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Circumventing the stability problems of graphene nanoribbon zigzag edges

Nature Chemistry volume 14, pages 1451–1458 (2022)Cite this article

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A Publisher Correction to this article was published on 14 December 2022

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Abstract

Carbon nanostructures with zigzag edges exhibit unique properties—such as localized electronic states and spins—with exciting potential applications. Such nanostructures however are generally synthesized under vacuum because their zigzag edges are unstable under ambient conditions: a barrier that must be surmounted to achieve their scalable integration into devices for practical purposes. Here we show two chemical protection/deprotection strategies, demonstrated on labile, air-sensitive chiral graphene nanoribbons. Upon hydrogenation, the chiral graphene nanoribbons survive exposure to air, after which they are easily converted back to their original structure by annealing. We also approach the problem from another angle by synthesizing a form of the chiral graphene nanoribbons that is functionalized with ketone side groups. This oxidized form is chemically stable and can be converted to the pristine hydrocarbon form by hydrogenation and annealing. In both cases, the deprotected chiral graphene nanoribbons regain electronic properties similar to those of the pristine nanoribbons. We believe both approaches may be extended to other graphene nanoribbons and carbon-based nanostructures.

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Fig. 1: Schematic representation of the degradation of (3,1)-chGNRs exposed to air and the prospective protection strategy by controlled hydrogenation.
Fig. 2: Scanning probe microscopy analysis of GNRs along the various steps in the cycle of synthesis, hydrogenation (protection), air exposure and annealing (deprotection).
Fig. 3: Reactant and product structure of pre-oxidized (protected) chGNRs.
Fig. 4: Electronic properties of pre-oxidized protected GNRs.
Fig. 5: Comparison of the chemical and electronic structures of the various GNRs studied.
Fig. 6: STM analysis of GNRs along the various steps in the synthesis process of its pre-oxidized (protected) form, hydrogenation and annealing (deprotection).

Data availability

All relevant data generated and analysed during this study, including STM and scanning tunnelling spectroscopy data and theoretical calculations, are included in this Article and its Supplementary Information and are also available from the authors upon reasonable request. Source data are provided with this paper.

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References

  1. Corso, M., Carbonell-Sanromà, E. & de Oteyza, D. G. in On-Surface Synthesis II 113–152 (Springer, 2018).

  2. Yano, Y., Mitoma, N., Ito, H. & Itami, K. A quest for structurally uniform graphene nanoribbons: synthesis, properties, and applications. J. Org. Chem. 85, 4–33 (2020).

    Article  CAS  Google Scholar 

  3. Zhou, X. & Yu, G. Modified engineering of graphene nanoribbons prepared via on‐surface synthesis. Adv. Mater. 32, 1905957 (2020).

    Article  CAS  Google Scholar 

  4. Chen, Y.-C. et al. Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions. Nat. Nanotechnol. 10, 156–160 (2015).

    Article  CAS  Google Scholar 

  5. Rizzo, D. J. et al. Topological band engineering of graphene nanoribbons. Nature 560, 204–208 (2018).

    Article  CAS  Google Scholar 

  6. Gröning, O. et al. Engineering of robust topological quantum phases in graphene nanoribbons. Nature 560, 209–213 (2018).

    Article  Google Scholar 

  7. Li, J. et al. Survival of spin state in magnetic porphyrins contacted by graphene nanoribbons. Sci. Adv. 4, eaaq0582 (2018).

    Article  Google Scholar 

  8. Li, J. et al. Electrically addressing the spin of a magnetic porphyrin through covalently connected graphene electrodes. Nano Lett. 19, 3288–3294 (2019).

    Article  Google Scholar 

  9. Mateo, L. M. et al. On‐surface synthesis and characterization of triply fused porphyrin–graphene nanoribbon hybrids. Angew. Chem. Int. Ed. 59, 1334–1339 (2020).

    Article  CAS  Google Scholar 

  10. Yazyev, O. V. A guide to the design of electronic properties of graphene nanoribbons. Acc. Chem. Res. 46, 2319–2328 (2013).

