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Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor

Nature Nanotechnology volume 12, pages 10771082 (2017) | Download Citation


The rational bottom-up synthesis of atomically defined graphene nanoribbon (GNR) heterojunctions represents an enabling technology for the design of nanoscale electronic devices. Synthetic strategies used thus far have relied on the random copolymerization of two electronically distinct molecular precursors to yield GNR heterojunctions. Here we report the fabrication and electronic characterization of atomically precise GNR heterojunctions prepared through late-stage functionalization of chevron GNRs obtained from a single precursor. Post-growth excitation of fully cyclized GNRs induces cleavage of sacrificial carbonyl groups, resulting in atomically well-defined heterojunctions within a single GNR. The GNR heterojunction structure was characterized using bond-resolved scanning tunnelling microscopy, which enables chemical bond imaging at T = 4.5 K. Scanning tunnelling spectroscopy reveals that band alignment across the heterojunction interface yields a type II heterojunction, in agreement with first-principles calculations. GNR heterojunction band realignment proceeds over a distance less than 1 nm, leading to extremely large effective fields.

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This research was supported by the Office of Naval Research BRC Program (spectroscopic imaging), by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under award no. DE-SC0010409 (design, synthesis, and characterization of molecular precursors) and Nanomachine Program award no. DE-AC02-05CH11231 (surface reaction characterization and band structure calculations), by DARPA, the US Army Research Laboratory and the US Army Research Office under contract/grant no. W911NF-15-1-0237 (tip-based manipulation), and by the National Science Foundation (NSF) under grant no. DMR-1508412 (development of theory formalism and STM analyses). Computational resources were provided by the DOE at Lawrence Berkeley National Laboratory's NERSC facility and by the NSF through XSEDE resources at NICS. Y.S. and J.R.C. acknowledge support from the US DOE under contract no. DOE/DE-FG02-06ER46286 (AFM simulation) and the Welch Foundation under grant F-1837 (image analysis). A.A.O. acknowledges support from the Swiss National Science Foundation (SNSF) Postdoctoral Research Fellowship under grant no. P2ELP2-151852.

Author information

Author notes

    • Giang D. Nguyen

    Present address: Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA

    • Giang D. Nguyen
    • , Hsin-Zon Tsai
    • , Arash A. Omrani
    • , Tomas Marangoni
    •  & Meng Wu

    These authors contributed equally.


  1. Department of Physics, University of California at Berkeley, Berkeley, California 94720, USA

    • Giang D. Nguyen
    • , Hsin-Zon Tsai
    • , Arash A. Omrani
    • , Meng Wu
    • , Daniel J. Rizzo
    • , Griffin F. Rodgers
    • , Franklin Liou
    • , Andrew S. Aikawa
    • , Steven G. Louie
    •  & Michael F. Crommie
  2. Department of Chemistry, University of California at Berkeley, Berkeley, California 94720, USA

    • Tomas Marangoni
    • , Ryan R. Cloke
    • , Rebecca A. Durr
    •  & Felix R. Fischer
  3. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    • Meng Wu
    • , Steven G. Louie
    • , Felix R. Fischer
    •  & Michael F. Crommie
  4. Center for Computational Materials, Institute for Computational Engineering and Sciences, Departments of Physics and Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712, USA

    • Yuki Sakai
    •  & James R. Chelikowsky
  5. Kavli Energy NanoSciences Institute at the University of California Berkeley and the Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    • Felix R. Fischer
    •  & Michael F. Crommie


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T.M., R.R.C., R.A.D. and F.R.F. designed, synthesized and characterized the molecular precursors. G.D.N., H.T., A.A.O., D.J.R., G.F.R., F.L. and A.S.A. performed STM and nc-AFM measurements. G.D.N., H.T., A.A.O. and D.J.R. performed data analysis. M.W. and S.G.L. performed DFT calculations and interpretation of STM data. Y.S. and J.R.C. performed theoretical simulation for BRSTM imaging. M.F.C. supervised the experimental scanned probe measurements and helped to interpret the results. All authors contributed to the scientific discussion and helped in writing the manuscript.

Competing interests

The authors declare no competing financial interests.

Corresponding authors

Correspondence to Steven G. Louie or Felix R. Fischer or Michael F. Crommie.

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