Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy (original) (raw)

Nature volume 464, pages 571–574 (2010)Cite this article

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Abstract

Direct imaging and chemical identification of all the atoms in a material with unknown three-dimensional structure would constitute a very powerful general analysis tool. Transmission electron microscopy should in principle be able to fulfil this role, as many scientists including Feynman realized early on[1](/articles/nature08879#ref-CR1 "Feynman, R. P. in Feynman and Computation (ed. Hey, J. G.) 63–76 (Perseus Press, Cambridge, Massachusetts, 1999); text of original 1959 lecture also available at 〈 http://feynman.caltech.edu/plenty.html

            〉 (2001)"). It images matter with electrons that scatter strongly from individual atoms and whose wavelengths are about 50 times smaller than an atom. Recently the technique has advanced greatly owing to the introduction of aberration-corrected optics[2](/articles/nature08879#ref-CR2 "Haider, M. et al. Electron microscopy image enhanced. Nature 392, 768–769 (1998)"),[3](/articles/nature08879#ref-CR3 "Batson, P. E., Dellby, N. & Krivanek, O. L. Sub-ångstrom resolution using aberration corrected electron optics. Nature 418, 617–620 (2002)"),[4](/articles/nature08879#ref-CR4 "Hawkes, P. W. ed. Aberration-Corrected Electron Microscopy (Advances in Imaging and Electron Physics, Vol. 153, Elsevier, 2008)"),[5](/articles/nature08879#ref-CR5 "Girit, Ç. Ö. et al. Graphene at the edge: stability and dynamics. Science 323, 1705–1708 (2009)"),[6](/articles/nature08879#ref-CR6 "Jia, C. L., Lentzen, M. & Urban, K. Atomic resolution imaging of oxygen in perovskite ceramics. Science 299, 870–873 (2003)"),[7](/articles/nature08879#ref-CR7 "Muller, D. A. et al. Atomic-scale chemical imaging of composition and bonding by aberration-corrected microscopy. Science 319, 1073–1076 (2008)"),[8](/articles/nature08879#ref-CR8 "Suenaga, K. et al. Visualizing and identifying single atoms using electron energy-loss spectroscopy with low accelerating voltage. Nature Chem. 1, 415–418 (2009)"). However, neither electron microscopy nor any other experimental technique has yet been able to resolve and identify all the atoms in a non-periodic material consisting of several atomic species. Here we show that annular dark-field imaging in an aberration-corrected scanning transmission electron microscope optimized for low voltage operation can resolve and identify the chemical type of every atom in monolayer hexagonal boron nitride that contains substitutional defects. Three types of atomic substitutions were found and identified: carbon substituting for boron, carbon substituting for nitrogen, and oxygen substituting for nitrogen. The substitutions caused in-plane distortions in the boron nitride monolayer of about 0.1 Å magnitude, which were directly resolved, and verified by density functional theory calculations. The results demonstrate that atom-by-atom structural and chemical analysis of all radiation-damage-resistant atoms present in, and on top of, ultra-thin sheets has now become possible.

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Acknowledgements

We thank L. M. Brown, J. N. Coleman, P. Rez and J. C. H. Spence for discussions. Research at Oak Ridge National Laboratory (M.F.C., T.J.P., M.P.O., S.T.P. and S.J.P.) was sponsored by the Division of Materials Sciences and Engineering of the US Department of Energy. Research at Vanderbilt was supported in part by the US Department of Energy grant DE-FG02- 09ER46554 and the McMinn Endowment. Computations were performed at the National Energy Research Scientific Computing Center at Lawrence Berkeley National Laboratory.

Author Contributions O.L.K. initiated the project and wrote the paper, M.F.C., N.D., O.L.K. and M.F.M. recorded preliminary experimental data, M.F.C. improved the imaging and recorded the data used in the paper, V.N. prepared the samples, O.L.K. and N.D. performed data processing and analysis, T.J.P. and S.T.P. performed DFT calculations, M.P.O. performed image calculations, S.J.P. initiated the aberration-corrected microscopy project at ORNL and advised on the paper, and G.J.C., N.D., O.L.K., M.F.M, C.S.O. and Z.S.S. designed and built the electron microscope. All the authors read and commented on the manuscript.

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Authors and Affiliations

  1. Nion Co., 1102 8th Street, Kirkland, Washington 98033, USA ,
    Ondrej L. Krivanek, George J. Corbin, Niklas Dellby, Matthew F. Murfitt, Christopher S. Own & Zoltan S. Szilagyi
  2. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6069, USA,
    Matthew F. Chisholm, Timothy J. Pennycook, Mark P. Oxley, Sokrates T. Pantelides & Stephen J. Pennycook
  3. Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, UK,
    Valeria Nicolosi
  4. Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37235, USA,
    Timothy J. Pennycook, Mark P. Oxley, Sokrates T. Pantelides & Stephen J. Pennycook

Authors

  1. Ondrej L. Krivanek
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  2. Matthew F. Chisholm
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  3. Valeria Nicolosi
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  4. Timothy J. Pennycook
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  5. George J. Corbin
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  6. Niklas Dellby
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  7. Matthew F. Murfitt
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  8. Christopher S. Own
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  9. Zoltan S. Szilagyi
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  10. Mark P. Oxley
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  11. Sokrates T. Pantelides
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  12. Stephen J. Pennycook
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Correspondence toOndrej L. Krivanek.

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G.J.C., N.D., O.L.K., M.F.M. and Z.S.S. have a financial interest in Nion Co.

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Krivanek, O., Chisholm, M., Nicolosi, V. et al. Atom-by-atom structural and chemical analysis by annular dark-field electron microscopy.Nature 464, 571–574 (2010). https://doi.org/10.1038/nature08879

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Editorial Summary

Elemental mapping atom-by-atom

An imaging technique able to resolve and identify all individual atoms in non-periodic solids would be a very useful tool for materials analysis. Annular dark-field (ADF) imaging in an aberration-corrected scanning transmission electron microscope optimized for low voltage operation allows such an analysis, as shown by Ondrej Krivanek and co-workers. The technique was used to examine a monolayer of boron nitride, in which it revealed individual atomic substitutions involving carbon and oxygen impurity atoms. Careful analysis of the data enables the construction of a detailed map of the atomic structure, with all the atoms of the four species resolved and identified.

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