Article | Published:

Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor

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

Abstract

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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    , & Half-metallic graphene nanoribbons. Nature 444, 347–349 (2006).

  2. 2.

    et al. Switchable ternary nanoporous supramolecular network on photo-regulation. Nano Lett. 11, 3245–3250 (2011).

  3. 3.

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

  4. 4.

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

  5. 5.

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

  6. 6.

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

  7. 7.

    et al. Bottom-up synthesis of N = 13 sulfur-doped graphene nanoribbons. J. Phys. Chem. C 120, 2684–2687 (2016).

  8. 8.

    et al. Site-specific substitutional boron doping of semiconducting armchair graphene nanoribbons. J. Am. Chem. Soc. 137, 8872–8875 (2015).

  9. 9.

    et al. Atomically controlled substitutional boron-doping of graphene nanoribbons. Nature Commun. 6, 8098 (2015).

  10. 10.

    , , , & Heterostructures through divergent edge reconstruction in nitrogen-doped segmented graphene nanoribbons. Eur. J. Chem. A 22, 13037–13040 (2016).

  11. 11.

    & Barrier-free tunneling in a carbon heterojunction transistor. Appl. Phys. Lett. 97, 33102 (2010).

  12. 12.

    , , & Graphene nanoribbon tunnel field effect transistor with lightly doped drain: numerical simulations. Superlattices Microstruct. 75, 245–256 (2014).

  13. 13.

    Semiconductor Physics and Devices: Basic Principles (McGraw-Hill, 2003).

  14. 14.

    , & Electronics using hybrid-molecular and mono-molecular devices. Nature 408, 541–548 (2000).

  15. 15.

    et al. Real-space investigation of energy transfer in heterogeneous molecular dimers. Nature 538, 364–367 (2016).

  16. 16.

    et al. Spatial resolution of a type II heterojunction in a single bipolar molecule. Nano Lett. 9, 3963–3967 (2009).

  17. 17.

    , , , & Large spatially resolved rectification in a donor–acceptor molecular heterojunction. Nano Lett. 16, 2603–2607 (2016).

  18. 18.

    et al. Graphene nanoribbon heterojunctions. Nature Nanotech. 9, 896–900 (2014).

  19. 19.

    et al. Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions. Nature Nanotech. 10, 156–160 (2015).

  20. 20.

    et al. Nitrogen-doping induced self-assembly of graphene nanoribbon-based two-dimensional and three-dimensional metamaterials. Nano Lett. 15, 5770–5777 (2015).

  21. 21.

    et al. Mechanism of high-resolution STM/AFM imaging with functionalized tips. Phys. Rev. B 90, 85421 (2014).

  22. 22.

    , , , & The chemical structure of a molecule resolved by atomic force microscopy. Science 325, 1110–1114 (2009).

  23. 23.

    , , & Real-space imaging of molecular structure and chemical bonding by single-molecule inelastic tunneling probe. Science 344, 885–888 (2014).

  24. 24.

    et al. Direct imaging of covalent bond structure in single-molecule chemical reactions. Science 340, 1434–1437 (2013).

  25. 25.

    Heterostructure bipolar transistors and integrated circuits. Proc. IEEE 70, 13–25 (1982).

  26. 26.

    , , , & Quasiparticle energies and band gaps in graphene nanoribbons. Phys. Rev. Lett. 99, 6–9 (2007).

  27. 27.

    et al. Giant bandgap renormalization and excitonic effects in a monolayer transition metal dichalcogenide semiconductor. Nature Mater. 13, 1091–1095 (2014).

  28. 28.

    et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).

  29. 29.

    & Efficient pseudopotentials for plane-wave calculations. Phys. Rev. B 43, 1993–2006 (1991).

Download references

Acknowledgements

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.

Affiliations

  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

Authors

  1. Search for Giang D. Nguyen in:

  2. Search for Hsin-Zon Tsai in:

  3. Search for Arash A. Omrani in:

  4. Search for Tomas Marangoni in:

  5. Search for Meng Wu in:

  6. Search for Daniel J. Rizzo in:

  7. Search for Griffin F. Rodgers in:

  8. Search for Ryan R. Cloke in:

  9. Search for Rebecca A. Durr in:

  10. Search for Yuki Sakai in:

  11. Search for Franklin Liou in:

  12. Search for Andrew S. Aikawa in:

  13. Search for James R. Chelikowsky in:

  14. Search for Steven G. Louie in:

  15. Search for Felix R. Fischer in:

  16. Search for Michael F. Crommie in:

Contributions

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.

Supplementary information

PDF files

  1. 1.

    Supplementary information

    Supplementary information

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nnano.2017.155

Further reading

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research