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Direct imaging of hydrogen-atom columns in a crystal by annular bright-field electron microscopy

Nature Materials volume 10, pages 278–281 (2011)Cite this article

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Abstract

Enhancing the imaging power of microscopy to identify all chemical types of atom, from low- to high-atomic-number elements,would significantly contribute for a direct determinationof material structures. Electron microscopes have successfully provided images of heavy-atom positions, particularly by the annular dark-field method1,2, but detection of light atoms was difficult owing to their weak scattering power. Recent developments of aberration-correction electron optics3,4,5 have significantly advanced the microscope performance, enabling identification of individual light atoms such as oxygen6,7,8,9, nitrogen7,9, carbon9,10,11, boron9 and lithium12,13. However, the lightest hydrogen atom has not yet been observed directly, except in the specific condition of hydrogen adatoms on a graphene membrane14. Here we show the first direct imaging of the hydrogen atom in a crystalline solid YH2, based on a classic ‘hollow-cone’ illumination theory15,16,17,18 combined with state-of-the-art scanning transmission electronmicroscopy. The optimizedhollow-cone condition derived from the aberration-corrected microscope parameters confirms that the information transfer can be extended to 22.5 nm−1, which corresponds to a spatial resolution of about 44.4 pm. These experimental conditions can be readily realized with the annular bright-field imaging in scanning transmission electron microscopy19,20 according to reciprocity21, revealing successfully the hydrogen-atom columns as dark dots, as anticipated from phase contrast of a weak-phase object22.

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Figure 1: Schematic ray diagrams of HCI–TEM/ABF–STEM and PCTF of HCI.
Figure 2: ABF, bright-field and ADF–STEM images of the crystalline compound YH2.
Figure 3: Experimental and simulated ABF intensity.

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References

  1. Crewe, A. V., Wall, J. & Langmore, J. Visibility of single atoms. Science 168, 1338–1340 (1970).

    Article  CAS  Google Scholar 

  2. Pennycook, S. J. & Boatner, L. A. Chemically sensitive structure-imaging with a scanning transmission electron microscope. Nature 336, 565–567 (1988).

    Article  CAS  Google Scholar 

  3. Haider, M. et al. Electron microscopy image enhanced. Nature 392, 768–769 (1998).

    Article  CAS  Google Scholar 

  4. Batson, P. E., Dellby, N. & Krivanek, O. L. Sub-ångstrom resolution using aberration corrected electron optics. Nature 418, 617–620 (2002).

    Article  CAS  Google Scholar 

  5. Sawada, H. et al. Correction of higher order geometrical aberration by triple 3-fold astigmatism field. J. Electron Microsc. 58, 341–347 (2009).

    Article  CAS  Google Scholar 

  6. Jia, C. L. & Urban, K. Atomic-resolution measurement of oxygen concentration in oxide materials. Science 303, 2001–2004 (2004).

    Article  CAS  Google Scholar 

  7. Okunishi, E. et al. Visualization of light elements at ultrahigh resolution by STEM annular bright field microscopy. Microsc. Microanal. 15, 164–165 (2009).

    Article  Google Scholar 

  8. Findlay, S. D. et al. Dynamics of annular bright field imaging in scanning transmission electron microscopy. Ultramicroscopy 110, 903–923 (2010).

    Article  CAS  Google Scholar 

  9. Krivanek, O. L. et al. Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy. Nature 464, 571–574 (2010).

    Article  CAS  Google Scholar 

  10. Liu, Z. et al. Imaging the dynamic behaviour of individual retinal chromophores confined inside carbon nanotubes. Nature Nanotech. 2, 422–425 (2007).

    Article  CAS  Google Scholar 

  11. Girit, Ö. Ç. et al. Graphene at the edge: Stability and dynamics. Science 323, 1705–1708 (2009).

    Article  CAS  Google Scholar 

  12. Shao-Horn, Y., Croguennec, L., Delmas, C., Nelson, E. C. & O’Keefe, M. A. Atomic resolution of lithium ions in LiCoO2 . Nature Mater. 2, 464–467 (2003).

    Article  Google Scholar 

  13. Oshima, Y. et al. Direct imaging of lithium atoms in LiV2O4 by spherical aberration-corrected electron microscopy. J. Electron Microsc. 59, 457–461 (2010).

    CAS  Google Scholar 

  14. Meyer, J. C., Girit, C. O., Crommie, M. F. & Zettl, A. Imaging and dynamics of light atoms and molecules on graphene. Nature 454, 319–322 (2008).

    Article  CAS  Google Scholar 

  15. Mathews, W. W. The use of hollow-cone illumination for increasing image contrast in microscopy. Trans. Am. Microsc. Soc. 2, 190–195 (1953).

