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Chemically homogeneous and thermally reversible oxidation of epitaxial graphene

Nature Chemistry volume 4, pages 305–309 (2012)Cite this article

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Abstract

With its exceptional charge mobility, graphene holds great promise for applications in next-generation electronics. In an effort to tailor its properties and interfacial characteristics, the chemical functionalization of graphene is being actively pursued. The oxidation of graphene via the Hummers method is most widely used in current studies, although the chemical inhomogeneity and irreversibility of the resulting graphene oxide compromises its use in high-performance devices. Here, we present an alternative approach for oxidizing epitaxial graphene using atomic oxygen in ultrahigh vacuum. Atomic-resolution characterization with scanning tunnelling microscopy is quantitatively compared to density functional theory, showing that ultrahigh-vacuum oxidization results in uniform epoxy functionalization. Furthermore, this oxidation is shown to be fully reversible at temperatures as low as 260 °C using scanning tunnelling microscopy and spectroscopic techniques. In this manner, ultrahigh-vacuum oxidation overcomes the limitations of Hummers-method graphene oxide, thus creating new opportunities for the study and application of chemically functionalized graphene.

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Figure 1: Atomic-scale imaging of chemisorbed atomic oxygen on epitaxial graphene.
Figure 2: Comparison of STM images and DFT calculations of oxygen adatoms on epitaxial graphene.
Figure 3: Reversible UHV oxidation and reduction of epitaxial graphene.
Figure 4: Spectroscopic verification of the reversibility of UHV oxidized epitaxial graphene.

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References

  1. Morozov, S. V. et al. Giant intrinsic carrier mobilities in graphene and its bilayer. Phys. Rev. Lett. 100, 016602 (2008).

    Article  CAS  Google Scholar 

  2. Lee, C., Wei, X., Kysar, J. W. & Hone, J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321, 385–388 (2008).

    Article  CAS  Google Scholar 

  3. Lin, Y. -M. et al. Wafer-scale graphene integrated circuit. Science 332, 1294–1297 (2011).

    Article  CAS  Google Scholar 

  4. Chiang, C. K. et al. Synthesis of highly conducting films of derivatives of polyacetylene. J. Am. Chem. Soc. 100, 1013–1015 (1978).

    Article  CAS  Google Scholar 

  5. Elias, D. C. et al. Control of graphene's properties by reversible hydrogenation: evidence for graphane. Science 323, 610–613 (2009).

    Article  CAS  Google Scholar 

  6. Robinson, J. T. et al. Properties of fluorinated graphene films. Nano Lett. 10, 3001–3005 (2010).

    Article  CAS  Google Scholar 

  7. Nair, R. R. et al. Fluorographene: a two-dimensional counterpart of Teflon. Small 6, 2877–2884 (2010).

    Article  CAS  Google Scholar 

  8. Niyogi, S. et al. Spectroscopy of covalently functionalized graphene. Nano Lett. 10, 4061–4066 (2010).

    Article  CAS  Google Scholar 

  9. Hossain, M. Z., Walsh, M. A. & Hersam, M. C. Scanning tunneling microscopy, spectroscopy, and nanolithography of epitaxial graphene chemically modified with aryl moieties. J. Am. Chem. Soc. 132, 15399–15403 (2010).

    Article  CAS  Google Scholar 

  10. Chen, W., Chen, S., Qi, D. C., Gao, X. Y. & Wee, A. T .S. Surface transfer p-type doping of epitaxial graphene. J. Am. Chem. Soc. 129, 10418–10422 (2007).

    Article  CAS  Google Scholar 

  11. Wang, X., Tabakman, S. M. & Dai, H. Atomic layer deposition of metal oxides on pristine and functionalized graphene. J. Am. Chem. Soc. 130, 8152–8153 (2008).

    Article  CAS  Google Scholar 

  12. Wang, Q. H. & Hersam, M. C. Room-temperature molecular-resolution characterization of self-assembled organic monolayers on epitaxial graphene. Nature Chem. 1, 206–211 (2009).

