Location via proxy:   [ UP ]  
[Report a bug]   [Manage cookies]                
Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Towards chirality control of graphene nanoribbons embedded in hexagonal boron nitride

Nature Materials volume 20, pages 202–207 (2021)Cite this article

Subjects

Abstract

The integrated in-plane growth of graphene nanoribbons (GNRs) and hexagonal boron nitride (h-BN) could provide a promising route to achieve integrated circuitry of atomic thickness. However, fabrication of edge-specific GNRs in the lattice of h-BN still remains a significant challenge. Here we developed a two-step growth method and successfully achieved sub-5-nm-wide zigzag and armchair GNRs embedded in h-BN. Further transport measurements reveal that the sub-7-nm-wide zigzag GNRs exhibit openings of the bandgap inversely proportional to their width, while narrow armchair GNRs exhibit some fluctuation in the bandgap-width relationship. An obvious conductance peak is observed in the transfer curves of 8- to 10-nm-wide zigzag GNRs, while it is absent in most armchair GNRs. Zigzag GNRs exhibit a small magnetic conductance, while armchair GNRs have much higher magnetic conductance values. This integrated lateral growth of edge-specific GNRs in h-BN provides a promising route to achieve intricate nanoscale circuits.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Synthetic strategy of oriented GNRs embedded in h-BN.
Fig. 2: Edge-specific nano-trenches and GNRs embedded in top layer of h-BN.
Fig. 3: Electronic transport through GNR devices on h-BN.
Fig. 4: Field-effect and magneto-electrical properties in relatively wide GNRs in h-BN.

Similar content being viewed by others

Data availability

The data represented in Figs. 3 and 4 are provided with the paper as source data. All other data that support results in this Article are available from the corresponding authors on reasonable request. Source data are provided with this paper.

References

  1. Son, Y.-W., Cohen, M. L. & Louie, S. G. Half-metallic graphene nanoribbons. Nature 444, 347–349 (2006).

    Article  CAS  Google Scholar 

  2. Llinas, J. P. et al. Short-channel field-effect transistors with 9-atom and 13-atom wide graphene nanoribbons. Nat. Commun. 8, 633 (2017).

    Article  Google Scholar 

  3. Baringhaus, J. et al. Exceptional ballistic transport in epitaxial graphene nanoribbons. Nature 506, 349–354 (2014).

    Article  CAS  Google Scholar 

  4. Nakada, K., Fujita, M., Dresselhaus, G. & Dresselhaus, M. S. Edge state in graphene ribbons: nanometer size effect and edge shape dependence. Phys. Rev. B 54, 17954–17961 (1996).

    Article  CAS  Google Scholar 

  5. Magda, G. Z. et al. Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons. Nature 514, 608–611 (2014).

    Article  CAS  Google Scholar 

  6. Ruffieux, P. et al. On-surface synthesis of graphene nanoribbons with zigzag edge topology. Nature 531, 489–492 (2016).

    Article  CAS  Google Scholar 

  7. 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, 186801 (2007).

    Article  Google Scholar 

  8. Son, Y.-W., Cohen, M. L. & Louie, S. G. Energy gaps in graphene nanoribbons. Phys. Rev. Lett. 97, 216803 (2006).

    Article  Google Scholar 

  9. Jia, X. et al. Graphene edges: a review of their fabrication and characterization. Nanoscale 3, 86–95 (2011).

    Article  CAS  Google Scholar 

  10. Wassmann, T. et al. Structure, stability, edge states, and aromaticity of graphene ribbons. Phys. Rev. Lett. 101, 096402 (2008).

    Article  Google Scholar 

  11. Seitsonen, A. P. et al. Structure and stability of graphene nanoribbons in oxygen, carbon dioxide, water, and ammonia. Phys. Rev. B 82, 115425 (2010).

    Article  Google Scholar 

  12. Jia, X. et al. Controlled formation of sharp zigzag and armchair edges in graphitic nanoribbons. Science 323, 1701–1705 (2009).

    Article  CAS  Google Scholar 

  13. Girit, Ç. Ö. et al. Graphene at the edge: stability and dynamics. Science 323, 1705–1708 (2009).

    Article  CAS  Google Scholar 

  14. Kim, K. et al. Atomically perfect torn graphene edges and their reversible reconstruction. Nat. Commun. 4, 2723 (2013).

    Article  Google Scholar 

  15. Geim, A. K. & Grigorieva, I. V. Van der Waals heterostructures. Nature 499, 419–425 (2013).

    Article  CAS  Google Scholar 

  16. Novoselov, K. S., Mishchenko, A., Carvalho, A. & Castro Neto, A. H. 2D materials and van der Waals heterostructures. Science 353, aac9439 (2016).

