Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Graphene nanoribbon heterojunctions

Abstract

Despite graphene's remarkable electronic properties1,2, the lack of an electronic bandgap severely limits its potential for applications in digital electronics3,4. In contrast to extended films, narrow strips of graphene (called graphene nanoribbons) are semiconductors through quantum confinement5,6, with a bandgap that can be tuned as a function of the nanoribbon width and edge structure7,8,9,10. Atomically precise graphene nanoribbons can be obtained via a bottom-up approach based on the surface-assisted assembly of molecular precursors11. Here we report the fabrication of graphene nanoribbon heterojunctions and heterostructures by combining pristine hydrocarbon precursors with their nitrogen-substituted equivalents. Using scanning probe methods, we show that the resulting heterostructures consist of seamlessly assembled segments of pristine (undoped) graphene nanoribbons (p-GNRs) and deterministically nitrogen-doped graphene nanoribbons (N-GNRs), and behave similarly to traditional p–n junctions12. With a band shift of 0.5 eV and an electric field of 2 × 108 V m–1 at the heterojunction, these materials bear a high potential for applications in photovoltaics and electronics.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Bottom-up fabrication of N-GNRs.
Figure 2: Fabrication and identification of p-N-GNR heterojunctions.
Figure 3: Band offset across p-N-GNR heterojunctions.
Figure 4: Differential conductance dI/dV maps of p-N-GNR heterostructures.

Similar content being viewed by others

References

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

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  3. Castro Neto, A. H., Guinea, F., Peres, N. M. R., Novoselov, K. S. & Geim, A. K. The electronic properties of graphene. Rev. Mod. Phys. 81, 109–162 (2009).

    Article  CAS  Google Scholar 

  4. Kotov, V. N., Uchoa, B., Pereira, V. M., Guinea, F. & Castro Neto, A. H. Electron–electron interactions in graphene: current status and perspectives. Rev. Mod. Phys. 84, 1067–1125 (2012).

    Article  CAS  Google Scholar 

  5. Wakabayashi, K. Electronic transport properties of nanographite ribbon junctions. Phys. Rev. B 64, 125428 (2001).

    Article  Google Scholar 

  6. 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 

  7. Chen, Y. et al. Tuning the band gap of graphene nanoribbons synthesized from molecular precursors. ACS Nano 7, 6123–6128 (2013).

    Article  CAS  Google Scholar 

  8. Son, Y. W., Cohen, M. L. & Louie, S. G. Half-metallic graphene nanoribbons. Nature 444, 347–349 (2006).

    Article  CAS  Google Scholar 

  9. Yang, L. et al. Quasiparticle energies and band gaps in graphene nanoribbons. Phys. Rev. Lett. 99, 186801 (2007).

    Article  Google Scholar 

  10. Ruffieux, P. et al. Electronic structure of atomically precise graphene nanoribbons. ACS Nano 6, 6930–6935 (2012).

    Article  CAS  Google Scholar 

  11. Cai, J. et al. Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 466, 470–473 (2010).

    Article  CAS  Google Scholar 

  12. Kittel, C. Introduction to Solid State Physics 5th edn (Wiley, 1976).

    Google Scholar 

  13. Girao, E. C., Liang, L., Cruz-Silva, E., Souza Filho, A. G. Meunier, V. Emergence of atypical properties in assembled graphene nanoribbons. Phys. Rev. Lett. 107, 135501 (2011).

    Article  Google Scholar 

  14. Wang, X. R. et al. N-doping of graphene through electrothermal reactions with ammonia. Science 324, 768–771 (2009).

    Article  CAS  Google Scholar 

  15. Panchakarla, L. S. et al. Synthesis, structure, and properties of boron- and nitrogen-doped graphene. Adv. Mater. 21, 4726–4730 (2009).

    CAS  Google Scholar 

  16. Wei, D. C. et al. Synthesis of N-doped graphene by chemical vapor deposition and its electrical properties. Nano Lett. 9, 1752–1758 (2009).

    Article  CAS  Google Scholar 

  17. Braun, K. F. & Rieder, K. H. Engineering electronic lifetimes in artificial atomic structures. Phys. Rev. Lett. 88, 096801 (2002).