    Article  CAS  Google Scholar 

  13. Brodie, B. C. On the atomic weight of graphite. Phil. Trans. R. Soc. 149, 249–259 (1859).

    Article  Google Scholar 

  14. Park, S. & Ruoff, R. S. Chemical methods for the production of graphenes. Nature Nanotech. 4, 317–224 (2009).

    Google Scholar 

  15. Hummers, W. S. & Offeman, R. E. Preparation of graphitic oxide. J. Am. Chem. Soc. 80, 1339 (1958).

    Article  CAS  Google Scholar 

  16. Dreyer, D. R., Park, S., Bielawski, C. W. & Ruoff, R. S. The chemistry of graphene oxide. Chem. Soc. Rev. 39, 228–240 (2010).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  18. Becerril, H. A., Mao, J., Liu, Z., Stoltenberg, R. M., Bao, Z. & Chen, Y. Evaluation of solution-processed reduced graphene oxide films as transparent conductors. ACS Nano 2, 463–470 (2008).

    Article  CAS  Google Scholar 

  19. Gomez-Navarro, C. et al. Atomic structure of reduced graphene oxide. Nano Lett. 10, 1144–1148 (2010).

    Article  CAS  Google Scholar 

  20. Bagri, A. et al. Structural evolution during the reduction of chemically derived graphene oxide. Nature Chem. 2, 581–587 (2010).

    Article  CAS  Google Scholar 

  21. Dikin, D. A. et al. Preparation and characterization of graphene oxide paper. Nature 448, 457–460 (2007).

    Article  CAS  Google Scholar 

  22. Park, S. et al. Biocompatible, robust free-standing paper composed of a TWEEN/graphene composite. Adv. Mater. 22, 1736–1740 (2010).

    Article  CAS  Google Scholar 

  23. Ferralis, N., Maboudian, R. & Carraro, C. Evidence of structural strain in epitaxial graphene layers on 6H-SiC(0001). Phys. Rev. Lett. 101, 156801 (2008).

    Article  Google Scholar 

  24. Röhrl, J. et al. Raman spectra of epitaxial graphene on SiC(0001). Appl. Phys. Lett. 92, 201918 (2008).

    Article  Google Scholar 

  25. Kumar, S., Hembram, K. P. & Waghmare, U. V. Intrinsic buckling strength of graphene: first-principles density functional theory calculations. Phys. Rev. B 82, 115411 (2010).

    Article  Google Scholar 

  26. Kudin, K. N. et al. Raman spectra of graphite oxide and functionalized graphene sheets. Nano Lett. 8, 36–39 (2008).

    Article  CAS  Google Scholar 

  27. Wang, Q. H. & Hersam, M. C. Nanofabrication of heteromolecular organic nanostructures on epitaxial graphene via room temperature feedback-controlled lithography. Nano Lett. 11, 589–593 (2011).

    Article  CAS  Google Scholar 

  28. Barinov, A. et al. Initial stages of oxidation on graphitic surfaces: photoemission study and density functional theory calculations. J. Phys. Chem. C 113, 9009–9013 (2009).

    Article  CAS  Google Scholar 

  29. Vinogradov, N. A. et al. Impact of atomic oxygen on the structure of graphene formed on Ir(111) and Pt(111). J. Phys. Chem. C 115, 9568–9577 (2011).

    Article  CAS  Google Scholar 

  30. Larciprete, R. et al. Dual path mechanism in the thermal reduction of graphene oxide. J. Am. Chem. Soc. 133, 17315–17321 (2011).

    Article  CAS  Google Scholar 

  31. Coletti, C. et al. Charge neutrality and band-gap tuning of epitaxial graphene on SiC by molecular doping. Phys. Rev. B 81, 235401 (2010).

    Article  Google Scholar 

  32. Foley, E. T., Yoder, N. L., Guisinger, N. P. & Hersam, M. C. Cryogenic variable temperature ultra-high vacuum scanning tunneling microscope for single molecule studies on silicon surfaces. Rev. Sci. Instrum. 75, 5280–5287 (2004).

