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Wafer-scale single-crystal monolayer graphene grown on sapphire substrate

Nature Materials volume 21, pages 740–747 (2022)Cite this article

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Abstract

The growth of inch-scale high-quality graphene on insulating substrates is desirable for electronic and optoelectronic applications, but remains challenging due to the lack of metal catalysis. Here we demonstrate the wafer-scale synthesis of adlayer-free ultra-flat single-crystal monolayer graphene on sapphire substrates. We converted polycrystalline Cu foil placed on Al2O3(0001) into single-crystal Cu(111) film via annealing, and then achieved epitaxial growth of graphene at the interface between Cu(111) and Al2O3(0001) by multi-cycle plasma etching-assisted–chemical vapour deposition. Immersion in liquid nitrogen followed by rapid heating causes the Cu(111) film to bulge and peel off easily, while the graphene film remains on the sapphire substrate without degradation. Field-effect transistors fabricated on as-grown graphene exhibited good electronic transport properties with high carrier mobilities. This work breaks a bottleneck of synthesizing wafer-scale single-crystal monolayer graphene on insulating substrates and could contribute to next-generation graphene-based nanodevices.

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Fig. 1: Wafer-scale single-crystal Cu(111) film formed on Al2O3(0001).
Fig. 2: Growth of single-crystal graphene at the Cu(111)–Al2O3(0001) interface.
Fig. 3: Synthesis of wafer-scale single-crystal graphene film on Al2O3(0001).
Fig. 4: DFT simulations and carbon diffusion model.
Fig. 5: Electronic transport properties of GFETs.

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Data availability

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

References

  1. Geim, A. K. Graphene: status and prospects. Science 324, 1530–1534 (2009).

    Article  CAS  Google Scholar 

  2. Novoselov, K. S. et al. A roadmap for graphene. Nature 490, 192–200 (2012).

    Article  CAS  Google Scholar 

  3. Akinwande, D. et al. Graphene and two-dimensional materials for silicon technology. Nature 573, 507–518 (2019).

    Article  CAS  Google Scholar 

  4. Cao, Y. et al. Correlated insulator behaviour at half-filling in magic-angle graphene superlattices. Nature 556, 80–84 (2018).

    Article  CAS  Google Scholar 

  5. Cao, Y. et al. Unconventional superconductivity in magic-angle graphene superlattices. Nature 556, 43–50 (2018).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  7. Kim, Y. et al. Synthesis of high quality graphene on capped (111) Cu thin films obtained by high temperature secondary grain growth on c-plane sapphire substrates. 2D Mater. 5, 035008 (2018).

    Article  Google Scholar 

  8. Li, J. et al. Fractal‐theory‐based control of the shape and quality of CVD‐grown 2D materials. Adv. Mater. 31, 1902431 (2019).

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  10. 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).

    Article  CAS  Google Scholar 

  11. Luo, D. et al. Adlayer-free large-area single crystal graphene grown on a Cu(111) foil. Adv. Mater. 31, 1903615 (2019).

  12. Vlassiouk, I. V. et al. Evolutionary selection growth of two-dimensional materials on polycrystalline substrates. Nat. Mater. 17, 318–322 (2018).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  14. Wang, M. et al. Single-crystal, large-area, fold-free monolayer graphene. Nature 596, 519–524 (2021).

    Article  CAS  Google Scholar 

  15. Chen, J. et al. Oxygen-aided synthesis of polycrystalline graphene on silicon dioxide substrates. J. Am. Chem. Soc. 133, 17548–17551 (2011).

    Article  CAS  Google Scholar 

  16. Chen, X. D. et al. Fast growth and broad applications of 25-inch uniform graphene glass. Adv. Mater. 29, 1603428 (2017).

    Article  Google Scholar 

  17. Pan, G. H. et al. Transfer-free growth of graphene on SiO2 insulator substrate from sputtered carbon and nickel films. Carbon 65, 349–358 (2013).