    Article  Google Scholar 

  18. Yan, Q. M. et al. Intrinsic current–voltage characteristics of graphene nanoribbon transistors and effect of edge doping. Nano Lett. 7, 1469–1473 (2007).

    Article  CAS  Google Scholar 

  19. Li, Y. F. et al. Spin gapless semiconductor–metal–half-metal properties in nitrogen-doped zigzag graphene nanoribbons. ACS Nano 3, 1952–1958 (2009).

    Article  CAS  Google Scholar 

  20. Boukhvalov, D. W. & Katsnelson, M. I. Chemical functionalization of graphene with defects. Nano Lett. 8, 4373–4379 (2008).

    Article  CAS  Google Scholar 

  21. Yu, S. S. et al. First principle calculations of the electronic properties of nitrogen-doped carbon nanoribbons with zigzag edges. Carbon 46, 537–543 (2008).

    Article  CAS  Google Scholar 

  22. Cocchi, C., Ruini, A., Prezzi, D., Caldas, M. J. & Molinari, E. Designing all-graphene nanojunctions by covalent functionalization. J. Phys. Chem. C 115, 2969–2973 (2011).

    Article  CAS  Google Scholar 

  23. Neamen, D. A. Semiconductor Physics and Devices: Basic Principles 3rd edn (McGraw-Hill, 2003).

    Google Scholar 

  24. Nag, B. R. Physics of Quantum Well Devices (Springer, 2000).

    Google Scholar 

  25. Bronner, C. et al. Aligning the band gap of graphene nanoribbons by monomer doping. Angew. Chem. Int. Ed. 52, 4422–4425 (2013).

    Article  CAS  Google Scholar 

  26. Bennett, P. B. et al. Bottom-up graphene nanoribbon field-effect transistors. Appl. Phys. Lett. 103, 253114 (2013).

    Article  Google Scholar 

  27. Goedecker, S., Teter, M. & Hutter, J. Separable dual-space Gaussian pseudopotentials. Phys. Rev. B 54, 1703–1710 (1996).

    Article  CAS  Google Scholar 

  28. Perdew, J. P., Burke, K. & Wang, Y. Generalized gradient approximation for the exchange-correlation hole of a many-electron system. Phys. Rev. B 54, 16533–16539 (1996).

    Article  CAS  Google Scholar 

  29. Giannozzi, P. et al. Quantum espresso: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).

    Article  Google Scholar 

  30. VandeVondele, J. et al. Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach. Comput. Phys. Commun. 167, 103–128 (2005).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Swiss National Science Foundation, by the State Secretariat for Education, Research and Innovation via the COST Action MP0901 ‘NanoTP’, by the European Science Foundation under the EUROCORES Program EuroGRAPHENE (GOSPEL), ERC NANOGRAPH, EU GENIUS project, Graphene Flagship and by the Office of Naval Research BRC Program. The Swiss Supercomputing Center, CSCS, is acknowledged for computational support (project s507). The authors thank D. Passerone for stimulating discussion. J.C. thanks R. Widmer, J. Liu and C. Sánchez for help with the experiments.

Author information

Authors and Affiliations

Authors

Contributions

J.C., P.R, R.F., X.F. and K.M. conceived and designed the experiments. R.B. synthesized the molecular precursors. J.C. performed the growth and scanning-probe experiments. J.C. and H.S. did the scanning tunnelling spectroscopy analysis. R.L. and X.F. developed the transfer process and performed the Raman measurements. C.A.P., L.T., L.L. and V.M. performed the simulations. J.C. and R.F. prepared the figures and wrote the paper. All authors discussed the results and implications, and commented on the manuscript.

Corresponding authors

Correspondence to Klaus Müllen or Roman Fasel.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary Information (PDF 1439 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Cai, J., Pignedoli, C., Talirz, L. et al. Graphene nanoribbon heterojunctions. Nature Nanotech 9, 896–900 (2014). https://doi.org/10.1038/nnano.2014.184

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2014.184

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing