There is a demand for the manufacture of two-dimensional (2D) materials with high-quality single crystals of large size. Usually, epitaxial growth is considered the method of choice1 in preparing single-crystalline thin films, but it requires single-crystal substrates for deposition. Here we present a different approach and report the synthesis of single-crystal-like monolayer graphene films on polycrystalline substrates. The technological realization of the proposed method resembles the Czochralski process and is based on the evolutionary selection2 approach, which is now realized in 2D geometry. The method relies on ‘self-selection’ of the fastest-growing domain orientation, which eventually overwhelms the slower-growing domains and yields a single-crystal continuous 2D film. Here we have used it to synthesize foot-long graphene films at rates up to 2.5 cm h−1 that possess the quality of a single crystal. We anticipate that the proposed approach could be readily adopted for the synthesis of other 2D materials and heterostructures.

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This research was supported by the Laboratory Directed Research and Development Program and the Technology Innovation Program of ORNL managed by UT-Battelle, LLC, for the US Department of Energy (I.V.V. and Y.S.) and by ARPA-e award number DE-AR0000651 (I.V.V. and S.N.S.). STEM/TEM was supported as part of the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center funded by the DOE BES (R.R.U.). A portion of this research was conducted at the Center for Nanophase Materials Sciences, ORNL, by the Scientific User Facilities Division, DOE. The authors thank H. Meyer for XPS data. Work at Rice was supported by the DOE BES (DE-SC0012547) and in part (graphene-ribbon electronics motivation) by the Office of Naval Research (N00014-15-1-2372).

Author information


  1. Oak Ridge National Laboratory, Oak Ridge, TN, USA

    • Ivan V. Vlassiouk
    • , Yijing Stehle
    • , Raymond R. Unocic
    • , Philip D. Rack
    • , Arthur P. Baddorf
    • , Ilia N. Ivanov
    • , Nickolay V. Lavrik
    •  & Frederick List
  2. Department of Materials Science and Engineering, University of Tennessee, Knoxville, TN, USA

    • Pushpa Raj Pudasaini
    •  & Philip D. Rack
  3. Department of Materials Science and Nanoengineering and Department of Chemistry, Rice University, Houston, TX, USA

    • Nitant Gupta
    • , Ksenia V. Bets
    •  & Boris I. Yakobson
  4. Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces, NM, USA

    • Sergei N. Smirnov


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S.N.S. and I.V.V. conceived the idea and designed and conducted graphene growth experiments. Y.S. contributed to sample preparation and analysis. F.L. contributed to designing the substrate pulling mechanism. B.I.Y., N.G. and K.V.B. provided theoretical support. P.R.P and P.D.R fabricated and characterized graphene FETs. R.R.U., A.P.B., N.V.L. and I.N.I. performed material characterizations. I.V.V., S.N.S. and B.I.Y. wrote the manuscript.

Competing interests

The authors declare no competing interests.

Corresponding authors

Correspondence to Ivan V. Vlassiouk or Boris I. Yakobson or Sergei N. Smirnov.

Supplementary information

  1. Supplementary Information

    Supplementary Tables: S1–S2, Supplementary Figures: Scheme S1, Figures S1–S29, Supplementary References 1–12


  1. Supplementary Video 1

    Interface tracking simulation results for k A /k Z > 2/√3

  2. Supplementary Video 2

    Interface tracking simulation results for k A /k Z = 0.95

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