    Article  CAS  Google Scholar 

  17. Ci, L. et al. Atomic layers of hybridized boron nitride and graphene domains. Nat. Mater. 9, 430–435 (2010).

    Article  CAS  Google Scholar 

  18. Liu, L. et al. Heteroepitaxial growth of two-dimensional hexagonal boron nitride templated by graphene edges. Science 343, 163–167 (2014).

    Article  CAS  Google Scholar 

  19. Levendorf, M. P. et al. Graphene and boron nitride lateral heterostructures for atomically thin circuitry. Nature 488, 627–632 (2012).

    Article  CAS  Google Scholar 

  20. Liu, Z. et al. In-plane heterostructures of graphene and hexagonal boron nitride with controlled domain sizes. Nat. Nanotechnol. 8, 119–124 (2013).

    Article  CAS  Google Scholar 

  21. Gong, Y. J. et al. Direct chemical conversion of graphene to boron- and nitrogen- and carbon-containing atomic layers. Nat. Commun. 5, 3193 (2014).

    Article  Google Scholar 

  22. Li, K. & Zhang, X.-H. Asymmetrical edges induced strong current-polarization in embedded graphene nanoribbons. Phys. Lett. A 382, 1167–1170 (2018).

    Article  CAS  Google Scholar 

  23. Ding, Y., Wang, Y. & Ni, J. Electronic properties of graphene nanoribbons embedded in boron nitride sheets. Appl. Phys. Lett. 95, 123105 (2009).

    Article  Google Scholar 

  24. Lu, X. et al. Graphene nanoribbons epitaxy on boron nitride. Appl. Phys. Lett. 108, 113103 (2016).

    Article  Google Scholar 

  25. Chen, L. et al. Edge control of graphene domains grown on hexagonal boron nitride. Nanoscale 9, 11475–11479 (2017).

    Article  CAS  Google Scholar 

  26. Tang, S. et al. Silane-catalysed fast growth of large single-crystalline graphene on hexagonal boron nitride. Nat. Commun. 6, 6499 (2015).

    Article  CAS  Google Scholar 

  27. Mashoff, T. et al. Bistability and oscillatory motion of natural nanomembranes appearing within monolayer graphene on silicon dioxide. Nano Lett. 10, 461–465 (2010).

    Article  CAS  Google Scholar 

  28. Susi, T. et al. Isotope analysis in the transmission electron microscope. Nat. Commun. 7, 13040 (2016).

    Article  CAS  Google Scholar 

  29. Hawkes, P. W. Advances in Imaging and Electron Physics Vol. 138 (Elsevier, 2005).

  30. Chen, L. et al. Oriented graphene nanoribbons embedded in hexagonal boron nitride trenches. Nat. Commun. 8, 14703 (2017).

    Article  Google Scholar 

  31. Javey, A., Guo, J., Wang, Q., Lundstrom, M. & Dai, H. Ballistic carbon nanotube field-effect transistors. Nature 424, 654–657 (2003).

    Article  CAS  Google Scholar 

  32. Mann, D., Javey, A., Kong, J., Wang, Q. & Dai, H. Ballistic transport in metallic nanotubes with reliable Pd ohmic contacts. Nano Lett. 3, 1541–1544 (2003).

    Article  CAS  Google Scholar 

  33. Pereira, V. M., Neto, A. H. C. & Peres, N. M. R. Tight-binding approach to uniaxial strain in graphene. Phys. Rev. B 80, 045401 (2009).

    Article  Google Scholar 

  34. Hunt, B. et al. Massive Dirac fermions and Hofstadter butterfly in a van der Waals heterostructure. Science 340, 1427–1430 (2013).

    Article  CAS  Google Scholar 

  35. Wu, S. et al. Magnetotransport properties of graphene nanoribbons with zigzag edges. Phys. Rev. Lett. 120, 216601 (2018).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  37. Heimes, A., Kotetes, P. & Schön, G. Majorana fermions from Shiba states in an antiferromagnetic chain on top of a superconductor. Phys. Rev. B 90, 060507 (2014).

