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Characterization and manipulation of individual defects in insulating hexagonal boron nitride using scanning tunnelling microscopy

Abstract

Defects play a key role in determining the properties and technological applications of nanoscale materials and, because they tend to be highly localized, characterizing them at the single-defect level is of particular importance. Scanning tunnelling microscopy has long been used to image the electronic structure of individual point defects in conductors1, semiconductors2,3,4 and ultrathin films5,6,7,8,9, but such single-defect electronic characterization remains an elusive goal for intrinsic bulk insulators. Here, we show that individual native defects in an intrinsic bulk hexagonal boron nitride insulator can be characterized and manipulated using a scanning tunnelling microscope. This would typically be impossible due to the lack of a conducting drain path for electrical current. We overcome this problem by using a graphene/boron nitride heterostructure, which exploits the atomically thin nature of graphene to allow the visualization of defect phenomena in the underlying bulk boron nitride. We observe three different defect structures that we attribute to defects within the bulk insulating boron nitride. Using scanning tunnelling spectroscopy we obtain charge and energy-level information for these boron nitride defect structures. We also show that it is possible to manipulate the defects through voltage pulses applied to the scanning tunnelling microscope tip.

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Figure 1: STM topography and corresponding dI/dV map for a graphene/BN device.
Figure 2: dI/dV maps and spatially dependent dI/dV spectroscopy determining the defect charge state.
Figure 3: dI/dV maps of ring defect enable energy-level characterization.
Figure 4: Manipulating defects in BN with an STM tip.

References

  1. Madhavan, V., Chen, W., Jamneala, T., Crommie, M. F. & Wingreen, N. S. Tunneling into a single magnetic atom: spectroscopic evidence of the Kondo resonance. Science 280, 567–569 (1998).

    CAS  Article  Google Scholar 

  2. Feenstra, R. M., Woodall, J. M. & Pettit, G. D. Observation of bulk defects by scanning tunneling microscopy and spectroscopy: arsenic antisite defects in GaAs. Phys. Rev. Lett. 71, 1176–1179 (1993).

    CAS  Article  Google Scholar 

  3. Teichmann, K. et al. Controlled charge switching on a single donor with a scanning tunneling microscope. Phys. Rev. Lett. 101, 076103 (2008).

    CAS  Article  Google Scholar 

  4. Lee, D. H. & Gupta, J. A. Tunable field control over the binding energy of single dopants by a charged vacancy in GaAs. Science 330, 1807–1810 (2010).

    CAS  Article  Google Scholar 

  5. Repp, J., Meyer, G., Olsson, F. E. & Persson, M. Controlling the charge state of individual gold adatoms. Science 305, 493–495 (2004).

    CAS  Article  Google Scholar 

  6. Pradhan, N. A., Liu, N. & Ho, W. Vibronic spectroscopy of single C60 molecules and monolayers with the STM. J. Phys. Chem. B 109, 8513–8518 (2005).

    CAS  Article  Google Scholar 

  7. Avouris, P. & Wolkow, R. Scanning tunneling microscopy of insulators: CaF2 epitaxy on Si(111). Appl. Phys. Lett. 55, 1074–1076 (1989).

    CAS  Article  Google Scholar 

  8. Repp, J., Meyer, G., Paavilainen, S., Olsson, F. E. & Persson, M. Scanning tunneling spectroscopy of Cl vacancies in NaCl films: strong electron–phonon coupling in double-barrier tunneling junctions. Phys. Rev. Lett. 95, 225503 (2005).

    Article  Google Scholar 

  9. Choi, T., Ruggiero, C. D. & Gupta, J. A. Incommensurability and atomic structure of c(2×2)N/Cu(100): a scanning tunneling microscopy study. Phys. Rev. B 78, 035430 (2008).

    Article  Google Scholar 

  10. Dean, C. R. et al. Boron nitride substrates for high-quality graphene electronics. Nature Nanotech. 5, 722–726 (2010).

    CAS  Article  Google Scholar 

  11. Britnell, L. et al. Strong light–matter interactions in heterostructures of atomically thin films. Science 340, 1311–1314 (2013).

    CAS  Article  Google Scholar 

  12. Watanabe, K., Taniguchi, T. & Kanda, H. Direct-bandgap properties and evidence for ultraviolet lasing of hexagonal boron nitride single crystal. Nature Mater. 3, 404–409 (2004).

    CAS  Article  Google Scholar 

  13. Taniguchi, T. & Watanabe, K. Synthesis of high-purity boron nitride single crystals under high pressure by using Ba–BN solvent. J. Cryst. Growth 303, 525–529 (2007).

    CAS  Article  Google Scholar 

  14. Remes, Z., Nesladek, M., Haenen, K., Watanabe, K. & Taniguchi, T. The optical absorption and photoconductivity spectra of hexagonal boron nitride single crystals. Phys. Status Solidi A 202, 2229–2233 (2005).

    CAS  Article  Google Scholar 

  15. Ju, L. et al. Photoinduced doping in heterostructures of graphene and boron nitride. Nature Nanotech. 9, 348–352 (2014).

    CAS  Article  Google Scholar 

  16. Xue, J. et al. Scanning tunnelling microscopy and spectroscopy of ultra-flat graphene on hexagonal boron nitride. Nature Mater. 10, 282–285 (2011).

    CAS  Article  Google Scholar 

  17. Decker, R. G. et al. Local electronic properties of graphene on a BN substrate via scanning tunneling microscopy. Nano Lett. 11, 2291–2295 (2011).

