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Atomic layers of hybridized boron nitride and graphene domains

Nature Materials volume 9, pages 430435 (2010) | Download Citation

Abstract

Two-dimensional materials, such as graphene and monolayer hexagonal BN (h-BN), are attractive for demonstrating fundamental physics in materials and potential applications in next-generation electronics. Atomic sheets containing hybridized bonds involving elements B, N and C over wide compositional ranges could result in new materials with properties complementary to those of graphene and h-BN, enabling a rich variety of electronic structures, properties and applications. Here we report the synthesis and characterization of large-area atomic layers of h-BNC material, consisting of hybridized, randomly distributed domains of h-BN and C phases with compositions ranging from pure BN to pure graphene. Our studies reveal that their structural features and bandgap are distinct from those of graphene, doped graphene and h-BN. This new form of hybrid h-BNC material enables the development of bandgap-engineered applications in electronics and optics and properties that are distinct from those of graphene and h-BN.

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References

  1. 1.

    & The rise of graphene. Nature Mater. 6, 183–191 (2007).

  2. 2.

    et al. N-doping of graphene through electrothermal reactions with ammonia. Science 324, 768–771 (2009).

  3. 3.

    , , & Electronic and transport properties of boron-doped graphene nanoribbons. Phys. Rev. Lett. 98, 196803 (2007).

  4. 4.

    , , , & Charge transport in chemically doped 2D graphene. Phys. Rev. Lett. 101, 036808 (2008).

  5. 5.

    et al. Synthesis of BxCyNz nanotubules. Phys. Rev. B 51, 11229–11232 (1995).

  6. 6.

    , , & Synthesis, analysis and electrical property measurements of compounds nanotubes in the ceramic B–C–N system. MRS Bull. 29, 38–42 (2004).

  7. 7.

    , , , & Boron–carbon–nitrogen materials of graphite-like structure. Mater. Res. Bull. 22, 399–404 (1987).

  8. 8.

    , & Atomic arrangement and electronic structure of BC2N. Phys. Rev. B 39, 1760–1765 (1989).

  9. 9.

    , , & Chiral tubules of hexagonal BC2N. Phys. Rev. B 50, 4976–4979 (1994).

  10. 10.

    , , & Elastic properties of C and BxCyNz composite nanotubes. Phys. Rev. Lett. 80, 4502–4505 (1998).

  11. 11.

    , & Syntheses and structures of new graphite-like materials of composition BCN(h) and BC2N(H). Chem. Mater. 8, 1197–1201 (1996).

  12. 12.

    et al. Synthesis of nanoparticles and nanotubes with well-separated layers of boron nitride and carbon. Science 278, 653–655 (1997).

  13. 13.

    , , & Transformation of BxCyNz nanotubes to pure BN nanotubes. Appl. Phys. Lett. 81, 1110–1112 (2002).

  14. 14.

    et al. Double atomic layers of graphene/monolayer h-BN on Ni(111) studied by scanning tunnelling microscopy and scanning tunnelling spectroscopy. Surf. Rev. Lett. 9, 1459–1464 (2002).

  15. 15.

    , , , & Substrate-induced band gap in graphene on hexagonal boron nitride: Ab initio density functional calculations. Phys. Rev. B 76, 073103 (2007).

  16. 16.

    , & Direct-band gap properties and evidence for ultraviolet lasing of hexagonal boron nitride single crystal. Nature Mater. 3, 404–409 (2004).

  17. 17.

    , , & Deep ultraviolet light–emitting hexagonal boron nitride synthesized at atmospheric pressure. Science 317, 932–934 (2007).

  18. 18.

    et al. Large area, few-layer graphene films on arbitrary substrates by chemical vapour deposition. Nano Lett. 9, 30–35 (2009).

  19. 19.

    et al. Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009).

  20. 20.

    , & Monolayer of h-BN chemisorbed on Cu(111) and Ni(111). Surf. Sci. 582, 21–30 (2005).

  21. 21.

    , , & Evolution of graphene growth on Cu and Ni studied by carbon isotope labeling. Nano Lett. 9, 4268–4272 (2009).

  22. 22.

    et al. Doping graphitic and carbon nanotube structures with boron and nitrogen. Science 266, 1683–1685 (1994).

  23. 23.

    et al. Novel aspects of graphite intercalation by fluorine and fluorides and new B/C, C/N and B/C/N materials based on the graphite network. Synth. Met. 34, 1–7 (1989).

  24. 24.

    , , , & Direct imaging of rotational stacking faults in few layer graphene. Nano Lett. 9, 102–106 (2009).

  25. 25.

    , , & Bonding characterization of BC2N thin films. Appl. Phys. Lett. 68, 2962–2964 (1996).

