Abstract

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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from $8.99

All prices are NET prices.

References

  1. 1.

    Lee, J. H. et al. Wafer-scale growth of single-crystal monolayer graphene on reusable hydrogen-terminated germanium. Science 344, 286–289 (2014).

  2. 2.

    van der Drift, A. Evolutionary selection, a principle governing growth orientation in vapor-deposited layers. Philips Res. Rep. 22, 267–288 (1967).

  3. 3.

    Duffar, T. Crystal Growth Processes Based on Capillarity: Czochralski, Floating Zone, Shaping and Crucible Techniques (Wiley, Chichester, 2010).

  4. 4.

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

  5. 5.

    Ferrari, A. C. et al. Science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems. Nanoscale 7, 4598–4810 (2014).

  6. 6.

    Huang, P. Y. et al. Grains and grain boundaries in single-layer graphene atomic patchwork quilts. Nature 469, 389–392 (2011).

  7. 7.

    Lee, G.-H. et al. High-strength chemical-vapor-deposited graphene and grain boundaries. Science 340, 1073–1076 (2013).

  8. 8.

    Song, Z., Artyukhov, V. I., Yakobson, B. I. & Xu, Z. Pseudo Hall–Petch strength reduction in polycrystalline graphene. Nano Lett. 13, 1829–1833 (2013).

  9. 9.

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

  10. 10.

    Vlassiouk, I. et al. Electrical and thermal conductivity of low temperature CVD graphene: the effect of disorder. Nanotechnology 22, 275716 (2011).

  11. 11.

    Bagri, A., Kim, S. P., Ruoff, R. S. & Shenoy, V. B. Thermal transport across twin grain boundaries in polycrystalline graphene from nonequilibrium molecular dynamics simulations. Nano Lett. 11, 3917–3921 (2011).

  12. 12.

    Grosse, K. L. et al. Direct observation of resistive heating at graphene wrinkles and grain boundaries. Appl. Phys. Lett. 105, 143109 (2014).

  13. 13.

    Ly, T. H. et al. Misorientation-angle-dependent electrical transport across molybdenum disulfide grain boundaries. Nat. Commun. 7, 10426 (2016).

  14. 14.

    van der Zande, A. M. et al. Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide. Nat. Mater. 12, 554–561 (2013).

  15. 15.

    Xu et al. Ultrafast epitaxial growth of metre-sized single-crystal graphene on industrial Cu foil. Sci. Bull. 62, 1074–1080 (2017).

  16. 16.

    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 (2015).

  17. 17.

    Alstrup, I., Chorkendorff, I. & Ullmann, S. The interaction of CH4 at high temperatures with clean and oxygen precovered Cu(100). Surf. Sci. 264, 95–102 (1992).

  18. 18.

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

  19. 19.

    Bhaviripudi, S., Jia, X., Dresselhaus, M. S. & Kong, J. Role of kinetic factors in chemical vapor deposition synthesis of uniform large area graphene using copper catalyst. Nano Lett. 10, 4128–4133 (2010).

  20. 20.

    Li, X. et al. Graphene films with large domain size by a two-step chemical vapor deposition process. Nano Lett. 10, 4328–4334 (2010).

  21. 21.

    Vlassiouk, I. et al. Role of hydrogen in chemical vapor deposition growth of large single-crystal graphene. ACS Nano 5, 6069–6076 (2011).

  22. 22.

    Wood, J. D., Schumucker, S. W., Lyons, A. S., Pop, E. & Lyding, J. W. Effects of polycrystalline Cu substrate on graphene growth by chemical vapor deposition. Nano Lett. 11, 4547–4554 (2011).

  23. 23.

    Gao, L., Guest, J. R. & Guisinger, N. P. Epitaxial graphene on Cu(111). Nano Lett. 10, 3512–3516 (2010).

  24. 24.

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

  25. 25.

    Chen, S. et al. Oxidation resistance of graphene-coated Cu and Cu/Ni alloy. ACS Nano 5, 1321–1327 (2011).

  26. 26.

    Kim, D. W., Kim, Y. H., Jeong, H. S. & Jung, H.-T. Direct visualization of large-area graphene domains and boundaries by optical birefringency. Nat. Nanotech. 7, 29–34 (2011).

  27. 27.

    Guo, W. et al. Governing rule for dynamic formation of grain boundaries in grown graphene. ACS Nano 9, 5792–5798 (2015).

  28. 28.

    Wang, H. et al. Controllable synthesis of submillimeter single-crystal monolayer graphene domains on copper foils by suppressing nucleation. J. Am. Chem. Soc. 134, 3627–3630 (2012).

  29. 29.

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

  30. 30.

    Artyukhov, V. I., Liu, Y. & Yakobson, B. I. Equilibrium at the edge and atomistic mechanisms of graphene growth. Proc. Natl Acad. Sci. USA 109, 15136–15140 (2012).

  31. 31.

    Ma, T. et al. Edge-controlled growth and kinetics of single-crystal graphene domains by chemical vapor deposition. Proc. Natl Acad. Sci. USA 110, 20386–20391 (2013).

  32. 32.

    Liu, Y., Bhowmick, S. & Yakobson, B. I. BN white graphene with ‘colorful’ edges: the energies and morphology. Nano Lett. 11, 3113–3116 (2011).

  33. 33.

    Artyukhov, V. I., Hu, Z., Zhang, Z. & Yakobson, B. I. Topochemistry of bowtie- and star-shaped metal dichalcogenide nanoisland formation. Nano Lett. 16, 3696–3702 (2016).

  34. 34.

    Vlassiouk, I. et al. Large scale atmospheric pressure chemical vapor deposition of graphene. Carbon 54, 58–67 (2013).

  35. 35.

    Butrymowicz, D. B., Manning, J. R. & Read, M. E. Diffusion in copper and copper alloys. Part IV. Diffusion in systems involving elements of group VIII. J. Phys. Chem. Ref. Data 5, 103–200 (1976).

  36. 36.

    Stehle, Y. et al. Synthesis of hexagonal boron nitride monolayer: control of nucleation and crystal morphology. Chem. Mater. 27, 8041–8047 (2015).

  37. 37.

    Wood, G. E. et al. Van der Waals epitaxy of monolayer hexagonal boron nitride on copper foil: growth, crystallography and electronic band structure. 2D Mater 2, 025003 (2015).

  38. 38.

    Lafkioti, M. et al. Graphene on a hydrophobic substrate: doping reduction and hysteresis suppression under ambient conditions. Nano Lett. 10, 1149–1153 (2010).

  39. 39.

    Vlassiouk, I., Rios, F., Vail, S. A., Gust, D. & Smirnov, S. Electrical conductance of hydrophobic membranes or what happens below the surface. Langmuir 23, 7784–7792 (2007).

  40. 40.

    Schwierz, F. Graphene transistors. Nat. Nanotech 5, 487–496 (2010).

  41. 41.

    Pudasaini, P. R. et al. Ionic liquid activation of amorphous metal-oxide semiconductors for flexible transparent electronic devices. Adv. Funct. Mater. 26, 2820–2825 (2016).

Download references

Acknowledgements

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

Affiliations

  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

Authors

  1. Search for Ivan V. Vlassiouk in:

  2. Search for Yijing Stehle in:

  3. Search for Pushpa Raj Pudasaini in:

  4. Search for Raymond R. Unocic in:

  5. Search for Philip D. Rack in:

  6. Search for Arthur P. Baddorf in:

  7. Search for Ilia N. Ivanov in:

  8. Search for Nickolay V. Lavrik in:

  9. Search for Frederick List in:

  10. Search for Nitant Gupta in:

  11. Search for Ksenia V. Bets in:

  12. Search for Boris I. Yakobson in:

  13. Search for Sergei N. Smirnov in:

Contributions

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

Videos

  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

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/s41563-018-0019-3