    Article  CAS  Google Scholar 

  18. Su, C. Y. et al. Direct formation of wafer scale graphene thin layers on insulating substrates by chemical vapor deposition. Nano Lett. 11, 3612–3616 (2011).

    Article  CAS  Google Scholar 

  19. Kim, H. et al. Copper-vapor-assisted chemical vapor deposition for high-quality and metal-free single-layer graphene on amorphous SiO2 substrate. ACS Nano 7, 6575–6582 (2013).

    Article  CAS  Google Scholar 

  20. Mishra, N. et al. Wafer‐scale synthesis of graphene on sapphire: toward fab‐compatible graphene. Small 15, 1904906 (2019).

    Article  CAS  Google Scholar 

  21. Li, B. W. et al. Orientation-dependent strain relaxation and chemical functionalization of graphene on a Cu(111) foil. Adv. Mater. 30, 1706504 (2018).

    Article  Google Scholar 

  22. Chen, T. A. et al. Wafer-scale single-crystal hexagonal boron nitride monolayers on Cu(111). Nature 579, 219–223 (2020).

    Article  CAS  Google Scholar 

  23. Constable, F. H. The cause of the colours shown during the oxidation of metallic copper. Proc. R. Soc. Lond., Ser. A 115, 570–588 (1927).

    Article  CAS  Google Scholar 

  24. 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).

    Article  CAS  Google Scholar 

  25. Zhao, Z. et al. Study on the diffusion mechanism of graphene grown on copper pockets. Small 11, 1418–1422 (2015).

    Article  CAS  Google Scholar 

  26. Fuks, D. et al. Carbon in copper and silver: diffusion and mechanical properties. J. Mol. Struct. Theochem 539, 199–214 (2001).

    Article  CAS  Google Scholar 

  27. Morgan, W. L., Whitten, B. L. & Bardsley, J. N. Plasma shielding effects on ionic recombination. Phys. Rev. Lett. 45, 2021–2024 (1980).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  29. Sojka, F., Meissner, M., Zwick, C., Forker, R. & Fritz, T. Determination and correction of distortions and systematic errors in low-energy electron diffraction. Rev. Sci. Instrum. 84, 015111 (2013).

    Article  Google Scholar 

  30. Sojka, F. et al. To tilt or not to tilt: correction of the distortion caused by inclined sample surfaces in low-energy electron diffraction. Ultramicroscopy 133, 35–40 (2013).

    Article  CAS  Google Scholar 

  31. Schaal, M. et al. Hybridization vs decoupling: influence of an h-BN interlayer on the physical properties of a lander-type molecule on Ni(111). Beilstein J. Nanotechnol. 11, 1168–1177 (2020).

    Article  CAS  Google Scholar 

  32. Berner, A. et al. Microstructure of Cu-C interface in Cu-based metal matrix composite. Sens. Actuator A. Phys. 74, 86–90 (1999).

    Article  CAS  Google Scholar 

  33. Kurganov, A. & Tadmor, E. New high-resolution central schemes for nonlinear conservation laws and convection-diffusion equations. J. Comput. Phys. 160, 241–282 (2000).

    Article  CAS  Google Scholar 

  34. Paradisi, P., Cesari, R., Mainardi, F. & Tampieri, F. The fractional Fick’s law for non-local transport processes. Phys. A Stat. Mech. Appl. 293, 130–142 (2001).

    Article  CAS  Google Scholar 

  35. Kim, S. et al. Realization of a high mobility dual-gated graphene field-effect transistor with Al2O3 dielectric. Appl. Phys. Lett. 94, 062107 (2009).

    Article  Google Scholar 

  36. Chen, X., Wu, B. & Liu, Y. Direct preparation of high quality graphene on dielectric substrates. Chem. Soc. Rev. 45, 2057–2074 (2016).