  26. 26.

    et al. Studying disorder in graphite-based systems by Raman spectroscopy. Phys. Chem. Chem. Phys. 9, 1276–1291 (2007).

  27. 27.

    , & Optical properties and electronic structure of amorphous germanium. Phys. Status Solidi 15, 627–637 (1966).

  28. 28.

    Effects of the layer thickness on the electronic character in GaAs–AlAs superlattices. Appl. Phys. Lett. 50, 1068–1070 (1987).

  29. 29.

    , , & Electrical properties of BC2N thin films prepared by chemical vapour deposition. J. Appl. Phys. 78, 2880–2882 (1995).

  30. 30.

    , , & Visible-light-emitting layered BC2N semiconductor. Phys. Rev. Lett. 77, 187–189 (1996).

  31. 31.

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

  32. 32.

    , , & Energy band-gap engineering of graphene nanoribbons. Phys. Rev. Lett. 98, 206805 (2007).

  33. 33.

    , , , & Band gap scaling of graphene nanohole superlattices. Phys. Rev. B 80, 233405 (2009).

  34. 34.

    Phase stability of boron carbon nitride in a heterographene structure. Phys. Rev. B 79, 144109 (2009).

  35. 35.

    Effects of nanodomain formation on the electronic structure of doped carbon nanotubes. Phys. Rev. Lett. 81, 2332–2335 (1998).

  36. 36.

    et al. Localization and the Kosterlitz–Thouless transition in disordered graphene. Phys. Rev. Lett. 102, 106401 (2009).

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Acknowledgements

P.M.A. acknowledges support from Rice University start-up funds and funding support from the Office of Naval Research (ONR) through the MURI programme on graphene and the Basic Energy Sciences division of the Department of Energy (DOE). L.C. (for work carried out on graphene growth and structural characterization) was supported by the ONR MURI programme (award No N00014-09-1-1066) and L.S. (for work done in device fabrication and electrical characterization) by DOE-BES programme DE-SC0001479. C.J. acknowledges the International Balzan Foundation for financial support through Meijo University. F.L. acknowledges support from DOE-BES programme DE-FG0203ER46027. Y.L. acknowledges a scholarship from the Chinese State Scholarship fund. A.S. acknowledges support from the BOYSCAST scheme sponsored by the Department of Science and Technology (DST), India. K.S. acknowledges support from the National Science Foundation Major Research Instrumentation programme (NSF-MRI) DMR-0619801 (for the dilution refrigerator) and the Department of Energy National Nuclear Security Administration (DOE-NNSA) DE-FG52-05NA27036 (17 T magnet and 3He system) and the PVAMU Title III Program US Department of Education (infrastructure). L.B. acknowledges support from DOE-BES and NHMFL-UCGP programmes.

Author information

Author notes

    • Lijie Ci
    •  & Li Song

    These authors contributed equally to this work

    • Deep Jariwala
    • , Yongjie Li
    •  & Anchal Srivastava

    Present addresses: Department of Metallurgical Engineering, Banaras Hindu University, Varanasi 221005, India (D.J.); Department of Physics, Banaras Hindu University, Varanasi 221005, India (A.S.); Department of Chemistry, Lanzhou University, Lanzhou 730000, China (Y.L.)

Affiliations

  1. Department of Mechanical Engineering & Materials Science, Rice University, Houston, Texas 77005, USA

    • Lijie Ci
    • , Li Song
    • , Deep Jariwala
    • , Yongjie Li
    • , Anchal Srivastava
    •  & Pulickel M. Ajayan
  2. Nanotube Research Center, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8565, Japan

    • Chuanhong Jin
  3. Department of Materials Science & Engineering, University of Utah, Salt Lake City, Utah 84112, USA

    • Dangxin Wu
    • , Z. F. Wang
    •  & Feng Liu
  4. Department of Physics, Prairie View A&M University, Prairie View, Texas 77446, USA

    • Kevin Storr
  5. National High Magnetic Field Laboratory, Tallahassee, Florida 32310, USA

    • Luis Balicas

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Contributions

L.C. and L.S. contributed equally to this work. L.C. and L.S. designed and carried out most of the experiments (CVD, TEM, AFM, XPS, Raman, ultraviolet–visible spectra, electrical test), and analysed the data. C.J. carried out atomically resolved HRTEM work. D.J. and A.S. conducted part of the CVD growth. Y.L. conducted part of the XPS measurement. K.S., L.B. and L.S. conducted electrical measurements and data analysis. D.W., Z.F.W. and F.L. carried out the modelling. P.M.A was responsible for the project planning. L.C., L.S., P.M.A. and F.L. co-wrote the paper. All the authors discussed the results.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Pulickel M. Ajayan.

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DOI

https://doi.org/10.1038/nmat2711

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