    Article  CAS  Google Scholar 

  11. Yazyev, O. V. Emergence of magnetism in graphene materials and nanostructures. Rep. Prog. Phys. 73, 056501 (2010).

    Article  Google Scholar 

  12. Fairbrother, A. et al. High vacuum synthesis and ambient stability of bottom-up graphene nanoribbons. Nanoscale 9, 2785–2792 (2017).

    Article  CAS  Google Scholar 

  13. Ma, C. et al. Oxidization stability of atomically precise graphene nanoribbons. Phys. Rev. Mater. 2, 014006 (2018).

    Article  CAS  Google Scholar 

  14. Berdonces-Layunta, A. et al. Chemical stability of (3,1)-chiral graphene nanoribbons. ACS Nano 15, 5610–5617 (2021).

    Article  CAS  Google Scholar 

  15. Yoon, K.-Y. & Dong, G. Liquid-phase bottom-up synthesis of graphene nanoribbons. Mater. Chem. Front. 4, 29–45 (2020).

    Article  CAS  Google Scholar 

  16. Narita, A., Wang, X.-Y., Feng, X. & Müllen, K. New advances in nanographene chemistry. Chem. Soc. Rev. 44, 6616–6643 (2015).

    Article  CAS  Google Scholar 

  17. Kan, E., Li, Z., Yang, J. & Hou, J. G. Half-metallicity in edge-modified zigzag graphene nanoribbons. J. Am. Chem. Soc. 130, 4224–4225 (2008).

    Article  CAS  Google Scholar 

  18. Carbonell-Sanromà, E. et al. Doping of graphene nanoribbons via functional group edge modification. ACS Nano 11, 7355–7361 (2017).

    Article  Google Scholar 

  19. Li, J. et al. Band depopulation of graphene nanoribbons induced by chemical gating with amino groups. ACS Nano 14, 1895–1901 (2020).

    Article  CAS  Google Scholar 

  20. Anthony, J. E. The larger acenes: versatile organic semiconductors. Angew. Chem. Int. Ed. 47, 452–483 (2008).

    Article  CAS  Google Scholar 

  21. Greene, T. W. & Wuts, P. G. M. Protective Groups in Organic Synthesis (Wiley, 1999).

  22. Chia, C.-I. & Crespi, V. H. Stabilizing the zigzag edge: graphene nanoribbons with sterically constrained terminations. Phys. Rev. Lett. 109, 076802 (2012).

    Article  Google Scholar 

  23. Li, Y., Zhou, Z., Cabrera, C. R. & Chen, Z. Preserving the edge magnetism of zigzag graphene nanoribbons by ethylene termination: insight by Clar’s rule. Sci. Rep. 3, 2030 (2013).

    Article  Google Scholar 

  24. Sun, Z. et al. Dibenzoheptazethrene isomers with different biradical characters: an exercise of Clar’s aromatic sextet rule in singlet biradicaloids. J. Am. Chem. Soc. 135, 18229–18236 (2013).

    Article  CAS  Google Scholar 

  25. Clair, S. & de Oteyza, D. G. Controlling a chemical coupling reaction on a surface: tools and strategies for on-surface synthesis. Chem. Rev. 119, 4717–4776 (2019).

    Article  CAS  Google Scholar 

  26. Wang, T. & Zhu, J. Confined on-surface organic synthesis: strategies and mechanisms. Surf. Sci. Rep. 74, 97–140 (2019).

    Article  CAS  Google Scholar 

  27. Held, P. A., Fuchs, H. & Studer, A. Covalent-bond formation via on-surface chemistry. Chem. Eur. J. 23, 5874–5892 (2017).

    Article  CAS  Google Scholar 

  28. Song, S. et al. On-surface synthesis of graphene nanostructures with π-magnetism. Chem. Soc. Rev. 50, 3238–3262 (2021).

    Article  CAS  Google Scholar 

  29. Liu, J. & Feng, X. Synthetic tailoring of graphene nanostructures with zigzag‐edged topologies: progress and perspectives. Angew. Chem. Int. Ed. 59, 23386–23401 (2020).