    Article  Google Scholar 

Download references

Acknowledgements

H.W. and X.X. thank J.H. Edgar (Kansas State University, USA) for supplying the partial h-BN crystals. H. S. Wang, L. Chen and H. Wang thank M. Liu, X. Qiu and J. Pan from NCNT of China, F. Liou, H. Tsai, M. Crommie from UCB, USA, J. Xue and P. Yu from ShanghaiTech University and S. Wang from SJTU for nc-AFM measurement. H. S. Wang, L. Chen and H. Wang thank B. Sun and S. Li from Hunan University for the fusion of the STEM image and the electron energy loss spectroscopy mapping images. Funding: The work was partially supported by the National Key R&D program (Grant No. 2017YFF0206106), the Strategic Priority Research Program of Chinese Academy of Sciences (Grant No. XDB30000000), the National Science Foundation of China (Grant No. 51772317, 51302096, 61774040, 91964102), the Science and Technology Commission of Shanghai Municipality (Grant No. 16ZR1442700, 16ZR1402500 18511110700), Shanghai Rising-Star Program (A type) (Grant No.18QA1404800), the Hubei Provincial Natural Science Foundation of China (Grant No. ZRMS2017000370), China Postdoctoral Science Foundation (Grant No. 2017M621563, 2018T110415), and the Fundamental Research Funds of Wuhan City (No. 2016060101010075). C.L. acknowledges support from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grants No. 656378 – Interfacial Reactions. T.J.P. acknowledges funding from European Union’s Horizon 2020 Research and Innovation Programme under the Marie Sklodowska-Curie grant agreement no. ~655760–DIGIPHASE. K.W. and T.T. acknowledge support from the Elemental Strategy Initiative conducted by the MEXT, Japan and the CREST (JPMJCR15F3), JST. C.X.C. acknowledges financial support from the National Young 1000 Talent Plan of China and the National Key R&D Program of China (No. 2018YFA0703700). L.H. acknowledges financial support from the programme of China Scholarships Council (No. 201706160037).

Author information

Author notes

  1. Jannik C. Meyer

    Present address: Institute of Applied Physics, University of Tübingen, Tübingen, Germany

  2. These authors contributed equally: Hui Shan Wang, Lingxiu Chen, Kenan Elibol, Li He.

Authors and Affiliations

  1. State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai, P. R. China

    Hui Shan Wang, Lingxiu Chen, Haomin Wang, Chen Chen, Chengxin Jiang, Tianru Wu & Xiaoming Xie

  2. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, P. R. China

    Hui Shan Wang, Haomin Wang, Chen Chen & Xiaoming Xie

  3. CAS Center for Excellence in Superconducting Electronics (CENSE), Shanghai, P. R. China

    Hui Shan Wang, Lingxiu Chen, Haomin Wang, Chen Chen, Chengxin Jiang, Tianru Wu & Xiaoming Xie

  4. Faculty of Physics, University of Vienna, Vienna, Austria

    Kenan Elibol, Timothy J. Pennycook, Giacomo Argentero & Jannik C. Meyer

  5. School of Chemistry, CRANN - Advanced Microscopy Laboratory, Trinity College Dublin, Dublin, Ireland

    Kenan Elibol

  6. School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan, P. R. China

    Li He & Daoli Zhang

  7. School of Physical Science and Technology, ShanghaiTech University, Shanghai, P. R. China

    Chengxin Jiang & Xiaoming Xie

  8. Department of Lithospheric Research, University of Vienna, Vienna, Austria

    Chen Li

  9. Electron Microscopy for Materials Research (EMAT), University of Antwerpen, Antwerpen, Belgium

    Chen Li & Timothy J. Pennycook

  10. State Key Laboratory of ASIC & System, School of Information Science and Technology, Fudan University, Shanghai, P. R. China

    Chun Xiao Cong

  11. National Institute for Materials Science, Tsukuba, Japan

    Kenji Watanabe & Takashi Taniguchi

  12. State Key Laboratory of Precision Spectroscopy, School of Physics and Material Science, East China Normal University, Shanghai, P. R. China

    Wenya Wei & Qinghong Yuan

  13. Centre for Theoretical and Computational Molecular Science, Australian Institute for Bioengineering and Nanotechnology, The University of Queensland, Brisbane, Australia

    Wenya Wei & Qinghong Yuan

Authors
  1. Hui Shan Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lingxiu Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Kenan Elibol
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Li He
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Haomin Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Chen Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Chengxin Jiang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Chen Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Tianru Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Chun Xiao Cong
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Timothy J. Pennycook
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Giacomo Argentero
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Daoli Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Kenji Watanabe
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Takashi Taniguchi
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Wenya Wei
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Qinghong Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Jannik C. Meyer
    View author publications

    You can also search for this author in PubMed Google Scholar

  19. Xiaoming Xie
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

H.W. and X.X. directed the research work. H.W. conceived and designed the research. L.H., H.S.W. and C.C. performed the etching processes on h-BN. T.W. suggested the use of platinum as the cutting particle. L.C. and C.J. performed the growth experiments for the GNRs. L.C., C.C., C.J. and H.S.W. performed the AFM measurements. H.S.W. fabricated the electronic devices and performed the transport measurements. C.X.C. performed the Raman measurements. K.E., C.L., T.J.P., G.A. and J.C.M. carried out the STEM measurements. K.W. and T.T. fabricated the h-BN crystals. W.W. and Q.Y. performed the thermodynamic simulation for h-BN edges and GNR growth. H.W., H.S.W., L.C., J.C.M., K.E., L.H. and C.X.C. analysed the experimental data and designed the figures. H.W., H.S.W. and J.C.M. co-wrote the manuscript, and all authors contributed to critical discussions of the manuscript.

