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Evolutionary selection growth of two-dimensional materials on polycrystalline substrates

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.

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Fig. 1: Experimental set-up and the graphene morphology on stationary substrates.
Fig. 2: Visualization of the graphene crystal orientations using etched hexagons.
Fig. 3: Crystallographic orientation of etched holes and characterization of the grown graphene.
Fig. 4: Fastest front-line crystallographic orientation and Wulff construction in 2D.

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).

    Article  Google Scholar 

  2. 2.

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

    Google Scholar 

  3. 3.

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

    Book  Google Scholar 

  4. 4.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  6. 6.

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

    Article  Google Scholar 

  7. 7.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  9. 9.

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

    Article  Google Scholar 

  10. 10.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  12. 12.

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

    Article  Google Scholar 

  13. 13.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  15. 15.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  18. 18.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  23. 23.

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

    Article  Google Scholar 

  24. 24.

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

    Article  Google Scholar 

  25. 25.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  27. 27.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  34. 34.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  36. 36.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  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).

    Article  Google Scholar 

  40. 40.

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

    Article  Google Scholar 

  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).

    Article  Google Scholar 

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).

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Authors

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.

Corresponding authors

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

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The authors declare no competing interests.

Supplementary information

Supplementary Information

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

Videos

Supplementary Video 1

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

Supplementary Video 2

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

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Vlassiouk, I.V., Stehle, Y., Pudasaini, P.R. et al. Evolutionary selection growth of two-dimensional materials on polycrystalline substrates. Nature Mater 17, 318–322 (2018). https://doi.org/10.1038/s41563-018-0019-3

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