    Article  Google Scholar 

  16. Hanssen, K. J. & Trepte, L. Die Kontrastübertragung im elektronemikroskop bei partiell kohärentercbeleuchtung (in German). Optik 33, 166–181 (1971).

    Google Scholar 

  17. Rose, H. Nonstandard imaging methods in electron microscopy. Ultramicroscopy 2, 251–267 (1977).

    Article  CAS  Google Scholar 

  18. Dinges, C., Kohl, H. & Rose, H. High-resolution imaging of crystalline objects by hollow-cone illumination. Ultrmicroscopy 55, 91–100 (1994).

    Article  CAS  Google Scholar 

  19. Rose, H. Phase-contrast in scanning transmission electron microscopy. Optik 39, 416–436 (1974).

    Google Scholar 

  20. Cowley, J. M., Hansen, M. S. & Wang, S-Y. Imaging modes with an annular detector in STEM. Ultramicroscopy 58, 18–24 (1995).

    Article  CAS  Google Scholar 

  21. Cowley, J. M. Image contrast in a transmission scanning electron microscope. Appl. Phys. Lett. 15, 58–59 (1969).

    Article  Google Scholar 

  22. Scherzer, O. The theoretical resolution limit of the electron microscope. J. Appl. Phys. 20, 20–29 (1949).

    Article  CAS  Google Scholar 

  23. Komoda, T. Electron microscopic observation of crystal lattices on the level with atomic dimension. Jpn. J. Appl. Phys. 5, 603–607 (1966).

    Article  CAS  Google Scholar 

  24. Kunath, W., Zemlin, F. & Weiss, K. Apodization in phase-contrast electron microscopy realized with hollow-cone illumination. Ultramicroscopy 16, 123–138 (1985).

    Article  CAS  Google Scholar 

  25. O’Keefe, M. A. et al. Sub-ångstrom high-resolution transmission electron microscopy at 300 keV. Ultramicroscopy 89, 215–241 (2001).

    Article  Google Scholar 

  26. Nellist, P. D. et al. Direct sub-ångstrom imaging of a crystal lattice. Science 305, 1741 (2004).

    Article  CAS  Google Scholar 

  27. Sawada, H. et al. STEM imaging of 47 pm-separated atomic columns by a spherical aberration-corrected electron microscope with a 300-kV cold field emission gun. J. Electron Microsc. 58, 357–361 (2009).

    Article  CAS  Google Scholar 

  28. Egerton, R. F. Electron Energy-Loss Spectroscopy in the Electron Microscope 2nd edn (Plenum, 1996).

    Book  Google Scholar 

  29. Ishizuka, K. A practical approach for STEM image simulation based on the FFT multislice method. Ultramicroscopy 90, 71–83 (2002).

    Article  CAS  Google Scholar 

  30. Kabius, B. et al. First application of Cc-corrected imaging for high-resolution and energy-filtered TEM. J. Electron Microsc. 58, 147–155 (2009).

    Article  CAS  Google Scholar 

  31. Findlay, S. et al. Direct imaging of hydrogen within a crystalline environment. Appl. Phys. Express 3, 116603 (2010).

    Article  Google Scholar 

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Acknowledgements

R.I. was supported as a Japan Society for the Promotion of Science research fellow. E.A. acknowledges support from a Grant-in-Aid for Scientific Research on Priority Areas ‘Atomic scale modification’ from the Ministry of Education, Culture, Sports, Science and Technology of Japan.

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Authors and Affiliations

  1. Department of Materials Science & Engineering, University of Tokyo, Tokyo 113-8656, Japan

    Ryo Ishikawa & Eiji Abe

  2. Electron Optics Division, JEOL Ltd., Tokyo 196-8558, Japan

    Eiji Okunishi, Hidetaka Sawada, Yukihito Kondo & Fumio Hosokawa

Authors
  1. Ryo Ishikawa
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  2. Eiji Okunishi
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  3. Hidetaka Sawada
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  4. Yukihito Kondo
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  5. Fumio Hosokawa
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  6. Eiji Abe
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Contributions

E.A. initiated and designed the research, interpreted the data and wrote the paper. R.I. designed the experiments, analysed the data and carried out computer simulations. E.O., R.I. and E.A. carried out electron microscope experiments. H.S., Y.K. and F.H. contributed to interpretations of ABF imaging.

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Correspondence to Eiji Abe.

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The authors declare no competing financial interests.

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Ishikawa, R., Okunishi, E., Sawada, H. et al. Direct imaging of hydrogen-atom columns in a crystal by annular bright-field electron microscopy. Nature Mater 10, 278–281 (2011). https://doi.org/10.1038/nmat2957

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