    Article  CAS  Google Scholar 

  37. Fanton, M. A. et al. Characterization of graphene films and transistors grown on sapphire by metal-free chemical vapor deposition. ACS Nano 5, 8062–8069 (2011).

    Article  CAS  Google Scholar 

  38. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple [Phys. Rev. Lett. 77: 3865 (1996)]. Phys. Rev. Lett. 78, 1396 (1997).

  39. Kresse, G., & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B. 54, 11169 (1996).

    Article  CAS  Google Scholar 

  40. Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).

    Article  Google Scholar 

Download references

Acknowledgements

We thank A. Chen for providing suggestions on device fabrication. We thank F. Laquai and Y. Gao for help with UV–vis spectrum measurements, and N. Wehbe for help with D-SIMS measurements. We thank D. Luo and M. Wang for comments. X.Z. acknowledges the support from KAUST, under award numbers OSR-2018-CRG7-3717 and OSR-2016-CRG5-2996, and R.S.R. acknowledges the support from IBS-R-019-D1.

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Authors and Affiliations

  1. Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia

    Junzhu Li, Mingguang Chen, Abdus Samad, Haocong Dong, Avijeet Ray, Udo Schwingenschlögl, Cailing Chen, Yu Han, Bo Tian & Xixiang Zhang

  2. Eleven-Dimensional Nanomaterial Research Institute, Xiamen, China

    Junzhu Li, Haocong Dong, Xiaochuan Jiang & Bo Tian

  3. School of Materials and Energy, Electron Microscopy Centre of Lanzhou University and Key Laboratory of Magnetism and Magnetic Materials of Ministry of Education, Lanzhou University, Lanzhou, China

    Junwei Zhang

  4. Department of Physics, Xiamen University, Xiamen, China

    Xiaochuan Jiang

  5. Institute of Solid State Physics (IFK), Friedrich Schiller University Jena, Jena, Germany

    Jari Domke & Torsten Fritz

  6. Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), Ulsan, Republic of Korea

    Rodney S. Ruoff

  7. Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Rodney S. Ruoff

  8. Department of Materials Science and Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Rodney S. Ruoff

  9. School of Chemical Engineering and Energy Science, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Rodney S. Ruoff

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  1. Junzhu Li
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Contributions

J.L. and B.T. conceived the experiments. X.Z. supervised the project. J.L. and H.D. performed the annealing of the Cu foils and their characterizations. J.L., M.C., X.J. and H.D. performed the graphene growth and transfer experiments. J.L., H.D. and B.T. performed the Raman, SEM, AFM and XRD characterizations. J.Z. performed the TEM characterization for 2D materials. C.C., Y.H. and B.T. performed the focused ion beam analysis, HR–TEM, HAADF–STEM and energy dispersive spectroscopy characterizations for the cross-section. J.D. and T.F. performed the LEED and STM characterizations. A.S., A.R. and U.S. performed the DFT simulations. B.T. performed the fabrication of GFETs and electronic transport property measurements. R.S.R. provided various insights and particularly about the role of nitrogen in causing deformation of the Cu(111) film. U.S., T.F., R.S.R. and X.Z. provided comments on the paper. R.S.R. did a major revision of the paper and Supplementary Information document. J.L. and B.T. wrote the paper. All coauthors revised and commented on the paper.

Corresponding authors

Correspondence to Bo Tian or Xixiang Zhang.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–35, Discussion and Tables 1–4.

Supplementary Video 1

Schematic animation of direct growth of single-crystalline graphene on insulating substrates by MPE–CVD.

Supplementary Video 2

Schematic animation of the liquid nitrogen-assisted separation methods.

Supplementary Video 3

A video recording of the sample immersion in liquid nitrogen followed by its rapid heating to 500 °C.

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Li, J., Chen, M., Samad, A. et al. Wafer-scale single-crystal monolayer graphene grown on sapphire substrate. Nat. Mater. 21, 740–747 (2022). https://doi.org/10.1038/s41563-021-01174-1

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