    CAS  Article  Google Scholar 

  18. Zhang, Y. et al. Giant phonon-induced conductance in scanning tunneling spectroscopy of gate-tunable graphene. Nature Phys. 4, 627–630 (2008).

    CAS  Article  Google Scholar 

  19. Wang, Y. et al. Mapping Dirac quasiparticles near a single Coulomb impurity on graphene. Nature Phys. 8, 653–657 (2012).

    CAS  Article  Google Scholar 

  20. Wang, Y. et al. Observing atomic collapse resonances in artificial nuclei on graphene. Science 340, 734–737 (2013).

    CAS  Article  Google Scholar 

  21. Brar, V. W. et al. Gate-controlled ionization and screening of cobalt adatoms on a graphene surface. Nature Phys. 7, 43–47 (2011).

    CAS  Article  Google Scholar 

  22. Scheffler, M. et al. Probing local hydrogen impurities in quasi-free-standing graphene. ACS Nano 6, 10590–10597 (2012).

    CAS  Article  Google Scholar 

  23. Fanciulli, M. & Moustakas, T. D. Study of defects in wide band gap semiconductors by electron paramagnetic resonance. Physica B 185, 228–233 (1993).

    CAS  Article  Google Scholar 

  24. Katzir, A., Suss, J. T., Zunger, A. & Halperin, A. Point defects in hexagonal boron nitride. I. EPR, thermoluminescence, and thermally-stimulated-current measurements. Phys. Rev. B 11, 2370–2377 (1975).

    CAS  Article  Google Scholar 

  25. Andrei, E. Y., Katzir, A. & Suss, J. T. Point defects in hexagonal boron nitride. III. EPR in electron-irradiated BN. Phys. Rev. B 13, 2831–2834 (1976).

    CAS  Article  Google Scholar 

  26. Zunger, A. & Katzir, A. Point defects in hexagonal boron nitride. II. Theoretical studies. Phys. Rev. B 11, 2378–2390 (1975).

    CAS  Article  Google Scholar 

  27. Attaccalite, C., Bockstedte, M., Marini, A., Rubio, A. & Wirtz, L. Coupling of excitons and defect states in boron-nitride nanostructures. Phys. Rev. B 83, 144115 (2011).

    Article  Google Scholar 

  28. Das Sarma, S., Adam, S., Hwang, E. H. & Rossi, E. Electronic transport in two-dimensional graphene. Rev. Mod. Phys. 83, 407–470 (2011).

    CAS  Article  Google Scholar 

  29. Woodside, M. T. & McEuen, P. L. Scanned probe imaging of single-electron charge states in nanotube quantum dots. Science 296, 1098–1101 (2002).

    CAS  Article  Google Scholar 

  30. Pradhan, N. A., Liu, N., Silien, C. & Ho, W. Atomic scale conductance induced by single impurity charging. Phys. Rev. Lett. 94, 076801 (2005).

    CAS  Article  Google Scholar 

  31. Kharche, N. & Nayak, S. K. Quasiparticle band gap engineering of graphene and graphone on hexagonal boron nitride substrate. Nano Lett. 11, 5274–5278 (2011).

    CAS  Article  Google Scholar 

  32. Garleff, J. K., Wijnheijmer, A. P., v. d. Enden, C. N. & Koenraad, P. M. Bistable behavior of silicon atoms in the (110) surface of gallium arsenide. Phys. Rev. B 84, 075459 (2011).

    Article  Google Scholar 

  33. Zomer, P. J., Dash, S. P., Tombros, N. & van Wees, B. J. A transfer technique for high mobility graphene devices on commercially available hexagonal boron nitride. Appl. Phys. Lett. 99, 232104–232107 (2011).

    Article  Google Scholar 

Download references

Acknowledgements

The authors thank P. Jarillo-Herrero, N. Gabor, A. Young, P. Yu and A. Rubio for discussions. This research was supported by the sp2 programme (STM measurement and device fabrication) and the LBNL Molecular Foundry (graphene growth characterization) funded by the Director, Office of Science, Office of Basic Energy Sciences of the US Department of Energy (contract no. DE-AC02-05CH11231). Support was also provided by National Science Foundation award CMMI-1235361 (device characterization, image analysis). J.V.J. acknowledges support from the UC President's Postdoctoral Fellowship. D.W. was supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program. S.K. acknowledges support from the Qualcomm Scholars Research Fellowship.

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L.J. and J.V.J. conceived the work and designed the research strategy. J.V.J., D.W., S.K. and J.L. performed data analysis. J.V.J., S.K., L.J. and A.Z. facilitated sample fabrication. D.W., J.L. and J.V.J. carried out STM/ scanning tunnelling spectroscopy (STS) measurements. J.V.J. and S.K. carried out electron transport measurements. K.W. and T.T. synthesized the hBN samples. D.W., J.V.J. and L.J. formulated the theoretical model with advice from F.W. and M.F.C. M.F.C. supervised the STM/STS experiments. J.V.J., D.W. and M.F.C. co-wrote the manuscript. J.V.J. and M.F.C. coordinated the collaboration. All authors discussed the results and commented on the paper.

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Correspondence to Michael F. Crommie.

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Wong, D., Velasco, J., Ju, L. et al. Characterization and manipulation of individual defects in insulating hexagonal boron nitride using scanning tunnelling microscopy. Nature Nanotech 10, 949–953 (2015). https://doi.org/10.1038/nnano.2015.188

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