Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor
Source abstract
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.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Graphene research and applications · Molecular Junctions and Nanostructures · Quantum and electron transport phenomena
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (29)
Show source-provided references
1. Son, Y.-W., Cohen, M. L. & Louie, S. G. Half-metallic graphene nanoribbons. Nature 444, 347–349 (2006).10.1038/nature05180 ↗
2. Shen, Y. T. et al. Switchable ternary nanoporous supramolecular network on photo-regulation. Nano Lett. 11, 3245–3250 (2011).10.1021/nl201504x ↗
3. Cai, J. et al. Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 466, 470–473 (2010).10.1038/nature09211 ↗
4. Bennett, P. B. et al. Bottom-up graphene nanoribbon field-effect transistors. Appl. Phys. Lett. 103, 253114 (2013).10.1063/1.4855116 ↗
5. Chen, Y. C. et al. Tuning the band gap of graphene nanoribbons synthesized from molecular precursors. ACS Nano 7, 6123–6128 (2013).10.1021/nn401948e ↗
6. Bronner, C. et al. Aligning the band gap of graphene nanoribbons by monomer doping. Angew. Chem. Int. Ed. 52, 4422–4425 (2013).10.1002/anie.201209735 ↗
7. Nguyen, G. D. et al. Bottom-up synthesis of N = 13 sulfur-doped graphene nanoribbons. J. Phys. Chem. C 120, 2684–2687 (2016).10.1021/acs.jpcc.5b09986 ↗
8. Cloke, R. R. et al. Site-specific substitutional boron doping of semiconducting armchair graphene nanoribbons. J. Am. Chem. Soc. 137, 8872–8875 (2015).10.1021/jacs.5b02523 ↗
9. Kawai, S. et al. Atomically controlled substitutional boron-doping of graphene nanoribbons. Nature Commun. 6, 8098 (2015).10.1038/ncomms9098 ↗
10. 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).10.1002/chem.201603497 ↗
11. Yoon, Y. & Salahuddin, S. Barrier-free tunneling in a carbon heterojunction transistor. Appl. Phys. Lett. 97, 33102 (2010).10.1063/1.3431661 ↗
12. 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).10.1016/j.spmi.2014.07.042 ↗
13. Neamen, D. A. Semiconductor Physics and Devices: Basic Principles (McGraw-Hill, 2003).
14. Joachim, C., Gimzewski, J. K. & Aviram, A. Electronics using hybrid-molecular and mono-molecular devices. Nature 408, 541–548 (2000).10.1038/35046000 ↗
15. Imada, H. et al. Real-space investigation of energy transfer in heterogeneous molecular dimers. Nature 538, 364–367 (2016).10.1038/nature19765 ↗
16. Tao, C. et al. Spatial resolution of a type II heterojunction in a single bipolar molecule. Nano Lett. 9, 3963–3967 (2009).10.1021/nl901860n ↗
17. 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).10.1021/acs.nanolett.6b00171 ↗
18. Cai, J. et al. Graphene nanoribbon heterojunctions. Nature Nanotech. 9, 896–900 (2014).10.1038/nnano.2014.184 ↗
19. Chen, Y.-C. et al. Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions. Nature Nanotech. 10, 156–160 (2015).10.1038/nnano.2014.307 ↗
20. 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).10.1021/acs.nanolett.5b01723 ↗
21. Hapala, P. et al. Mechanism of high-resolution STM/AFM imaging with functionalized tips. Phys. Rev. B 90, 85421 (2014).10.1103/PhysRevB.90.085421 ↗
22. 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).10.1126/science.1176210 ↗
23. 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).10.1126/science.1253405 ↗
24. de Oteyza, D. G. et al. Direct imaging of covalent bond structure in single-molecule chemical reactions. Science 340, 1434–1437 (2013).10.1126/science.1238187 ↗
25. Kroemer, H. Heterostructure bipolar transistors and integrated circuits. Proc. IEEE 70, 13–25 (1982).10.1109/PROC.1982.12226 ↗
26. 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).
27. Ugeda, M. M. et al. Giant bandgap renormalization and excitonic effects in a monolayer transition metal dichalcogenide semiconductor. Nature Mater. 13, 1091–1095 (2014).10.1038/nmat4061 ↗
28. 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).10.1088/0953-8984/21/39/395502 ↗
29. Troullier, N. & Martins, J. L. Efficient pseudopotentials for plane-wave calculations. Phys. Rev. B 43, 1993–2006 (1991).10.1103/PhysRevB.43.1993 ↗