School of Mechanical Engineering, Sungkyunkwan University, Suwon, 440-746, Korea

    Ji Won Suk

  8. Department of Materials Science and Engineering, University of Central Florida, Orlando, 32816, Florida, USA

    Tengfei Jiang

  9. Department of Mechanical and Aerospace Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, 999077, China

    Tengfei Liang & Wenjing Ye

  10. Department of Physics, Columbia University, New York, 10027, New York, USA

    Cory R. Dean

  11. Department of Physics, Harvard University, Cambridge, 02138, Massachusetts, USA

    Philip Kim

  12. Texas Instruments, Dallas, 75243, Texas, USA

    Luigi Colombo

  13. Center for Multidimensional Carbon Materials, Institute for Basic Science, Ulsan National Institute of Science and Technology, Ulsan, 689-798, Korea

    Rodney S. Ruoff

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  1. Yufeng Hao
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Contributions

Y.F.H., R.S.R., and L.C. conceived the experiments. Y.F.H. designed and performed all the growth experiments and graphene transfer. R.S.R., J.H. and L.C. supervised the project. Y.F.H., H.C., L.C., J.H., K.F.M., X.W., C.T., J.W.S., and R.S.R. analysed experimental results and the data. L.W., Y.F.H., J.H., P.K., and C.R.D. performed electrical measurements. Y.L. and B.I.Y. performed DFT calculations. K.F.M. and S.N. performed LEEM and LEED experiments. T. J. performed the focus ion beam cutting. T.L., J.X., and W.Y. performed the gas exchange rate calculations. Y.F.H., H.C., J.H., R.S.R., and L.C. wrote the manuscript. All co-authors revised and commented on the manuscript.

Corresponding authors

Correspondence to James Hone, Luigi Colombo or Rodney S. Ruoff.

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Hao, Y., Wang, L., Liu, Y. et al. Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene. Nature Nanotech 11, 426–431 (2016). https://doi.org/10.1038/nnano.2015.322

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