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.
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The data that support the findings of this study are available from the corresponding author on reasonable request.
Zhang, Y. et al. Direct observation of a widely tunable bandgap in bilayer graphene. Nature 459, 820–823 (2009).
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).
Li, X. et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009).
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).
Zhou, H. et al. Chemical vapour deposition growth of large single crystals of monolayer and bilayer graphene. Nat. Commun. 4, 2096 (2013).
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).
Zhao, P. et al. Equilibrium chemical vapor deposition growth of Bernal-stacked bilayer graphene. ACS Nano 8, 11631–11638 (2014).
Nie, S. et al. Growth from below: graphene bilayers on Ir (111). ACS Nano 5, 2298–2306 (2011).
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).
Sutter, P., Hybertsen, M., Sadowski, J. & Sutter, E. Electronic structure of few-layer epitaxial graphene on Ru (0001). Nano Lett. 9, 2654–2660 (2009).
López, G. & Mittemeijer, E. The solubility of C in solid Cu. Scr. Mater. 51, 1–5 (2004).
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).
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).
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).
Liu, X. et al. Segregation growth of graphene on Cu–Ni alloy for precise layer control. J. Phys. Chem. C. 115, 11976–11982 (2011).
Takesaki, Y. et al. Highly uniform bilayer graphene on epitaxial Cu-Ni(111) alloy. Chem. Mater. 18, 4583–4592 (2016).
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).
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).
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).
Bakharev, P. V. et al. Chemically induced transformation of chemical vapour deposition grown bilayer graphene into fluorinated single-layer diamond. Nat. Nanotechnol. https://doi.org/10.1038/s41565-019-0582-z (2019).
Huang, M. et al. Highly oriented monolayer graphene grown on a Cu/Ni(111) alloy foil. ACS Nano 12, 6117–6127 (2018).
Jin, S. et al. Colossal grain growth yields single-crystal metal foils by contact-free annealing. Science 362, 1021–1025 (2018).
Lee, S., Lee, K. & Zhong, Z. Wafer scale homogeneous bilayer graphene films by chemical vapor deposition. Nano Lett. 10, 4702–4707 (2010).
Graf, D. et al. Spatially resolved Raman spectroscopy of single-and few-layer graphene. Nano Lett. 7, 238–242 (2007).
Ferrari, A. C. et al. Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 97, 187401 (2006).
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).
Nicholson, M. The solubility of carbon in nickel-copper alloy at 1000 °C. Trans. Metall. Soc. AIME 224, 533–535 (1962).
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).
Nguyen, V. L. et al. Wafer‐scale single‐crystalline AB‐stacked bilayer graphene. Adv. Mater. 28, 8177–8183 (2016).
Suh, Y., Park, S. & Kim, M. High resolution TEM and electron diffraction study of graphene layers. Microsc. Microanal. 15, 1168–1169 (2009).
Meyer, J. C. et al. The structure of suspended graphene sheets. Nature 446, 60–63 (2007).
Li, Q. et al. Growth of adlayer graphene on Cu studied by carbon isotope labeling. Nano Lett. 13, 486–490 (2013).
Wang, Z.-J. et al. Stacking sequence and interlayer coupling in few-layer graphene revealed by in situ imaging. Nat. Commun. 7, 13256 (2016).
Nair, R. R. et al. Fine structure constant defines visual transparency of graphene. Science 320, 1308–1308 (2008).
Bae, S. et al. Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nat. Nanotechnol. 5, 574–578 (2010).
Wang, G. et al. Synthesis of layer‐tunable graphene: a combined kinetic implantation and thermal ejection approach. Adv. Funct. Mater. 25, 3666–3675 (2015).
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).
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).
Hao, Y. et al. Oxygen-activated growth and bandgap tunability of large single-crystal bilayer graphene. Nat. Nanotechnol. 11, 426–431 (2016).
Balandin, A. A. et al. Superior thermal conductivity of single-layer graphene. Nano Lett. 8, 902–907 (2008).
Li, H. et al. Thermal conductivity of twisted bilayer graphene. Nanoscale 6, 13402–13408 (2014).
Limbu, T. B. et al. Grain size-dependent thermal conductivity of polycrystalline twisted bilayer graphene. Carbon 117, 367–375 (2017).
Ghosh, S. et al. Dimensional crossover of thermal transport in few-layer graphene. Nat. Mater. 9, 555–558 (2010).
Wang, B. et al. Camphor‐enabled transfer and mechanical testing of centimeter‐scale ultrathin films. Adv. Mater. 30, 1800888 (2018).
Hosseinian, E. & Pierron, O. N. Quantitative in situ TEM tensile fatigue testing on nanocrystalline metallic ultrathin films. Nanoscale 5, 12532–12541 (2013).
Emery, R. & Povirk, G. Tensile behavior of free-standing gold films. Part II: fine-grain films. Acta Mater. 51, 2079–2087 (2003).
Kim, J.-H. et al. Tensile testing of ultra-thin films on water surface. Nat. Commun. 4, 2520 (2013).
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).
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).
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).
Neek-Amal, M. & Peeters, F. Nanoindentation of a circular sheet of bilayer graphene. Phys. Rev. B. 81, 235421 (2010).
Wang, L. & Zhang, Q. Elastic behavior of bilayer graphene under in-plane loadings. Curr. Appl. Phys. 12, 1173–1177 (2012).
Zhang, P. et al. Fracture toughness of graphene. Nat. Commun. 5, 3782 (2014).
We acknowledge support from the Institute for Basic Science (IBS-R019-D1).
The authors declare no competing interests.
Peer review information Nature Nanotechnology thanks Jeremy Robinson and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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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). https://doi.org/10.1038/s41565-019-0622-8
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