    Article  CAS  Google Scholar 

  30. Li, J. et al. Single spin localization and manipulation in graphene open-shell nanostructures. Nat. Commun. 10, 200 (2019).

    Article  Google Scholar 

  31. Mishra, S. et al. Topological frustration induces unconventional magnetism in a nanographene. Nat. Nanotechnol. 15, 22–28 (2020).

    Article  CAS  Google Scholar 

  32. Zuzak, R. et al. On-surface synthesis of chlorinated narrow graphene nanoribbon organometallic hybrids. J. Phys. Chem. Lett. 11, 10290–10297 (2020).

    Article  CAS  Google Scholar 

  33. Zuzak, R., Jančařík, A., Gourdon, A., Szymonski, M. & Godlewski, S. On-surface synthesis with atomic hydrogen. ACS Nano 14, 13316–13323 (2020).

    Article  CAS  Google Scholar 

  34. de Oteyza, D. G. et al. Substrate-independent growth of atomically precise chiral graphene nanoribbons. ACS Nano 10, 9000–9008 (2016).

    Article  Google Scholar 

  35. Merino-Díez, N. et al. Transferring axial molecular chirality through a sequence of on-surface reactions. Chem. Sci. 11, 5441–5446 (2020).

    Article  Google Scholar 

  36. Merino-Díez, N. et al. Unraveling the electronic structure of narrow atomically-precise chiral graphene nanoribbons. J. Phys. Chem. Lett. 9, 25–30 (2018).

    Article  Google Scholar 

  37. Li, J. et al. Topological phase transition in chiral graphene nanoribbons: from edge bands to end states. Nat. Commun. 12, 5538 (2021).

    Article  CAS  Google Scholar 

  38. Konishi, A. & Kubo, T. Benzenoid quinodimethanes. Top. Curr. Chem. 375, 83 (2017).

    Article  Google Scholar 

  39. Clar, E. The Aromatic Sextet (J. Wiley, 1972).

  40. Mohammed, M. S. G. et al. Electronic decoupling of polyacenes from the underlying metal substrate by sp3 carbon atoms. Commun. Phys. 3, 159 (2020).

    Article  CAS  Google Scholar 

  41. Merino-Díez, N. et al. Width-dependent band gap in armchair graphene nanoribbons reveals Fermi level pinning on Au(111). ACS Nano 11, 11661–11668 (2017).

    Article  Google Scholar 

  42. Endo, O., Nakamura, M., Amemiya, K. & Ozaki, H. Graphene nanoribbons formed from n-alkane by thermal dehydrogenation on Au(111) surface. Surf. Sci. 635, 44–48 (2015).

    Article  CAS  Google Scholar 

  43. Wang, T. et al. Magnetic interactions between radical pairs in chiral graphene nanoribbons. Nano Lett. 22, 164–171 (2022).

    Article  Google Scholar 

  44. Itoh, T., Matsuno, M., Kamiya, E., Hirai, K. & Tomioka, H. Preparation of copper ion complexes of sterically congested diaryldiazomethanes having a pyridine ligand and characterization of their photoproducts. J. Am. Chem. Soc. 127, 7078–7093 (2005).

    Article  CAS  Google Scholar 

  45. Di Giovannantonio, M. et al. On-surface growth dynamics of graphene nanoribbons: the role of halogen functionalization. ACS Nano 12, 74–81 (2018).

    Article  Google Scholar 

  46. Berdonces-Layunta, A. et al. Order from a mess: the growth of 5-armchair graphene nanoribbons. ACS Nano 15, 16552–16561 (2021).

    Article  CAS  Google Scholar 

  47. Blum, V. et al. Ab initio molecular simulations with numeric atom-centered orbitals. Comput. Phys. Commun. 180, 2175–2196 (2009).

    Article  CAS  Google Scholar 

  48. Becke, A. D. Density‐functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993).

    Article  CAS  Google Scholar 

  49. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  CAS  Google Scholar 

  50. Tkatchenko, A. & Scheffler, M. Accurate molecular van der Waals interactions from ground-state electron density and free-atom reference data. Phys. Rev. Lett. 102, 073005 (2009).

