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Growth and low-energy electron microscopy characterization of monolayer hexagonal boron nitride on epitaxial cobalt

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Abstract

Low-energy electron microscopy (LEEM) has been used to study the structure, initial growth orientation, growth progression, and the number of layers of atomically thin hexagonal boron nitride (h-BN) films. The h-BN films are grown on heteroepitaxial Co using chemical vapor deposition (CVD) at low pressure. Our findings from LEEM studies include the growth of monolayer film having two, oppositely oriented, triangular BN domains commensurate with the Co lattice. The growth of h-BN appears to be self-limiting at a monolayer, with thicker domains only appearing in patches, presumably initiated between domain boundaries. Reflectivity measurements of the thicker h-BN films show oscillations resulting from the resonant electron transmission through quantized electronic states of the h-BN films, with the number of minima scaling up with the number of h-BN layers. First principles density functional theory (DFT) calculations show that the positions of oscillations are related to the electronic band structure of h-BN.

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References

  1. Novoselov, K. S.; Jiang, D.; Schedin, F.; Booth, T. J.; Khotkevich, V. V.; Morozov, S. V.; Geim, A. K. Two-dimensional atomic crystals. Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 10451–10453.

    Article  CAS  Google Scholar 

  2. Neto, A. H. C.; Novoselov, K. New directions in science and technology: Two-dimensional crystals. Rep. Prog. Phys. 2011, 74, 082501.

    Article  Google Scholar 

  3. Kim, K. K.; Hsu, A.; Jia, X. T.; Kim, S. M.; Shi, Y. M.; Dresselhaus, M.; Palacios, T.; Kong, J. Synthesis and characterization of hexagonal boron nitride film as a dielectric layer for graphene devices. ACS Nano 2012, 6, 8583–8590.

    Article  CAS  Google Scholar 

  4. Watanabe, K.; Taniguchi, T.; Kanda, H. Direct-bandgap properties and evidence for ultraviolet lasing of hexagonal boron nitride single crystal. Nat. Mater. 2004, 3, 404–409.

    Article  CAS  Google Scholar 

  5. Kubota, Y.; Watanabe, K.; Tsuda, O.; Taniguchi, T. Deep ultraviolet light-emitting hexagonal boron nitride synthesized at atmospheric pressure. Science 2007, 317, 932–934.

    Article  CAS  Google Scholar 

  6. Watanabe, K.; Taniguchi, T.; Niiyama, T.; Miya, K.; Taniguchi, M. Far-ultraviolet plane-emission handheld device based on hexagonal boron nitride. Nat. Photonics 2009, 3, 591–594.

    Article  CAS  Google Scholar 

  7. Giovannetti, G.; Khomyakov, P. A.; Brocks, G.; Kelly, P. J.; van den Brink, J. Substrate-induced band gap in graphene on hexagonal boron nitride: Ab initio density functional calculations. Phys. Rev. B 2007, 76, 073103.

    Article  Google Scholar 

  8. Dean, C. R.; Young, A. F.; Meric, I.; Lee, C.; Wang, L.; Sorgenfrei, S.; Watanabe, K.; Taniguchi, T.; Kim, P.; Shepard, K. L.; Hone, J. Boron nitride substrates for high-quality graphene electronics. Nat. Nanotechnol. 2010, 5, 722–726.

    Article  CAS  Google Scholar 

  9. Lee, K. H.; Shin, H. J.; Lee, J.; Lee, I. Y.; Kim, G. H.; Choi, J. Y.; Kim, S. W. Large-scale synthesis of high-quality hexagonal boron nitride nanosheets for large-area graphene electronics. Nano Lett. 2012, 12, 714–718.

    Article  CAS  Google Scholar 

  10. Ramasubramaniam, A.; Naveh, D.; Towe, E. Tunable band gaps in bilayer graphene-BN heterostructures. Nano Lett. 2011, 11, 1070–1075.

    Article  CAS  Google Scholar 

  11. Ci, L. J.; Song, L.; Jin, C. H.; Jariwala, D.; Wu, D. X.; Li, Y. J.; Srivastava, A.; Wang, Z. F.; Storr, K.; Balicas, L.; Liu, F.; Ajayan, P. M. Atomic layers of hybridized boron nitride and graphene domains. Nat. Mater. 2010, 9, 430–435.

    Article  CAS  Google Scholar 

  12. Nagashima, A.; Tejima, N.; Gamou, Y.; Kawai, T.; Oshima, C. Electronic dispersion relations of monolayer hexagonal boron nitride formed on the Ni(111) surface. Phys. Rev. B 1995, 51, 4606–4613.

    Article  CAS  Google Scholar 

  13. Nagashima, A.; Tejima, N.; Gamou, Y.; Kawai, T.; Oshima, C. Electronic structure of monolayer hexagonal boron nitride physisorbed on metal surfaces. Phys. Rev. Lett. 1995, 75, 3918–3921.

    Article  CAS  Google Scholar 

  14. Auwärter, W.; Kreutz, T. J.; Greber, T.; Osterwalder, J. XPD and STM investigation of hexagonal boron nitride on Ni(111). Surf. Sci. 1999, 429, 229–236.

    Article  Google Scholar 

  15. Auwärter, W.; Suter, H. U.; Sachdev, H.; Greber, T. Synthesis of one monolayer of hexagonal boron nitride on Ni(111) from B-trichloroborazine (ClBNH)3. Chem. Mater. 2004, 16, 343–345.

    Article  Google Scholar 

  16. Auwärter, W.; Muntwiler, M.; Osterwalder, J.; Greber, T. Defect lines and two-domain structure of hexagonal boron nitride films on Ni(111). Surf. Sci. 2003, 545, L735–L740.

    Article  Google Scholar 

  17. Song, L.; Ci, L. J.; Lu, H.; Sorokin, P. B.; Jin, C. H.; Ni, J.; Kvashnin, A. G.; Kvashnin, D. G.; Lou, J.; Yakobson, B. I. et al. Large scale growth and characterization of atomic hexagonal boron nitride layers. Nano Lett. 2010, 10, 3209–3215.

    Article  CAS  Google Scholar 

  18. Shi, Y. M.; Hamsen, C.; Jia, X. T.; Kim, K. K.; Reina, A.; Hofmann, M.; Hsu, A. L.; Zhang, K.; Li, H. N.; Juang, Z. Y. et al. Synthesis of few-layer hexagonal boron nitride thin film by chemical vapor deposition. Nano Lett. 2010, 10, 4134–4139.

    Article  CAS  Google Scholar 

  19. Ismach, A.; Chou, H.; Ferrer, D. A.; Wu, Y. P.; McDonnell, S.; Floresca, H. C.; Covacevich, A.; Pope, C.; Piner, R.; Kim, M. J. et al. Toward the controlled synthesis of hexagonal boron nitride films. ACS Nano 2012, 6, 6378–6385.

    Article  CAS  Google Scholar 

  20. Kim, K. K.; Hsu, A.; Jia, X. T.; Kim, S. M.; Shi, Y. M.; Hofmann, M.; Nezich, D.; Rodriguez-Nieva, J. F.; Dresselhaus, M.; Palacios, T. et al. Synthesis of monolayer hexagonal boron nitride on Cu foil using chemical vapor deposition. Nano Lett. 2012, 12, 161–166.

    Article  Google Scholar 

  21. Ago, H.; Ito, Y.; Mizuta, N.; Yoshida, K.; Hu, B. S.; Orofeo, C. M.; Tsuji, M.; Ikeda, K.; Mizuno, S. Epitaxial chemical vapor deposition growth of single-layer graphene over cobalt film crystallized on sapphire. ACS Nano 2010, 4, 7407–7414.

    Article  CAS  Google Scholar 

  22. Orofeo, C. M.; Ago, H.; Hu, B. S.; Tsuji, M. Synthesis of large area, homogenous, single layer graphene films by annealing amorphous carbon on Co and Ni. Nano Res. 2011, 4, 531–540.

    Article  CAS  Google Scholar 

  23. Ogawa, Y.; Hu, B. S.; Orofeo, C. M.; Tsuji, M.; Ikeda, K.; Mizuno, S.; Hibino, H.; Ago, H. Domain structure and boundary in single-layer graphene grown on Cu(111) and Cu(100) films. J. Phys. Chem. Lett. 2012, 3, 219–226.

    Article  CAS  Google Scholar 

  24. Young, D. A. Phase Diagrams of the Elements; University of California Press: Berkeley, 1991.

    Google Scholar 

  25. Suzuki, S.; Hibino, H. Chemical vapor deposition of hexagonal boron nitride. e-J. Surf. Sci. Nanotech. 2012, 10, 133–138.

    Article  CAS  Google Scholar 

  26. Ferrari, A. C.; Meyer, J. C.; Scardaci, V.; Casiraghi, C.; Lazzeri, M.; Mauri, F.; Piscanec, S.; Jiang, D.; Novoselov, K. S.; Roth, S. et al. Raman spectrum of graphene and graphene layers. Phys. Rev. Lett. 2006, 97, 187401.

    Article  CAS  Google Scholar 

  27. Gorbachev, R. V.; Riaz, I.; Nair, R. R.; Jalil, R.; Britnell, L.; Belle, B. D.; Hill, E. W.; Novoselov, K. S.; Watanabe, K.; Taniguchi, T. et al. Hunting for monolayer boron nitride: Optical and Raman signatures. Small 2011, 7, 465–468.

    Article  CAS  Google Scholar 

  28. Reich, S.; Ferrari, A. C.; Arenal, R.; Loiseau, A.; Bello, I.; Robertson, J. Resonant Raman scattering in cubic and hexagonal boron nitride. Phys. Rev. B 2005, 71, 205201.

    Article  Google Scholar 

  29. Wang, Y. Y.; Ni, Z. H.; Yu, T.; Shen, Z. X.; Wang, H. M.; Wu, Y. H.; Chen, W.; Wee, A. T. S. Raman studies of monolayer graphene: The substrate effect. J. Phys. Chem. C 2008, 112, 10637–10640.

    Article  CAS  Google Scholar 

  30. Blase, X.; Rubio, A.; Louie, S. G.; Cohen, M. L. Quasiparticle band structure of bulk hexagonal boron nitride and related systems. Phys. Rev. B 1995, 51, 6868–6875.

    Article  CAS  Google Scholar 

  31. Britnell, L.; Gorbachev, R. V.; Jalil, R.; Belle, B. D.; Schedin, F.; Katsnelson, M. I.; Eaves, L.; Morozov, S. V.; Mayorov, A. S.; Peres, N. M. R. et al. Electron tunneling through ultrathin boron nitride crystalline barriers. Nano Lett. 2012, 12, 1707–1710.

    Article  CAS  Google Scholar 

  32. Hibino, H.; Kageshima, H.; Maeda, F.; Nagase, M.; Kobayashi, Y.; Yamaguchi, H. Microscopic thickness determination of thin graphite films formed on SiC from quantized oscillation in reflectivity of low-energy electrons. Phys. Rev. B 2008, 77, 075413.

    Article  Google Scholar 

  33. Hibino, H.; Kageshima, H.; Nagase, M. Epitaxial few-layer graphene: Towards single crystal growth. J. Phys. D: Appl. Phys. 2010, 43, 374005.

    Article  Google Scholar 

  34. Strocov, V. N.; Blaha, P.; Starnberg, H. I.; Rohlfing, M.; Claessen, R.; Debever, J. M.; Themlin, J. M. Three-dimensional unoccupied band structure of graphite: Very-low-energy electron diffraction and band calculations. Phys. Rev. B 2000, 61, 4994–5001.

    Article  CAS  Google Scholar 

  35. Sutter, P.; Sadowski, J. T.; Sutter, E. Graphene on Pt(111): Growth and substrate interaction. Phys. Rev. B 2009, 80, 245411.

    Article  Google Scholar 

  36. Suzuki, S.; Pallares, R. M.; Hibino, H. Growth of atomically thin hexagonal boron nitride films by diffusion through a metal film and precipitation. J. Phys. D: Appl. Phys. 2012, 45, 385304.

    Article  Google Scholar 

  37. Ago, H.; Ogawa, Y.; Tsuji, M.; Mizuno, S.; Hibino, H. Catalytic growth of graphene: Toward large-area single-crystalline graphene. J. Phys. Chem. Lett. 2012, 3, 2228–2236.

    Article  CAS  Google Scholar 

  38. Sutter, P.; Lahiri, J.; Albrecht, P.; Sutter, E. Chemical vapor deposition and etching of high-quality monolayer hexagonal boron nitride films. ACS Nano 2011, 5, 7303–7309.

    Article  CAS  Google Scholar 

  39. Grad, G. B.; Blaha, P.; Schwarz, K.; Auwärter, W.; Greber, T. Density functional theory investigation of the geometric and spintronic structure of h-BN/Ni(111) in view of photoemission and STM experiments. Phys. Rev. B 2003, 68, 085404.

    Article  Google Scholar 

  40. Liu, Y. Y.; Bhowmick, S.; Yakobson, B. I. BN white graphene with “colorful” edges: The energies and morphology. Nano Lett. 2011, 11, 3113–3116.

    Article  CAS  Google Scholar 

  41. Frueh, S.; Kellett, R.; Mallery, C.; Molter, T.; Willis, W. S.; King’ondu, C.; Suib, S. L. Pyrolytic decomposition of ammonia borane to boron nitride. Inorg. Chem. 2011, 50, 783–792.

    Article  CAS  Google Scholar 

  42. Kageshima, H.; Shiraishi, K. Momentum-matrix-element calculation using pseudopotentials. Phys. Rev. B 1997, 56, 14985–14992.

    Article  CAS  Google Scholar 

  43. Vanderbilt, D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys. Rev. B 1990, 41, 7892–7895.

    Article  Google Scholar 

  44. Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.

    Article  CAS  Google Scholar 

  45. Kurdyumov, A. V.; Solozhenko, V. L.; Zelyavski, W. B. Lattice parameters of boron nitride polymorphous modifications as a function of their crystal-structure perfection. J. Appl. Cryst. 1995, 28, 540–545.

    Article  CAS  Google Scholar 

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Correspondence to Hiroki Hibino.

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Orofeo, C.M., Suzuki, S., Kageshima, H. et al. Growth and low-energy electron microscopy characterization of monolayer hexagonal boron nitride on epitaxial cobalt. Nano Res. 6, 335–347 (2013). https://doi.org/10.1007/s12274-013-0310-1

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  • DOI: https://doi.org/10.1007/s12274-013-0310-1

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