    Article  CAS  Google Scholar 

  33. Soler, J. M. et al. The SIESTA method for ab initio order-N materials simulation. J. Phys. Condens. Matter 14, 2745–2779 (2002).

    Article  CAS  Google Scholar 

  34. Riedl, C., Coletti, C. & Starke, U. Structural and electronic properties of epitaxial graphene on SiC(0001): a review of growth, characterization, transfer doping and hydrogen intercalation. J. Phys. D 43, 374009 (2010).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Science Foundation (award nos EEC-0647560, DMR-0906025 and DMR-1121262), the Office of Naval Research (award nos N00014-09-1-0180 and N00014-11-1-0463) and the US Department of Energy (award no. DE-SC0001785). K.H.B. acknowledges support from NSERC (Canada), M.C.H. acknowledges a W. M. Keck Foundation Science and Engineering Grant, and M.Z.H. acknowledges partial support by the Program to Disseminate Tenure-Track System of the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT) granted to Gunma University. The authors thank J. Lyding for the use of his STM control software. S.Y., K.M., T.K. and J.Y. thank K. Mase at KEK-PF for maintenance of BL13A. Computational resources were provided by the National Science Foundation Network for Computational Nanotechnology.

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Author notes

  1. Md. Zakir Hossain & Kirk H. Bevan

    Present address: Present address: Advanced Engineering Research Team, Advanced Scientific Research Leaders Development Unit, Gunma University, Kiryu-City 376-8515, Japan (M.Z.H.), Department of Mining and Materials Engineering, McGill University, Montreal, Quebec H3A 2T8, Canada (K.H.B.),

Authors and Affiliations

  1. Department of Materials Science and Engineering, Northwestern University, Evanston, 60208, Illinois, USA

    Md. Zakir Hossain, James E. Johns, Hunter J. Karmel, Yu Teng Liang & Mark C. Hersam

  2. Department of Medicine, Northwestern University, Evanston, 60208, Illinois, USA

    James E. Johns & Mark C. Hersam

  3. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, 37831, Tennessee, USA

    Kirk H. Bevan

  4. The Institute for Solid State Physics, University of Tokyo, Kashiwa, Chiba, Japan

    Shinya Yoshimoto, Kozo Mukai, Tatanori Koitaya & Jun Yoshinobu

  5. Department of Advanced Materials Science, University of Tokyo, Kashiwa, Chiba, Japan

    Maki Kawai

  6. Advanced Science Institute, RIKEN, Wako, Japan

    Maki Kawai

  7. Department of Chemistry, Indiana University, Bloomington, 47405, Indiana, USA

    Amanda M. Lear & Steven L. Tait

  8. Department of Physics, Indiana University, Bloomington, 47405, Indiana, USA

    Larry L. Kesmodel

  9. Department of Chemistry, Northwestern University, Evanston, 60208, Illinois, USA

    Mark C. Hersam

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  1. Md. Zakir Hossain
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Contributions

M.Z.H. developed the UHV oxidation procedures for epitaxial graphene, performed STM, XPS and UPS characterization and analysis, and wrote the first draft of the manuscript. J.E.J. and Y.T.L. performed the Raman spectroscopy and analysis. K.H.B. performed the DFT calculations and analysis. H.J.K. contributed to the experimental set-up for dosing oxygen in UHV. A.M.L., S.L.T. and L.L.K. performed AES characterization and analysis. S.Y., K.M., T.K. and J.Y. performed the HR-XPS measurements. M.K. contributed to the UPS measurement. M.C.H. oversaw all research phases and revised the manuscript in collaboration with all co-authors.

Corresponding author

Correspondence to Mark C. Hersam.

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Hossain, M., Johns, J., Bevan, K. et al. Chemically homogeneous and thermally reversible oxidation of epitaxial graphene. Nature Chem 4, 305–309 (2012). https://doi.org/10.1038/nchem.1269

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