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:

Visualizing and identifying single atoms using electron energy-loss spectroscopy with low accelerating voltage

Abstract

Visualizing atoms and discriminating between those of different elements is a goal in many analytical techniques. The use of electron energy-loss spectroscopy (EELS) in such single-atom analyses is hampered by an inherent difficulty related to the damage caused to specimens by incident electrons. Here, we demonstrate the successful EELS single-atom spectroscopy of various metallofullerene-doped single-wall nanotubes (known as peapods) without massive structural destruction. This is achieved by using an incident electron probe with a low accelerating voltage (60 kV). Single calcium atoms inside the peapods were unambiguously identified for the first time using EELS. Elemental analyses of lanthanum, cerium and erbium atoms were also demonstrated, which shows that single atoms with adjacent atomic numbers can be successfully discriminated with this technique.

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

Access options

Buy this article

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

Figure 1: Endohedral metallofullerenes and their peapods.
Figure 2: STEM–EELS analysis of a Ca metallofullerene peapod.
Figure 3: Element-selective imaging of single La and Er atoms.
Figure 4: Single-atom spectroscopy for La and Ce.

Similar content being viewed by others

References

  1. Isaacson, M. & Johnson, D. The microanalysis of light elements using transmitted energy loss electrons. Ultramicroscopy 1, 33–52 (1975).

    Article  CAS  Google Scholar 

  2. Suenaga, K. et al. Element-selective single atom imaging. Science 290, 2280–2282 (2000).

    Article  CAS  Google Scholar 

  3. Smith, B. W. & Luzzi, D. E. Electron irradiation effects in single wall carbon nanotubes. J. Appl. Phys. 90, 3509–3515 (2001).

    Article  CAS  Google Scholar 

  4. Zobelli, A., Gloter, A., Ewels, C. P., Seifert, G. & Colliex, C. Electron knock-on cross section of carbon and boron nitride nanotubes. Phys. Rev. B 75, 245402 (2007).

    Article  Google Scholar 

  5. Sawada, H. et al. Correction of higher order geometrical aberration by triple three-fold astigmatism field. J. Electron Micros. (in the press).

  6. Urita, K. et al. Defect-induced atomic migration in carbon nanopeapod: tracking the single-atom dynamic behavior. Nano Lett. 4, 2451–2454 (2004).

    Article  CAS  Google Scholar 

  7. Andrews, S. B., Leapman, R. D., Landis, D. M. & Reese, T. S. Distribution of calcium and potassium in presynaptic nerve terminals from cerebellar cortex. Proc. Natl Acad. Sci. USA 84, 1713–1717 (1987).

    Article  CAS  Google Scholar 

  8. Leapman, R. D. Detecting single atoms of calcium and iron in biological structures by electron energy-loss spectrum-imaging. J. Micros. 210, 5–15 (2003).

    Article  CAS  Google Scholar 

  9. Muller, D. & Silcox, J. Delocalization in inelastic scattering. Ultramicroscopy 59, 195–213 (1995).

    Article  CAS  Google Scholar 

  10. Kimoto, K. et al. Element-selective imaging of atomic columns in a crystal using STEM and EELS. Nature 450, 702–704 (2007).

    Article  CAS  Google Scholar 

  11. Mory, C. & Colliex, C. Elemental analysis near the single-atom detection level by processing sequences of energy-filtered images. Ultramicroscopy 28, 339–346 (1989).

    Article  CAS  Google Scholar 

  12. Gloter, A. et al. Structural evolutions of carbon nano-peapods under electron microscopic observation. Chem. Phys. Lett. 390, 462–466 (2004).

    Article  CAS  Google Scholar 

  13. Sato, Y. et al. Correlation between atomic rearrangement in defective fullerenes and migration behavior of encaged metal ions. Phys. Rev. B 73, 233409 (2006).

    Article  Google Scholar 

  14. Shimada, T. et al. Tunable field-effect transistor device with metallofullerene nanopeapods. Jpn. J. Appl. Phys. 44, 469–472 (2005).

    Article  CAS  Google Scholar 

  15. Varela, M. et al. Spectroscopic imaging of single atoms within a bulk solid. Phys. Rev. Lett. 92, 095502 (2004).

    Article  CAS  Google Scholar 

  16. Shinohara, H. Endohedral metallofullerenes. Rep. Prog. Phys. 63, 843–892 (2000).

    Article  CAS  Google Scholar 

  17. Kodama, T. et al. Structural study of four Ca@C82 isomers by 13C NMR spectroscopy. Chem. Phys. Lett. 377, 197–200 (2003).

    Article  CAS  Google Scholar 

  18. Hirahara, K. et al. One-dimensional metallofullerene crystal generated inside single-walled carbon nanotubes. Phys. Rev. Lett. 85, 5384–5387 (2000).

    Article  CAS  Google Scholar 

  19. Jeanguillaume, C. & Colliex, C. Spectrum-image: the next step in EELS digital acquisition and processing. Ultramicroscopy 28, 252–257 (1989).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Japan Science and Technology Agency—Core Research for Evolutional Science and Technology.

Author information

Authors and Affiliations

Authors

Contributions

K.S. and K.K. designed and conceived the experiments. H.K. and T.O. contributed the specimens. H.S., T.S., K.O., T.T., T.K. and Y.K. designed and developed the microscope. K.S., Y.S. and Z.L. analysed data and co-wrote the paper.

Corresponding author

Correspondence to Kazu Suenaga.

Supplementary information

Supplementary information

Supplementary information (PDF 1061 kb)

Supplementary information

Supplementary movie S1 (MOV 1207 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Suenaga, K., Sato, Y., Liu, Z. et al. Visualizing and identifying single atoms using electron energy-loss spectroscopy with low accelerating voltage. Nature Chem 1, 415–418 (2009). https://doi.org/10.1038/nchem.282

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nchem.282

This article is cited by

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