    Article  Google Scholar 

  51. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976).

    Article  Google Scholar 

  52. Lewis, J. P. et al. Advances and applications in the FIREBALL ab initio tight-binding molecular-dynamics formalism. Phys. Status Solidi B 248, 1989–2007 (2011).

    Article  CAS  Google Scholar 

  53. Hapala, P. et al. Mechanism of high-resolution STM/AFM imaging with functionalized tips. Phys. Rev. B 90, 085421 (2014).

  54. Krejčí, O., Hapala, P., Ondráček, M. & Jelínek, P. Principles and simulations of high-resolution STM imaging with a flexible tip apex. Phys. Rev. B 95, 045407 (2017).

    Article  Google Scholar 

Download references

Acknowledgements

Research was supported by MCIN/AEI/10.13039/501100011033 (grant nos PID2019-107338RB-C62 (D.P.), PID2019-107338RB-C63 (M.C. and D.G.d.O.) and FJC2019-041202-I (F.S.)); the European Union’s Horizon 2020 programme (grant nos 863098 (D.P.) and 635919 (D.G.d.O.), and Marie Skłodowska-Curie Actions Individual Fellowship no. 101022150 (T.W.)); the Gobierno Vasco (grant no. PIBA_2020_1_0036 (D.G.d.O.)); the Xunta de Galicia (Centro Singular de Investigación de Galicia, 2019–2022, grant no. ED431G2019/03 (D.P.)); the European Regional Development Fund; the Praemium Academie of the Academy of Science of the Czech Republic (GACR project no. 20-13692X (P.J.)); the Czech Nanolab Research Infrastructure supported by MEYS CR (project no. LM2018110 (P.J.)); and the Operational Programme for Research, Development and Education of the European Regional Development Fund (project no. CZ.02.1.01/0.0/0.0/16_019/0000754 (P.J.)). The funders had no role in study design, data collection and analysis, decision to publish or preparation of the manuscript.

Author information

Author notes

  1. These authors contributed equally: James Lawrence, Alejandro Berdonces-Layunta.

Authors and Affiliations

  1. Donostia International Physics Center, San Sebastián, Spain

    James Lawrence, Alejandro Berdonces-Layunta, Tao Wang, Mohammed S. G. Mohammed, Frederik Schiller, Martina Corso & Dimas G. de Oteyza

  2. Centro de Física de Materiales (MPC), CSIC-UPV/EHU, San Sebastián, Spain

    James Lawrence, Alejandro Berdonces-Layunta, Tao Wang, Rodrigo Castrillo-Bodero, Paula Angulo-Portugal, Mohammed S. G. Mohammed, Frederik Schiller, Martina Corso & Dimas G. de Oteyza

  3. Institute of Physics, Czech Academy of Sciences, Prague, Czech Republic

    Shayan Edalatmanesh, Alejandro Jimenez-Martin, Bruno de la Torre, Adam Matěj & Pavel Jelinek

  4. Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, Santiago de Compostela, Spain

    Jesús Castro-Esteban, Manuel Vilas-Varela & Diego Peña

  5. Regional Centre of Advanced Technologies and Materials, Czech Advanced Technology and Research Institute (CATRIN), Palacký University Olomouc, Olomouc, Czech Republic

    Alejandro Jimenez-Martin, Bruno de la Torre, Adam Matěj & Pavel Jelinek

  6. Faculty of Nuclear Sciences and Physical Engineering, Czech Technical University in Prague, Prague, Czech Republic

    Alejandro Jimenez-Martin

  7. Ikerbasque, Basque Foundation for Science, Bilbao, Spain

    Dimas G. de Oteyza

  8. Nanomaterials and Nanotechnology Research Center (CINN), CSIC-UNIOVI-PA, El Entrego, Spain

    Dimas G. de Oteyza

Authors
  1. James Lawrence
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Contributions

D.P. and D.G.d.O. conceived the research. J.C.-E., M.V.-V. and D.P. synthesized the reactants. J.L., A.B.-L., T.W., M.S.G.M. and D.G.d.O. performed on-surface synthesis and STM and scanning tunnelling spectroscopy characterization and analysis. A.J.-M. and B.d.l.T. performed on-surface synthesis and nc-AFM characterization and analysis. A.B.-L., R.C.-B., P.A.-P., F.S. and M.C. performed on-surface synthesis and XPS characterization and analysis. S.E., A.M. and P.J. performed the theoretical calculations. All authors contributed to the scientific discussion, as well as to the review and editing of the manuscript.