Corresponding authors

Correspondence to Haomin Wang or Jannik C. Meyer.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 AFM investigation on h-BN nano-trenches obtained via nickel and platinum nano-particle etching.

a, AFM friction image of zigzag oriented trenches produced by nickel particles. The trenches exhibit about -30°, 30° or 90° with respect to h-BN wrinkles which are armchair oriented. The green dash line represents a trench orientation while the white dash line denotes a wrinkle orientation. Inset is a zoom-in view of the selected region in-lattice-resolution, confirming that the trenches are along the zigzag direction. The lattice-resolution AFM friction image is Fourier filtered for clarity. b, Occurrences of all trenches obtained via nickel assisted etching versus their azimuthal angle. Histogram shows that three specific angles (-30°, 30°and 90°) are preferred. It indicates that zigzag direction dominates in the trenches etched by Ni nanoparticles. c, AFM friction image of armchair oriented trenches on h-BN cut by platinum particles. The trenches exhibit about -60°, 0° or 60° with respect to the h-BN wrinkles. The green dash line represents a trench orientation while the white dash line denotes a wrinkle orientation. Inset is a zoom-in view of the selected region shown in (c), showing Fourier filtered lattice-resolution AFM friction image, confirming that the trenches are along the armchair direction. d, Occurrences of all trenches obtained via platinum assisted etching versus their azimuthal angle. Histogram shows three specific angles (-60°, 0°and 60°) are preferred by the Pt assisted etching. It means that armchair orientation dominates in all trenches etched by Pt nanoparticles.

Extended Data Fig. 2 High resolution analysis of ZZ-oriented nano-trenches and ZGNRs embedded in h-BN lattices.

a-d, AFM height images of mono-layered ZZ-oriented nano-trenches in h-BN surface by Ni particle-catalyzed cutting. The scale bars are 500, 100, 100 and 200 nm, respectively. The circular inset in (a) shows an atomic-resolution friction image of the h-BN. All the trenches are found along ZZ direction. b,c, show nano-trenches narrower than 5 nm. d, For a ~ 78 nm-wide trench, the depth profile shows that etching occurs only at the top layer of h-BN substrate. e-h, AFM height images of GNRs embedded in the ZZ-oriented nano-trenches. The width of ZGNRs is less than 10 nm. The scale bars are 500, 200, 100 and 100 nm, respectively. i, A STEM MAADF-α×HAADF image for a ZGNR sample. The scale bar is 200 nm. j, A zoomed-in MAADF image of a region shown in the middle of white dashed frame in (i). The scale bar is 10 nm. k, A Wiener-filtered MAADF image of the region shown in the dashed frame in j, The STEM investigation indicates that the boundaries between GNR and h-BN can be distinguished with a scale bar of 2 nm. The measured in-plane width of the GNR is ~3.2 nm.

Extended Data Fig. 3 High-resolution characterization of AC-oriented nano-trenches and AGNRs embedded in h-BN trenches.

a-d, AFM height images of mono-layered AC-oriented trenches obtained via Pt particle-assisted etching. The scale bars are 500, 100, 100 and 50 nm, respectively. The inset circular in (a) shows atomic-resolution friction image of h-BN. The white hexagons in the inset help with the identification of the atomic structure of GNR. All the trenches are found along AC directions. The width of the trench is less than 5 nm. d, shows an AC-oriented trench in width of ~23 nm, the profile of the depth indicates that etching occurs only at the top layer of h-BN surface. e-h, AFM height images of AGNRs embedded in the AC nano-trenches. The scale bars are 500, 200, 100 and 100 nm, respectively. The width of AGNRs is less than 10 nm. i, STEM-MAADF images of an AGNR sample. j, The magnified image of the AGNR area pointed to by the arrow in i, and the two dashed lines show the boundary between h-BN and AGNR. The scale bar in (i) is 100 nm and in (j) is 3 nm. The width of the GNR is ~5.3 nm. k, The fast Fourier transform (FFT) image for (j), indicating that the GNR is along the AC lattice direction.

Supplementary information

Supplementary Information

Supplementary text, Figs. 1–39 and Tables 1 and 2.

Source data

Source Data Fig. 3

Experimental data points of Fig. 3a–f.

Source Data Fig. 4

Experimental data points of Fig. 4a–f.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, H.S., Chen, L., Elibol, K. et al. Towards chirality control of graphene nanoribbons embedded in hexagonal boron nitride. Nat. Mater. 20, 202–207 (2021). https://doi.org/10.1038/s41563-020-00806-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-020-00806-2

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing