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On-surface synthesis of graphene nanoribbons with zigzag edge topology

Nature volume 531, pages 489–492 (2016)Cite this article

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Abstract

Graphene-based nanostructures exhibit electronic properties that are not present in extended graphene. For example, quantum confinement in carbon nanotubes and armchair graphene nanoribbons leads to the opening of substantial electronic bandgaps that are directly linked to their structural boundary conditions1,2. Nanostructures with zigzag edges are expected to host spin-polarized electronic edge states and can thus serve as key elements for graphene-based spintronics3. The edge states of zigzag graphene nanoribbons (ZGNRs) are predicted to couple ferromagnetically along the edge and antiferromagnetically between the edges4, but direct observation of spin-polarized edge states for zigzag edge topologies—including ZGNRs—has not yet been achieved owing to the limited precision of current top-down approaches5,6,7,8,9,10. Here we describe the bottom-up synthesis of ZGNRs through surface-assisted polymerization and cyclodehydrogenation of specifically designed precursor monomers to yield atomically precise zigzag edges. Using scanning tunnelling spectroscopy we show the existence of edge-localized states with large energy splittings. We expect that the availability of ZGNRs will enable the characterization of their predicted spin-related properties, such as spin confinement11 and filtering12,13, and will ultimately add the spin degree of freedom to graphene-based circuitry.

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Figure 1: Synthetic strategy to GNRs with zigzag edges.
Figure 2: Synthesis and characterization of atomically precise 6-ZGNRs.
Figure 3: Edge-state characterization of 6-ZGNRs.
Figure 4: Synthesis and characterization of edge-modified 6-ZGNRs.

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Acknowledgements

This work was supported by the Swiss National Science Foundation, the Office of Naval Research BRC Program, the European Research Council (grant NANOGRAPH), the DFG Priority Program SPP 1459, the Graphene Flagship (No. CNECT-ICT-604391), and the European Union Projects UPGRADE, GENIUS and MoQuaS. We acknowledge the Swiss Supercomputing Center (CSCS) for computational resources (project s507). We thank A. Ferretti for his contribution to this project and O. Gröning for discussions.

Author information

Author notes

  1. Pascal Ruffieux, Shiyong Wang, Carlos Sánchez-Sánchez and Jia Liu: These authors contributed equally to this work.

Authors and Affiliations

  1. Empa, Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, 8600, Switzerland

    Pascal Ruffieux, Shiyong Wang, Carlos Sánchez-Sánchez, Jia Liu, Thomas Dienel, Leopold Talirz, Prashant Shinde, Carlo A. Pignedoli, Daniele Passerone & Roman Fasel

  2. Max Planck Institute for Polymer Research, Mainz, 55128, Germany

    Bo Yang, Tim Dumslaff & Klaus Müllen

  3. NCCR MARVEL, Empa, Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, 8600, Switzerland

    Carlo A. Pignedoli

  4. Center for Advancing Electronics Dresden & Department of Chemistry and Food Chemistry, Technische Universität Dresden, Dresden, 01062, Germany

    Xinliang Feng

  5. Department of Chemistry and Biochemistry, University of Bern, Bern, 3012, Switzerland

    Roman Fasel

Authors
  1. Pascal Ruffieux
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Contributions

P.R., R.F., X.F. and K.M. conceived and supervised the experiments. B.Y. and T.Du. synthesized the precursor monomers. J.L. and C.S. developed the on-surface synthesis protocols and did the STM analysis. T.Di., J.L. and S.W. performed the AFM imaging; S.W. and J.L. did the spectroscopic analysis. P.S., L.T., C.A.P. and D.P. performed the simulations. C.S., S.W. and P.R. made the figures. P.R., K.M. and R.F. wrote the paper. All authors discussed the results and implications and commented on the manuscript at all stages.

Corresponding authors

Correspondence to Klaus Müllen or Roman Fasel.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Methods (syntheses of monomers), Supplementary Figures 1-11 and additional references. (PDF 5251 kb)

Supplementary Data

This file contains Crystal Structure Data 1a (single crystal of BrBD-Umbrella). (CIF 21 kb)

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Ruffieux, P., Wang, S., Yang, B. et al. On-surface synthesis of graphene nanoribbons with zigzag edge topology. Nature 531, 489–492 (2016). https://doi.org/10.1038/nature17151

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