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Bandgap opening in graphene induced by patterned hydrogen adsorption


Graphene, a single layer of graphite, has recently attracted considerable attention owing to its remarkable electronic and structural properties and its possible applications in many emerging areas such as graphene-based electronic devices1. The charge carriers in graphene behave like massless Dirac fermions, and graphene shows ballistic charge transport, turning it into an ideal material for circuit fabrication2,3. However, graphene lacks a bandgap around the Fermi level, which is the defining concept for semiconductor materials and essential for controlling the conductivity by electronic means. Theory predicts that a tunable bandgap may be engineered by periodic modulations of the graphene lattice4,5,6, but experimental evidence for this is so far lacking. Here, we demonstrate the existence of a bandgap opening in graphene, induced by the patterned adsorption of atomic hydrogen onto the Moiré superlattice positions of graphene grown on an Ir(111) substrate.

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Figure 1: Observation of a gap opening in hydrogenated graphene.
Figure 2: STM images of hydrogen adsorbate structures following and preserving the Moiré pattern of graphene on Ir(111).
Figure 3: DFT calculations of hydrogen adsorbate structures on graphene on Ir(111).
Figure 4: Hydrogen adsorbate structures, calculated band structures and bandgaps.


  1. Geim, A. & Novoselov, K. The rise of graphene. Nature Mater. 6, 183–191 (2007).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  3. Hass, J. et al. Highly ordered graphene for two-dimensional electronics. Appl. Phys. Lett. 89, 143106 (2006).

    Article  Google Scholar 

  4. Duplock, E. J., Scheffler, M. & Lindan, P. J. D. Hallmark of perfect graphene. Phys. Rev. Lett. 92, 225502 (2004).

    Article  Google Scholar 

  5. Chernozatonskiǐ, L., Sorokin, P., Belova, E., Brüning, J. & Fedorov, A. Superlattices consisting of lines of adsorbed hydrogen atom pairs on graphene. JETP Lett. 85, 77–81 (2007).

    Article  Google Scholar 

  6. Pedersen, T. et al. Graphene antidot lattices: Designed defects and spin qubits. Phys. Rev. Lett. 100, 136804 (2008).

    Article  Google Scholar 

  7. Giovannetti, G., Khomyakov, P. A., Brocks, G., Kelly, P. J. & van den Brink, J. Substrate-induced band gap in graphene on hexagonal boron nitride: Ab initio density functional calculations. Phys. Rev. B 76, 073103 (2007).

    Article  Google Scholar 

  8. Son, Y., Cohen, M. & Louie, S. Energy gaps in graphene nanoribbons. Phys. Rev. Lett. 97, 1–4 (2006).

    Google Scholar 

  9. Zhou, S. Y. et al. Origin of the energy bandgap in epitaxial graphene—reply. Nature Mater. 7, 259–260 (2008).

    Article  CAS  Google Scholar 

  10. Rotenberg, E. et al. Origin of the energy bandgap in epitaxial graphene. Nature Mater. 7, 258–259 (2008).

    Article  CAS  Google Scholar 

  11. Berger, C. Electronic confinement and coherence in patterned epitaxial graphene. Science 312, 1191–1196 (2006).

    Article  CAS  Google Scholar 

  12. Han, M. Y., Oezyilmaz, B., Zhang, Y. & Kim, P. Energy band-gap engineering of graphene nanoribbons. Phys. Rev. Lett. 98, 206805 (2007).

    Article  Google Scholar 

  13. Barone, V., Hod, O. & Scuseria, G. E. Electronic structure and stability of semiconducting graphene nanoribbons. Nano Lett. 6, 2748–2754 (2006).

    Article  CAS  Google Scholar 

  14. Lu, Y. H. et al. Effects of edge passivation by hydrogen on electronic structure of armchair graphene nanoribbon and band gap engineering. Appl. Phys. Lett. 94, 122111 (2009).

    Article  Google Scholar 

  15. Vanevic, M., Stojanovic, V. M. & Kindermann, M. Character of electronic states in graphene antidot lattices: Flat bands and spatial localization. Phys. Rev. B 80, 045410 (2009).

    Article  Google Scholar 

  16. Eroms, J. & Weiss, D. Weak localization and transport gap in graphene antidot lattices. New J. Phys. 11, 095021 (2009).

    Article  Google Scholar 

  17. Sofo, J. O., Chaudhari, A. S. & Barber, G. D. Graphane: A two-dimensional hydrocarbon. Phys. Rev. B 75, 153401 (2007).

    Article  Google Scholar 

  18. Zhou, J., Wu, M. M., Zhou, X. & Sun, Q. Tuning electronic and magnetic properties of graphene by surface modification. Appl. Phys. Lett. 95, 103108 (2009).

    Article  Google Scholar 

  19. Bostwick, A. et al. Quasiparticle transformation during a metal–insulator transition in graphene. Phys. Rev. Lett. 103, 1–4 (2009).

    Article  Google Scholar 

  20. Elias, D. et al. Control of graphene’s properties by reversible hydrogenation: Evidence for graphane. Science 323, 610–613 (2009).

    Article  CAS  Google Scholar 

  21. Guisinger, N., Rutter, G., Crain, J., First, P. & Stroscio, J. Exposure of epitaxial graphene on SiC(0001) to atomic hydrogen. Nano Lett. 9, 1462–1466 (2009).

    Article  CAS  Google Scholar 

  22. Balog, R. et al. Atomic hydrogen adsorbate structures on graphene. J. Am. Chem. Soc. 131, 8744–8745 (2009).

    Article  CAS  Google Scholar 

  23. Pletikosic, I. et al. Dirac cones and minigaps for graphene on Ir(111). Phys. Rev. Lett. 102, 056808 (2009).

    Article  CAS  Google Scholar 

  24. Coraux, J., N′Diaye, A. T., Busse, C. & Michely, T. Structural coherency of graphene on Ir(111). Nano Lett. 8, 565–570 (2008).

    Article  CAS  Google Scholar 

  25. N′Diaye, A. T., Bleikamp, S., Feibelman, P. J. & Michely, T. Two-dimensional Ir cluster lattice on a graphene moire on Ir(111). Phys. Rev. Lett. 97, 215501 (2006).

    Article  Google Scholar 

  26. Feibelman, P. J. Pinning of graphene to Ir(111) by flat Ir dots. Phys. Rev. B 77, 165419 (2008).

    Article  Google Scholar 

  27. Hornekaer, L. et al. Metastable structures and recombination pathways for atomic hydrogen on the graphite (0001) surface. Phys. Rev. Lett. 96, 156104 (2006).

    Article  CAS  Google Scholar 

  28. Casolo, S., Lovvik, O. M., Martinazzo, R. & Tantardini, G. F. Understanding adsorption of hydrogen atoms on graphene. J. Chem. Phys. 130, 054704 (2009).

    Article  Google Scholar 

  29. Boukhvalov, D. W. Hydrogen on graphene: Electronic structure, total energy, structural distortions and magnetism from first-principles calculations. Phys. Rev. B 77, 035427 (2008).

    Article  Google Scholar 

  30. Ferro, Y. et al. Stability and magnetism of hydrogen dimers on graphene. Phys. Rev. B 78, 085417 (2008).

    Article  Google Scholar 

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The authors gratefully acknowledge financial support from the European Research Council under ERC starting grant HPAH, no. 208344, The Danish Council for Independent Research and the Lundbeck Foundation. M.B. thanks the University of Trieste and Aarhus University (AU) for supporting his stay at AU. The research leading to these results has received financial support from the European Community’s Seventh Framework Programme (FP7/2007-2013) under grant agreement no. 226716.

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Authors and Affiliations



P.H. and L.H. planned the project; R.B., B.J., L.N., S.L., P.H. and L.H. designed the experiments; A.B. and S.L. supplied the procedure for graphene preparation; R.B., B.J., E.R., M.B., M.F., S.L. and P.H. carried out the UPS measurements; R.B., L.N. and M.A. carried out the STM measurements; E.L. provided technical support for the STM measurements; Z.S. and T.G.P. carried out the calculations; R.B., B.J., L.N., M.A., E.R., S.L., B.H., T.G.P., P.H. and L.H. analysed the data and interpreted the results; R.B., P.H. and L.H. wrote the manuscript; A.B., E.L., F.B. and B.H. advised on the project; all authors discussed the results and commented on the manuscript.

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Correspondence to Liv Hornekær.

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The authors declare no competing financial interests.

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Balog, R., Jørgensen, B., Nilsson, L. et al. Bandgap opening in graphene induced by patterned hydrogen adsorption. Nature Mater 9, 315–319 (2010).

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