Letter | Published:

Intermixing and periodic self-assembly of borophene line defects

Nature Materialsvolume 17pages783788 (2018) | Download Citation

Abstract

Two-dimensional (2D) boron (that is, borophene) was recently synthesized following theoretical predictions1,2,3,4,5. Its metallic nature and high in-plane anisotropy combine many of the desirable attributes of graphene6 and monolayer black phosphorus7. As a synthetic 2D material, its structural properties cannot be deduced from bulk boron, which implies that the intrinsic defects of borophene remain unexplored. Here we investigate borophene line defects at the atomic scale with ultrahigh vacuum (UHV) scanning tunnelling microscopy/spectroscopy (STM/STS) and density functional theory (DFT). Under suitable growth conditions, borophene phases that correspond to the v1/6 and v1/5 models are found to intermix and accommodate line defects in each other with structures that match the constituent units of the other phase. These line defects energetically favour spatially periodic self-assembly that gives rise to new borophene phases, which ultimately blurs the distinction between borophene crystals and defects. This phenomenon is unique to borophene as a result of its high in-plane anisotropy and energetically and structurally similar polymorphs. Low-temperature measurements further reveal subtle electronic features that are consistent with a charge density wave (CDW), which are modulated by line defects. This atomic-level understanding is likely to inform ongoing efforts to devise and realize applications based on borophene.

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References

  1. 1.

    Mannix, A. J. et al. Synthesis of borophenes: anisotropic, two-dimensional boron polymorphs. Science 350, 1513–1516 (2015).

  2. 2.

    Feng, B. et al. Experimental realization of two-dimensional boron sheets. Nat. Chem. 8, 563–568 (2016).

  3. 3.

    Zhang, Z., Yang, Y., Gao, G. & Yakobson, B. I. Two-dimensional boron monolayers mediated by metal substrates. Angew. Chem. Int. Ed. 54, 13022–13026 (2015).

  4. 4.

    Wu, X. et al. Two-dimensional boron monolayer sheets. ACS Nano 6, 7443–7453 (2012).

  5. 5.

    Tang, H. & Ismail-Beigi, S. Self-doping in boron sheets from first principles: a route to structural design of metal boride nanostructures. Phys. Rev. B 80, 170 (2009).

  6. 6.

    Novoselov, K. S. et al. Electric field effect in atomically thin carbon films. Science 306, 666–669 (2004).

  7. 7.

    Liu, X., Ryder, C. R., Wells, S. A. & Hersam, M. C. Resolving the in-plane anisotropic properties of black phosphorus. Small Methods 1, 1700143 (2017).

  8. 8.

    Mannix, A. J., Kiraly, B., Hersam, M. C. & Guisinger, N. P. Synthesis and chemistry of elemental 2D materials. Nat. Rev. Chem. 1, 0014 (2017).

  9. 9.

    Zhang, Z. et al. Substrate-induced nanoscale undulations of borophene on silver. Nano Lett. 16, 6622–6627 (2016).

  10. 10.

    Tsafack, T. & Yakobson, B. I. Thermomechanical analysis of two-dimensional boron monolayers. Phys. Rev. B 93, 165434 (2016).

  11. 11.

    Wang, H. et al. Strain effects on borophene: ideal strength, negative Poisson’s ratio and phonon instability. New J. Phys. 18, 073016 (2016).

  12. 12.

    Zhang, Z., Yang, Y., Penev, E. S. & Yakobson, B. I. Elasticity, flexibility, and ideal strength of borophenes. Adv. Funct. Mater. 27, 1605059 (2017).

  13. 13.

    Liu, X. et al. Self-assembly of electronically abrupt borophene/organic lateral heterostructures. Sci. Adv. 3, e1602356 (2017).

  14. 14.

    Feng, B. et al. Dirac fermions in borophene. Phys. Rev. Lett. 118, 096401 (2017).

  15. 15.

    Penev, E. S., Kutana, A. & Yakobson, B. I. Can two-dimensional boron superconduct? Nano Lett. 16, 2522–2526 (2016).

  16. 16.

    Huang, P. Y. et al. Grains and grain boundaries in single-layer graphene atomic patchwork quilts. Nature 469, 389–392 (2011).

  17. 17.

    Zhao, L. et al. Visualizing individual nitrogen dopants in monolayer graphene. Science 333, 999–1003 (2011).

  18. 18.

    van der Zande, A. M. Grains and grain boundaries in highly crystalline monolayer molybdenum disulphide. Nat. Mater. 12, 554–561 (2013).

  19. 19.

    Liu, X., Balla, I., Bergeron, H. & Hersam, M. C. Point defects and grain boundaries in rotationally commensurate MoS2 on epitaxial graphene. J. Phys. Chem. C 120, 20798–20805 (2016).

  20. 20.

    Hong, J. et al. Exploring atomic defects in molybdenum disulphide monolayers. Nat. Commun. 6, 6293 (2015).

  21. 21.

    Muzychenko, D. A., Schouteden, K., Panov, V. I. & Van Haesendonck, C. Formation of Co/Ge intermixing layers after Co deposition on Ge(111)2 × 1 surfaces. Nanotechnology 23, 435605 (2012).

