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Understanding and controlling the substrate effect on graphene electron-transfer chemistry via reactivity imprint lithography

Nature Chemistry volume 4, pages 724–732 (2012)Cite this article

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Abstract

Graphene has exceptional electronic, optical, mechanical and thermal properties, which provide it with great potential for use in electronic, optoelectronic and sensing applications. The chemical functionalization of graphene has been investigated with a view to controlling its electronic properties and interactions with other materials. Covalent modification of graphene by organic diazonium salts has been used to achieve these goals, but because graphene comprises only a single atomic layer, it is strongly influenced by the underlying substrate. Here, we show a stark difference in the rate of electron-transfer reactions with organic diazonium salts for monolayer graphene supported on a variety of substrates. Reactions proceed rapidly for graphene supported on SiO2 and Al2O3 (sapphire), but negligibly on alkyl-terminated and hexagonal boron nitride (hBN) surfaces, as shown by Raman spectroscopy. We also develop a model of reactivity based on substrate-induced electron–hole puddles in graphene, and achieve spatial patterning of chemical reactions in graphene by patterning the substrate.

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Figure 1: Chemical reactivity of graphene supported on different substrates.
Figure 2: Raman spectroscopy peak parameter analysis.
Figure 3: Spatial control of reactivity of graphene on patterned substrates.
Figure 4: Patterning of proteins on graphene.
Figure 5: Modelling of substrate-influenced reactivity.

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Acknowledgements

This work was primarily funded by a 2009 US Office of Naval Research Multi University Research Initiative (MURI) grant on Graphene Advanced Terahertz Engineering (GATE) at MIT, Harvard and Boston University. J.D.S.-Y. and P.J.-H. acknowledge support from an NSF CAREER award (DMR-0845287). K.K.K. acknowledges an NSF award (DMR-0845358) and support from the Materials, Structures and Device (MSD) Center of the Focus Center Research Program (FCRP) at the Semiconductor Research Corporation. The authors thank M.K. Mondol of the MIT Scanning Electron Beam Lithography facility for assistance.

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Authors and Affiliations

  1. Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Qing Hua Wang, Zhong Jin, Andrew J. Hilmer, Geraldine L. C. Paulus, Chih-Jen Shih & Michael S. Strano

  2. Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Ki Kang Kim & Jing Kong

  3. School of Materials Science and Engineering, Gwangju Institute of Science and Technology, Gwangju, 500-712, South Korea

    Moon-Ho Ham

  4. Department of Physics, Massachusetts Institute of Technology, Cambridge, 02139, Massachusetts, USA

    Javier D. Sanchez-Yamagishi & Pablo Jarillo-Herrero

  5. Advanced Materials Laboratory, National Institute for Materials Science, 1-1 Namiki, Tsukuba, 305-0044, Japan

    Kenji Watanabe & Takashi Taniguchi

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  1. Qing Hua Wang
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Contributions

Q.H.W. designed and conducted the substrate and patterning experiments, performed Raman spectroscopy, AFM and data analysis. Z.J. performed protein attachment, ATR–IR and fluorescence imaging. A.J.H., Q.H.W. and M.S.S. devised the model. K.K.K. synthesized the CVD graphene. K.W. and T.T. synthesized the hBN crystal. J.D.S.-Y. exfoliated the hBN crystal. G.L.C.P., C.-J.S. and M.-H.H. conducted additional experiments. Q.H.W. and M.S.S. wrote the manuscript. All authors contributed to the discussion and interpretation of results.

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Correspondence to Michael S. Strano.

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Wang, Q., Jin, Z., Kim, K. et al. Understanding and controlling the substrate effect on graphene electron-transfer chemistry via reactivity imprint lithography. Nature Chem 4, 724–732 (2012). https://doi.org/10.1038/nchem.1421

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