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.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Son, Y.-W., Cohen, M. L. & Louie, S. G. Half-metallic graphene nanoribbons. Nature 444, 347–349 (2006).
Shen, Y. T. et al. Switchable ternary nanoporous supramolecular network on photo-regulation. Nano Lett. 11, 3245–3250 (2011).
Cai, J. et al. Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 466, 470–473 (2010).
Bennett, P. B. et al. Bottom-up graphene nanoribbon field-effect transistors. Appl. Phys. Lett. 103, 253114 (2013).
Chen, Y. C. et al. Tuning the band gap of graphene nanoribbons synthesized from molecular precursors. ACS Nano 7, 6123–6128 (2013).
Bronner, C. et al. Aligning the band gap of graphene nanoribbons by monomer doping. Angew. Chem. Int. Ed. 52, 4422–4425 (2013).
Nguyen, G. D. et al. Bottom-up synthesis of N = 13 sulfur-doped graphene nanoribbons. J. Phys. Chem. C 120, 2684–2687 (2016).
Cloke, R. R. et al. Site-specific substitutional boron doping of semiconducting armchair graphene nanoribbons. J. Am. Chem. Soc. 137, 8872–8875 (2015).
Kawai, S. et al. Atomically controlled substitutional boron-doping of graphene nanoribbons. Nature Commun. 6, 8098 (2015).
Marangoni, T., Haberer, D., Rizzo, D. J., Cloke, R. R. & Fischer, F. R. Heterostructures through divergent edge reconstruction in nitrogen-doped segmented graphene nanoribbons. Eur. J. Chem. A 22, 13037–13040 (2016).
Yoon, Y. & Salahuddin, S. Barrier-free tunneling in a carbon heterojunction transistor. Appl. Phys. Lett. 97, 33102 (2010).
Ghoreishi, S. S., Saghafi, K., Yousefi, R. & Moravvej-Farshi, M. K. Graphene nanoribbon tunnel field effect transistor with lightly doped drain: numerical simulations. Superlattices Microstruct. 75, 245–256 (2014).
Neamen, D. A. Semiconductor Physics and Devices: Basic Principles (McGraw-Hill, 2003).
Joachim, C., Gimzewski, J. K. & Aviram, A. Electronics using hybrid-molecular and mono-molecular devices. Nature 408, 541–548 (2000).
Imada, H. et al. Real-space investigation of energy transfer in heterogeneous molecular dimers. Nature 538, 364–367 (2016).
Tao, C. et al. Spatial resolution of a type II heterojunction in a single bipolar molecule. Nano Lett. 9, 3963–3967 (2009).
Smerdon, J. A., Giebink, N. C., Guisinger, N. P., Darancet, P. & Guest, J. R. Large spatially resolved rectification in a donor–acceptor molecular heterojunction. Nano Lett. 16, 2603–2607 (2016).
Cai, J. et al. Graphene nanoribbon heterojunctions. Nature Nanotech. 9, 896–900 (2014).
Chen, Y.-C. et al. Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions. Nature Nanotech. 10, 156–160 (2015).
Vo, T. H. et al. Nitrogen-doping induced self-assembly of graphene nanoribbon-based two-dimensional and three-dimensional metamaterials. Nano Lett. 15, 5770–5777 (2015).
Hapala, P. et al. Mechanism of high-resolution STM/AFM imaging with functionalized tips. Phys. Rev. B 90, 85421 (2014).
Gross, L., Mohn, F., Moll, N., Liljeroth, P. & Meyer, G. The chemical structure of a molecule resolved by atomic force microscopy. Science 325, 1110–1114 (2009).
Chiang, C., Xu, C., Han, Z. & Ho, W. Real-space imaging of molecular structure and chemical bonding by single-molecule inelastic tunneling probe. Science 344, 885–888 (2014).
de Oteyza, D. G. et al. Direct imaging of covalent bond structure in single-molecule chemical reactions. Science 340, 1434–1437 (2013).
Kroemer, H. Heterostructure bipolar transistors and integrated circuits. Proc. IEEE 70, 13–25 (1982).
Yang, L., Park, C.-H., Son, Y.-W., Cohen, M. L. & Louie, S. G. Quasiparticle energies and band gaps in graphene nanoribbons. Phys. Rev. Lett. 99, 6–9 (2007).
Ugeda, M. M. et al. Giant bandgap renormalization and excitonic effects in a monolayer transition metal dichalcogenide semiconductor. Nature Mater. 13, 1091–1095 (2014).
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).
Troullier, N. & Martins, J. L. Efficient pseudopotentials for plane-wave calculations. Phys. Rev. B 43, 1993–2006 (1991).
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
Authors and Affiliations
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.
Corresponding authors
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 1157 kb)
Rights and permissions
About this article
Cite this article
Nguyen, G., Tsai, HZ., Omrani, A. et al. Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor. Nature Nanotech 12, 1077–1082 (2017). https://doi.org/10.1038/nnano.2017.155
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nnano.2017.155
This article is cited by
-
Deceptive orbital confinement at edges and pores of carbon-based 1D and 2D nanoarchitectures
Nature Communications (2024)
-
Exceptionally clean single-electron transistors from solutions of molecular graphene nanoribbons
Nature Materials (2023)
-
Observation of electron orbital signatures of single atoms within metal-phthalocyanines using atomic force microscopy
Nature Communications (2023)
-
On-surface synthesis and edge states of NBN-doped zigzag graphene nanoribbons
Nano Research (2023)
-
Energy band engineering via “Bite” defect located on N = 8 armchair graphene nanoribbons
Nano Research (2022)