Abstract

Fully exploiting the properties of graphene will require a method for the mass production of this remarkable material. Two main routes are possible: large-scale growth or large-scale exfoliation. Here, we demonstrate graphene dispersions with concentrations up to 0.01 mg ml−1, produced by dispersion and exfoliation of graphite in organic solvents such as N-methyl-pyrrolidone. This is possible because the energy required to exfoliate graphene is balanced by the solvent–graphene interaction for solvents whose surface energies match that of graphene. We confirm the presence of individual graphene sheets by Raman spectroscopy, transmission electron microscopy and electron diffraction. Our method results in a monolayer yield of 1 wt%, which could potentially be improved to 7–12 wt% with further processing. The absence of defects or oxides is confirmed by X-ray photoelectron, infrared and Raman spectroscopies. We are able to produce semi-transparent conducting films and conducting composites. Solution processing of graphene opens up a range of potential large-area applications, from device and sensor fabrication to liquid-phase chemistry.

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References

  1. 1.

    & The rise of graphene. Nature Mater. 6, 183–191 (2007).

  2. 2.

    et al. Two-dimensional gas of massless Dirac fermions in graphene. Nature 438, 197–200 (2005).

  3. 3.

    et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).

  4. 4.

    , , & Experimental observation of the quantum Hall effect and Berry's phase in graphene. Nature 438, 201–204 (2005).

  5. 5.

    et al. Breakdown of the adiabatic Born–Oppenheimer approximation in graphene. Nature Mater. 6, 198–201 (2007).

  6. 6.

    et al. Graphene-based liquid crystal device. Nano Lett. 8, 1704–1708 (2008).

  7. 7.

    et al. Two-dimensional atomic crystals. Proc. Natl Acad. Sci. USA 102, 10451–10453 (2005).

  8. 8.

    et al. Ultrahigh electron mobility in suspended graphene. Solid State Commun. 146, 351–355 (2008).

  9. 9.

    et al. Giant intrinsic carrier mobilities in graphene and its bilayer. Phys. Rev. Lett. 1, 016602 (2008).

  10. 10.

    , , & Approaching ballistic transport in suspended graphene. Nature Nanotech. 3, 491–495 (2008).

  11. 11.

    et al. Electronic confinement and coherence in patterned epitaxial graphene. Science 312, 1191–1196 (2006).

  12. 12.

    et al. Morphology of graphene thin film growth on SiC(0001). New J. Phys. 023034 (2008).

  13. 13.

    et al. Origin of the energy bandgap in epitaxial graphene—Reply. Nature Mater. 7, 259–260 (2008).

  14. 14.

    , & Scanning tunnelling microscopy of graphene on Ru(0001). Phys. Rev. B 76, 075429 (2007).

  15. 15.

    et al. Periodically rippled graphene: Growth and spatially resolved electronic structure. Phys. Rev. Lett. 1, 056807 (2008).

  16. 16.

    , & Epitaxial graphene on ruthenium. Nature Mater. 7, 406–411 (2008).

  17. 17.

    et al. Millimetre-scale, highly ordered single crystalline graphene grown on Ru (0001) surface. ArXiv:0709.2858 (2008).

  18. 18.

    , & Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material. Nature Nanotech. 3, 270–274 (2008).

  19. 19.

    et al. Processable aqueous dispersions of graphene nanosheets. Nature Nanotech. 3, 101–105 (2008).

  20. 20.

    et al. Graphene-based composite materials. Nature 442, 282–286 (2006).

  21. 21.

    , & Transparent, conductive graphene electrodes for dye-sensitized solar cells. Nano Lett. 8, 323–327 (2008).

  22. 22.

    et al. Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide. Carbon 45, 1558–1565 (2007).

  23. 23.

    et al. Simple approach for high-contrast optical imaging and characterization of graphene-based sheets. Nano Lett. 7, 3569–3575 (2007).

  24. 24.

    & Intercalation compounds of graphite. Adv. Phys. 30, 139–326 (1981).

  25. 25.

    , & A chemical route to carbon nanoscrolls. Science 299, 1361–1361 (2003).

  26. 26.

    et al. Preparation and characterization of graphite nanosheets from ultrasonic powdering technique. Carbon 42, 753–759 (2004).

  27. 27.

    et al. Chemically derived, ultrasmooth graphene nanoribbon semiconductors. Science 319, 1229–1232 (2008).

  28. 28.

    et al. Solution properties of graphite and graphene. J. Am. Chem. Soc. 128, 7720–7721 (2006).

  29. 29.

    et al. Debundling and dissolution of single-walled carbon nanotubes in amide solvents. J. Am. Chem. Soc. 126, 6095–6105 (2004).

  30. 30.

    et al. Debundling of single-walled nanotubes by dilution: observation of large populations of individual nanotubes in amide solvent dispersions. J. Phys. Chem. B 110, 15708–15718 (2006).

  31. 31.

    , , & Effects of alkyl amide solvents on the dispersion of single-wall carbon nanotubes. J. Phys. Chem. B 108, 17089–17095 (2004).

  32. 32.

    et al. Stabilization and ‘Debundling’ of single-wall carbon nanotube dispersions in N-methyl-2-pyrrolidone (NMP) by polyvinylpyrrolidone (PVP). J. Phys. Chem. C 111, 12594–12602 (2007).

  33. 33.

    et al. Exfoliation in ecstasy: liquid crystal formation and concentration-dependent debundling observed for single-wall nanotubes dispersed in the liquid drug γ-butyrolactone. Nanotechnology 18, 455705 (2007).

  34. 34.

    et al. Towards solutions of SWNT in common solvents. Adv. Mater. 20, 1876–1881 (2007).

  35. 35.

    & Optical and magneto-optical far-infrared properties of bi-layer graphene. Phys. Rev. B 75, 155430 (2007).

  36. 36.

    , & Regular and related solutions 1st edn (Van Nostrand Reinhold Company, New York, 1970).

  37. 37.

    The surface tension of pure liquids—thermodynamic components and corresponding states. Coll. Surf. A 156, 413–421 (1999).

  38. 38.

    & Thermodynamic investigation of N,N-dimethylformamide/toluene binary mixtures in the temperature range from 278.15 to 293.15 K. J. Chem. Therm. 38, 952–961 (2006).

  39. 39.

    et al. Microscopic determination of the interlayer binding energy in graphite. Chem. Phys. Lett. 286, 490–496 (1998).

  40. 40.

    & A theory for the estimation of surface and interfacial energies. 1. Derivation and application to interfacial tension. J. Phys. Chem. 61, 904–909 (1957).

  41. 41.

    & Fullerenes inside carbon nanotubes and multi-walled carbon nanotubes: optimum and maximum sizes. Chem. Phys. Lett. 350, 405–411 (2001).

  42. 42.

    , & Interlayer cohesive energy of graphite from thermal desorption of polyaromatic hydrocarbons. Phys. Rev. B 69, 155406 (2004).

  43. 43.

    et al. Preparation of aligned carbon nanotubes with prescribed dimensions: Template synthesis and sonication cutting approach. Chem. Mater. 14, 1859–1862 (2002).

  44. 44.

    et al. The structure of suspended graphene sheets. Nature 446, 60–63 (2007).

  45. 45.

    et al. On the roughness of single- and bi-layer graphene membranes. Solid State Commun. 143, 101–109 (2007).

  46. 46.

    et al. Carbon nanofilm with a new structure and property. Jpn J. Appl. Phys. Lett. 42, L1073–L1076 (2003).

  47. 47.

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

  48. 48.

    , , & Observation of percolation-like scaling, far from the percolation threshold, in high volume fraction, high conductivity polymer–nanotube composite films. Adv. Mater. 19, 4443–4447 (2007).

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Acknowledgements

We acknowledge the Centre for Research on Adaptive Nanostructures and Nanodevices and Science Foundation Ireland for financial support and Nacional de Grafite (Brazil) for supplying flake graphite. V.N. wishes to thank the EU project ESTEEM for facilitating access to the microscopy facilities in Oxford. A.C.F. acknowledges funding from the Leverhulme Trust and the Royal Society.

Author information

Author notes

    • Yenny Hernandez
    •  & Valeria Nicolosi

    These authors contributed equally to this work.

Affiliations

  1. School of Physics, Trinity College Dublin, Dublin 2, Ireland

    • Yenny Hernandez
    • , Valeria Nicolosi
    • , Mustafa Lotya
    • , Fiona M. Blighe
    • , Zhenyu Sun
    • , Sukanta De
    • , I. T. McGovern
    • , Brendan Holland
    •  & Jonathan N. Coleman
  2. Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College Dublin, Dublin 2, Ireland

    • Zhenyu Sun
    • , Sukanta De
    • , Yurii K. Gun'Ko
    • , John J. Boland
    • , Peter Niraj
    • , Georg Duesberg
    • , Satheesh Krishnamurthy
    •  & Jonathan N. Coleman
  3. School of Chemistry, Trinity College Dublin, Dublin 2, Ireland

    • Michele Byrne
    • , Yurii K. Gun'Ko
    • , John J. Boland
    • , Peter Niraj
    • , Georg Duesberg
    •  & Satheesh Krishnamurthy
  4. Department of Geology, School of Natural Sciences, Trinity College Dublin, Dublin 2, Ireland

    • Robbie Goodhue
  5. Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, UK

    • John Hutchison
  6. Engineering Department, University of Cambridge, 9 JJ Thomson Avenue, Cambridge CB3 0FA, UK

    • Vittorio Scardaci
    •  & Andrea C. Ferrari

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Contributions

J.N.C. conceived and designed the experiments. Y.H., V.N., M.L., F.M.B., Z.S., S.D., B.H., M.B., P.N., S.K., R.G. and V.S. performed the experiments. I.T.McG., R.G., A.C.F. and J.N.C. analysed the data. Y.K.G., J.J.B., G.D., R.G., J.H., A.C.F. and J.N.C. contributed materials/analysis tools. A.C.F. and J.N.C. co-wrote the paper. Y.H. and V.N. contributed equally to this work. All authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Jonathan N. Coleman.

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DOI

https://doi.org/10.1038/nnano.2008.215

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