  22. 22.

    Leibsle, F. M., Dhesi, S. S., Barrett, S. D. & Robinson, A. W. STM observations of Cu(100)−c(2×2)N surfaces: evidence for attractive interactions and an incommensurate c(2×2)structure. Surf. Sci. 317, 309–320 (1994).

  23. 23.

    Xu, T. T. et al. Crystalline boron nanoribbons: synthesis and characterization. Nano Lett. 4, 963–968 (2004).

  24. 24.

    Moras, P., Mentes, T. O., Sheverdyaeva, P. M., Locatelli, A. & Carbone, C. Coexistence of multiple silicene phases in silicon grown on Ag(111). J. Phys. Condens. Matter 26, 185001 (2014).

  25. 25.

    Feng, B. et al. Evidence of silicene in honeycomb structures of silicon on Ag(111). Nano Lett. 12, 3507–3511 (2012).

  26. 26.

    Zhuang, J. et al. Investigation of electron–phonon coupling in epitaxial silicene by in situ Raman spectroscopy. Phys. Rev. B 91, 161409 (2015).

  27. 27.

    Guan, J., Zhu, Z. & Tománek, D. High stability of faceted nanotubes and fullerenes of multiphase layered phosphorus: a computational study. Phys. Rev. Lett. 113, 226801 (2014).

  28. 28.

    Aierken, Y., Leenaerts, O. & Peeters, F. M. Defect-induced faceted blue phosphorene nanotubes. Phys. Rev. B 92, 104104 (2015).

  29. 29.

    Xiang, P. et al. Metallic borophene polytypes as lightweight anode materials for non-lithium-ion batteries. Phys. Chem. Chem. Phys. 19, 24945–24954 (2017).

  30. 30.

    Huang, Y., Shirodkar, S. N. & Yakobson, B. I. Two-dimensional boron polymorphs for visible range plasmonics: a first-principles exploration. J. Am. Chem. Soc. 139, 17181–17185 (2017).

  31. 31.

    Foley, E. T., Yoder, N. L., Guisinger, N. P. & Hersam, M. C. Cryogenic variable temperature ultrahigh vacuum scanning tunneling microscope for single molecule studies on silicon surfaces. Rev. Sci. Instrum. 75, 5280–5287 (2004).

  32. 32.

    Brockenbrough, R. T. & Lyding, J. W. Inertial tip translator for a scanning tunneling microscope. Rev. Sci. Instrum. 64, 2225–2228 (1993).

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Acknowledgements

X.L. and M.C.H. acknowledge support from the Office of Naval Research (ONR N00014-17-1-2993) and the National Science Foundation Materials Research Science and Engineering Center (NSF DMR-1720139). The computational work at Rice University was supported by the Army Research Office (W911NF-16-1-0255) and by the Robert Welch Foundation (C-1590); Z.Z. acknowledges NSFC-11772153 support at a later stage. Z.Z., L.W. and B.I.Y. also acknowledge support by the US DOE Office of Science (DOE DE-SC0012547) and the Research Fund of State Key Laboratory of Mechanics and Control of Mechanical Structures (no. MCMS-0415K01). X.L. further acknowledges support from a Ryan Fellowship that is administered through the Northwestern University International Institute for Nanotechnology. The authors thank A. J. Mannix, M. Han, I. Balla, S. Li, E. S. Penev and Q. Ruan for valuable discussions.

Author information

Affiliations

  1. Applied Physics Graduate Program, Northwestern University, Evanston, IL, USA

    • Xiaolong Liu
    •  & Mark C. Hersam
  2. Department of Materials Science and NanoEngineering, Rice University, Houston, TX, USA

    • Zhuhua Zhang
    • , Luqing Wang
    •  & Boris I. Yakobson
  3. State Key Laboratory of Mechanics and Control of Mechanical Structures and Institute of Nano Science, Nanjing University of Aeronautics and Astronautics, Nanjing, China

    • Zhuhua Zhang
  4. Department of Chemistry, Rice University, Houston, TX, USA

    • Boris I. Yakobson
  5. Department of Materials Science and Engineering, Northwestern University, Evanston, IL, USA

    • Mark C. Hersam
  6. Department of Chemistry, Northwestern University, Evanston, IL, USA

    • Mark C. Hersam
  7. Department of Electrical Engineering and Computer Science, Northwestern University, Evanston, IL, USA

    • Mark C. Hersam

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Contributions

X.L. and M.C.H. conceived the experiments. X.L. performed the sample preparation, STM/STS and XPS characterization. Z.Z., L.W. and B.I.Y. designed the models. Z.Z. and L.W. performed the DFT simulations. X.L. provided assistance with the model construction. All the authors contributed to the data interpretation and manuscript writing.

Competing interests

The authors declare no competing interests.

Corresponding author

Correspondence to Mark C. Hersam.

Supplementary information

  1. Supplementary Information

    Supplementary Figures 1–11, Supplementary Table 1 and Supplementary Note 1

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https://doi.org/10.1038/s41563-018-0134-1

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