Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Large-area single-crystal AB-bilayer and ABA-trilayer graphene grown on a Cu/Ni(111) foil


High-quality AB-stacked bilayer or multilayer graphene larger than a centimetre has not been reported. Here, we report the fabrication and use of single-crystal Cu/Ni(111) alloy foils with controllable concentrations of Ni for the growth of large-area, high-quality AB-stacked bilayer and ABA-stacked trilayer graphene films by chemical vapour deposition. The stacking order, coverage and uniformity of the graphene films were evaluated by Raman spectroscopy and transmission electron microscopy including selected area electron diffraction and atomic resolution imaging. Electrical transport (carrier mobility and band-gap tunability) and thermal conductivity (the bilayer graphene has a thermal conductivity value of about 2,300 W m−1 K−1) measurements indicated the superior quality of the films. The tensile loading response of centimetre-scale bilayer graphene films supported by a 260-nm thick polycarbonate film was measured and the average values of the Young’s modulus (478 GPa) and fracture strength (3.31 GPa) were obtained.

This is a preview of subscription content

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Fig. 1: Preparation and characterization of Cu/Ni(111) foils.
Fig. 2: Raman measurements of the bilayer and trilayer graphene.
Fig. 3: TEM and LEED characterization of a bilayer graphene film.
Fig. 4: Electrical transport measurements, thermal conductivity measurements and tensile tests of AB-stacked bilayer graphene film.

Data availability

The data that support the findings of this study are available from the corresponding author on reasonable request.


  1. 1.

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

    CAS  Google Scholar 

  2. 2.

    Oostinga, J. B., Heersche, H. B., Liu, X., Morpurgo, A. F. & Vandersypen, L. M. Gate-induced insulating state in bilayer graphene devices. Nat. Mater. 7, 151–157 (2008).

    CAS  Google Scholar 

  3. 3.

    Li, X. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009).

    CAS  Google Scholar 

  4. 4.

    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).

    CAS  Google Scholar 

  5. 5.

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

    Google Scholar 

  6. 6.

    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).

    CAS  Google Scholar 

  7. 7.

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

    CAS  Google Scholar 

  8. 8.

    Nie, S. et al. Growth from below: graphene bilayers on Ir (111). ACS Nano 5, 2298–2306 (2011).

    CAS  Google Scholar 

  9. 9.

    Sutter, P., Ciobanu, C. V. & Sutter, E. Real‐time microscopy of graphene growth on epitaxial metal films: role of template thickness and strain. Small 8, 2250–2257 (2012).

    CAS  Google Scholar 

  10. 10.

    Sutter, P., Hybertsen, M., Sadowski, J. & Sutter, E. Electronic structure of few-layer epitaxial graphene on Ru (0001). Nano Lett. 9, 2654–2660 (2009).

    CAS  Google Scholar 

  11. 11.

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

    Google Scholar 

  12. 12.

    Sung, C.-M. & Tai, M.-F. Reactivities of transition metals with carbon: implications to the mechanism of diamond synthesis under high pressure. Int. J. Refract. Met. Hard Mater. 15, 237–256 (1997).

    CAS  Google Scholar 

  13. 13.

    Chen, S. et al. Synthesis and characterization of large-area graphene and graphite films on commercial Cu–Ni alloy foils. Nano Lett. 11, 3519–3525 (2011).

    CAS  Google Scholar 

  14. 14.

    Wu, Y. et al. Growth mechanism and controlled synthesis of AB-stacked bilayer graphene on Cu–Ni alloy foils. ACS Nano 6, 7731–7738 (2012).

    CAS  Google Scholar 

  15. 15.

    Liu, X. et al. Segregation growth of graphene on Cu–Ni alloy for precise layer control. J. Phys. Chem. C. 115, 11976–11982 (2011).

    CAS  Google Scholar 

  16. 16.

    Takesaki, Y. et al. Highly uniform bilayer graphene on epitaxial Cu-Ni(111) alloy. Chem. Mater. 18, 4583–4592 (2016).

    Google Scholar 

  17. 17.

    Chernozatonskii, L. A., Sorokin, P. B., Kvashnin, A. Ge & Kvashnin, D. Ge Diamond-like C2H nanolayer, diamane: simulation of the structure and properties. JETP Lett. 90, 134–138 (2009).

    CAS  Google Scholar 

  18. 18.

    Odkhuu, D., Shin, D., Ruoff, R. S. & Park, N. Conversion of multilayer graphene into continuous ultrathin sp 3-bonded carbon films on metal surfaces. Sci. Rep. 3, 3276 (2013).

    Google Scholar 

  19. 19.

    Kvashnin, A. G., Chernozatonskii, L. A., Yakobson, B. I. & Sorokin, P. B. Phase diagram of quasi-two-dimensional carbon, from graphene to diamond. Nano Lett. 14, 676–681 (2014).

    CAS  Google Scholar 

  20. 20.

    Bakharev, P. V. et al. Chemically induced transformation of chemical vapour deposition grown bilayer graphene into fluorinated single-layer diamond. Nat. Nanotechnol. (2019).

  21. 21.

    Huang, M. et al. Highly oriented monolayer graphene grown on a Cu/Ni(111) alloy foil. ACS Nano 12, 6117–6127 (2018).

    CAS  Google Scholar 

  22. 22.

    Jin, S. et al. Colossal grain growth yields single-crystal metal foils by contact-free annealing. Science 362, 1021–1025 (2018).

    CAS  Google Scholar 

  23. 23.

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

    CAS  Google Scholar 

  24. 24.

    Graf, D. et al. Spatially resolved Raman spectroscopy of single-and few-layer graphene. Nano Lett. 7, 238–242 (2007).

    CAS  Google Scholar 

  25. 25.

    Ferrari, A. C. et al. Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 97, 187401 (2006).

    CAS  Google Scholar 

  26. 26.

    Gupta, A., Chen, G., Joshi, P., Tadigadapa, S. & Eklund, P. Raman scattering from high-frequency phonons in supported n-graphene layer films. Nano Lett. 6, 2667–2673 (2006).

    CAS  Google Scholar 

  27. 27.

    Nicholson, M. The solubility of carbon in nickel-copper alloy at 1000 °C. Trans. Metall. Soc. AIME 224, 533–535 (1962).

    CAS  Google Scholar 

  28. 28.

    Wu, T. et al. Fast growth of inch-sized single-crystalline graphene from a controlled single nucleus on Cu-Ni alloys. Nat. Mater. 15, 43–47 (2016).

    CAS  Google Scholar 

  29. 29.

    Nguyen, V. L. et al. Wafer‐scale single‐crystalline AB‐stacked bilayer graphene. Adv. Mater. 28, 8177–8183 (2016).

    CAS  Google Scholar 

  30. 30.

    Suh, Y., Park, S. & Kim, M. High resolution TEM and electron diffraction study of graphene layers. Microsc. Microanal. 15, 1168–1169 (2009).

    Google Scholar 

  31. 31.

    Meyer, J. C. et al. The structure of suspended graphene sheets. Nature 446, 60–63 (2007).

    CAS  Google Scholar 

  32. 32.

    Li, Q. et al. Growth of adlayer graphene on Cu studied by carbon isotope labeling. Nano Lett. 13, 486–490 (2013).

    CAS  Google Scholar 

  33. 33.

    Wang, Z.-J. et al. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging. Nat. Commun. 7, 13256 (2016).

    CAS  Google Scholar 

  34. 34.

    Nair, R. R. et al. Fine structure constant defines visual transparency of graphene. Science 320, 1308–1308 (2008).

    CAS  Google Scholar 

  35. 35.

    Bae, S. et al. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nat. Nanotechnol. 5, 574–578 (2010).

    CAS  Google Scholar 

  36. 36.

    Wang, G. et al. Synthesis of layer‐tunable graphene: a combined kinetic implantation and thermal ejection approach. Adv. Funct. Mater. 25, 3666–3675 (2015).

    CAS  Google Scholar 

  37. 37.

    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 (2013).

    Google Scholar 

  38. 38.

    Xia, F., Farmer, D. B., Lin, Y.-m & Avouris, P. Graphene field-effect transistors with high on/off current ratio and large transport band gap at room temperature. Nano Lett. 10, 715–718 (2010).

    CAS  Google Scholar 

  39. 39.

    Hao, Y. et al. Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene. Nat. Nanotechnol. 11, 426–431 (2016).

    CAS  Google Scholar 

  40. 40.

    Balandin, A. A. et al. Superior thermal conductivity of single-layer graphene. Nano Lett. 8, 902–907 (2008).

    CAS  Google Scholar 

  41. 41.

    Li, H. et al. Thermal conductivity of twisted bilayer graphene. Nanoscale 6, 13402–13408 (2014).

    CAS  Google Scholar 

  42. 42.

    Limbu, T. B. et al. Grain size-dependent thermal conductivity of polycrystalline twisted bilayer graphene. Carbon 117, 367–375 (2017).

    CAS  Google Scholar 

  43. 43.

    Ghosh, S. et al. Dimensional crossover of thermal transport in few-layer graphene. Nat. Mater. 9, 555–558 (2010).

    CAS  Google Scholar 

  44. 44.

    Wang, B. et al. Camphor‐enabled transfer and mechanical testing of centimeter‐scale ultrathin films. Adv. Mater. 30, 1800888 (2018).

    Google Scholar 

  45. 45.

    Hosseinian, E. & Pierron, O. N. Quantitative in situ TEM tensile fatigue testing on nanocrystalline metallic ultrathin films. Nanoscale 5, 12532–12541 (2013).

    CAS  Google Scholar 

  46. 46.

    Emery, R. & Povirk, G. Tensile behavior of free-standing gold films. Part II: fine-grain films. Acta Mater. 51, 2079–2087 (2003).

    CAS  Google Scholar 

  47. 47.

    Kim, J.-H. et al. Tensile testing of ultra-thin films on water surface. Nat. Commun. 4, 2520 (2013).

    Google Scholar 

  48. 48.

    Chen, X., Kirsch, B. L., Senter, R., Tolbert, S. H. & Gupta, V. Tensile testing of thin films supported on compliant substrates. Mech. Mater. 41, 839–848 (2009).

    Google Scholar 

  49. 49.

    Macionczyk, F., Brückner, W. & Reiss, G. Stress-strain curves by tensile testing of thin metallic films on thin polyimide foils: Al, AlCu, CuNi(Mn). Mater. Res. Soc. Symp. Proc. 505, 235–240 (1997).

    Google Scholar 

  50. 50.

    Lee, C., Wei, X., Kysar, J. W. & Hone, J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321, 385–388 (2008).

    CAS  Google Scholar 

  51. 51.

    Neek-Amal, M. & Peeters, F. Nanoindentation of a circular sheet of bilayer graphene. Phys. Rev. B. 81, 235421 (2010).

    Google Scholar 

  52. 52.

    Wang, L. & Zhang, Q. Elastic behavior of bilayer graphene under in-plane loadings. Curr. Appl. Phys. 12, 1173–1177 (2012).

    Google Scholar 

  53. 53.

    Zhang, P. et al. Fracture toughness of graphene. Nat. Commun. 5, 3782 (2014).

    CAS  Google Scholar 

Download references


We acknowledge support from the Institute for Basic Science (IBS-R019-D1).

Author information




R.S.R. proposed and supervised the research project. M.H. prepared the single-crystalline alloy foils, performed the graphene growth, conducted characterizations and data analyses. M.H. wrote the manuscript. M.H., P.V.B. and R.S.R. revised the manuscript. M.B. participated in graphene growth and Raman characterization. Z.J.-W. and M.-G.W. performed the in situ observation of the hydrogen etching of graphene. S.J. and Y.K. prepared the single-crystal copper foils. H.-J.P. and Z.L. carried out the HRTEM analysis. Z.Y., Y.L., D.Q. and W.-J.Y. made graphene devices and conducted transport measurements. B.W. and M.H. performed the tensile tests. P.V.B., X.C. and S.W.L. provided critical insights for the analysis and discussion. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Rodney S. Ruoff.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Nanotechnology thanks Jeremy Robinson and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary methods and notes, Figs. 1–26, Tables 1–5 and refs. 1–40.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Huang, M., Bakharev, P.V., Wang, ZJ. et al. Large-area single-crystal AB-bilayer and ABA-trilayer graphene grown on a Cu/Ni(111) foil. Nat. Nanotechnol. 15, 289–295 (2020).

Download citation

Further reading


Quick links

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research