Corresponding authors

Correspondence to Pavel Jelinek, Diego Peña or Dimas G. de Oteyza.

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Extended data

Extended Data Fig. 1 XPS analysis monitoring the hydrogenation/dehydrogenation process of pristine and ketone-functionalized ribbons.

(a) C1s XPS spectra (symbols) of p-chGNRs “as grown” (top), after hydrogenation (middle) and after subsequent annealing (bottom), along with the fit (solid curve) and its associated components (coloured peaks). The data reveal the successful hydrogenation and its reversibility. (b) C1s XPS spectra (symbols) of k-chGNRs “as grown” (top), after hydrogenation (middle) and after subsequent annealing (bottom), along with the fit (solid curve) and its associated components (coloured peaks). The data reveal the gradual deoxidation upon hydrogenation and the subsequent annealing. Dashed lines act as a guide to the eye to compare the maxima on each of the spectra. Details about the fitting procedure are given in the methods section.

Source data

Extended Data Fig. 2 Comparison of ‘typical’ and ‘metal-copordinated’ k-chGNRs.

Comparison between the structures of the two types of ketone-functionalized GNRs that were observed. (a) Typical STM image of a self-assembled island that contains both types of ketone-GNR. I = 50 pA, Vbias = −0.5 V. (b) BR-STM image of a metal-coordinated and (c) typical section of a ketone-NR island. Both constant height, CO tip, Vbias = 4 mV and 5 mV, respectively. Scale bars are both 500 pm. (d) and (e) Models of the metal-coordinated and typical islands, with suggested positions for gold adatoms in the metal-coordinated model.

Source data

Extended Data Fig. 3 STM analysis of the air exposed k-chGNR sample before and after annealing.

(a) Overview STM image of a ketone-GNR sample that was exposed to air for 24 minutes, without any further treatment. I = 50 pA; Vbias = 1.5 V. (b) and (c): STM images of the same sample after annealing to 200 °C for 1 hour. (b) I = 20 pA; Vbias = −0.8 V. (c) I = 30 pA; Vbias = −0.8 V. Although most have desorbed, a notable number of contaminants are still present on the surface after the annealing treatment. Islands of alkyl chain contamination from the ambient conditions are indicated in (c) with a blue arrow.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–18.

Supplementary Data 1

Source data for Supplementary Fig. 1.

Supplementary Data 2

Source data for Supplementary Fig. 9.

Source data

Source Data Fig. 2

Scanning probe microscopy images for Fig. 2.

Source Data Fig. 3

Scanning probe microscopy images for Fig. 3.

Source Data Fig. 4

Conductance spectra, scanning probe microscopy images, calculated band structure and calculated wavefunctions for Fig. 4.

Source Data Fig. 5

Conductance spectra and calculated atomic positions for Fig. 5

Source Data Fig. 6

Scanning probe microscopy images for Fig. 6.

Source Data Extended Data Fig. 1

Unprocessed XPS data for the pristine and ketone-functionalized ribbons as grown, after hydrogen exposure and after subsequent annealing.

Source Data Extended Data Fig. 2

Scanning probe microscopy images for Extended Data Fig. 2.

Source Data Extended Data Fig. 3

Scanning probe microscopy images for Extended Data Fig. 3.

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Lawrence, J., Berdonces-Layunta, A., Edalatmanesh, S. et al. Circumventing the stability problems of graphene nanoribbon zigzag edges. Nat. Chem. 14, 1451–1458 (2022). https://doi.org/10.1038/s41557-022-01042-8

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