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Three-dimensional atomic imaging of crystalline nanoparticles

Abstract

Determining the three-dimensional (3D) arrangement of atoms in crystalline nanoparticles is important for nanometre-scale device engineering and also for applications involving nanoparticles, such as optoelectronics or catalysis. A nanoparticle’s physical and chemical properties are controlled by its exact 3D morphology, structure and composition1. Electron tomography enables the recovery of the shape of a nanoparticle from a series of projection images2,3,4. Although atomic-resolution electron microscopy has been feasible for nearly four decades, neither electron tomography nor any other experimental technique has yet demonstrated atomic resolution in three dimensions. Here we report the 3D reconstruction of a complex crystalline nanoparticle at atomic resolution. To achieve this, we combined aberration-corrected scanning transmission electron microscopy5,6,7, statistical parameter estimation theory8,9 and discrete tomography10,11. Unlike conventional electron tomography, only two images of the target—a silver nanoparticle embedded in an aluminium matrix—are sufficient for the reconstruction when combined with available knowledge about the particle’s crystallographic structure. Additional projections confirm the reliability of the result. The results we present help close the gap between the atomic resolution achievable in two-dimensional electron micrographs and the coarser resolution that has hitherto been obtained by conventional electron tomography.

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Figure 1: Quantification of HAADF STEM images.
Figure 2: Analysis of scattered intensities.
Figure 3: Three-dimensional reconstruction.
Figure 4: Comparison of experimental images with projected 3D reconstructions.

References

  1. Olson, G. B. Designing a new material world. Science 288, 993–998 (2000)

    CAS  Article  Google Scholar 

  2. Arslan, I., Yates, T. J. V., Browning, N. D. & Midgley, P. A. Embedded nanostructures revealed in three dimensions. Science 309, 2195–2198 (2005)

    ADS  CAS  Article  Google Scholar 

  3. Midgley, P. A. & Dunin-Borkowski, R. E. Electron tomography and holography in materials science. Nature Mater. 8, 271–280 (2009)

    ADS  CAS  Article  Google Scholar 

  4. Batenburg, K. J. et al. 3D imaging of nanomaterials by discrete tomography. Ultramicroscopy 109, 730–740 (2009)

    CAS  Article  Google Scholar 

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

    ADS  CAS  Article  Google Scholar 

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

    ADS  CAS  Article  Google Scholar 

  7. Müller, H., Uhlemann, S., Hartel, P. & Haider, M. Advancing the hexapole Cs-corrector for the scanning transmission electron microscope. Microsc. Microanal. 12, 442–455 (2006)

    ADS  Article  Google Scholar 

  8. den Dekker, A. J., Van Aert, S., van den Bos, A. & Van Dyck, D. Maximum likelihood estimation of structure parameters from high resolution electron microscopy images. Part I: a theoretical framework. Ultramicroscopy 104, 83–106 (2005)

    CAS  Article  Google Scholar 

  9. Van Aert, S. et al. Quantitative atomic resolution mapping using high-angle annular dark field scanning transmission electron microscopy. Ultramicroscopy 109, 1236–1244 (2009)

    CAS  Article  Google Scholar 

  10. Batenburg, K. J. A network flow algorithm for reconstructing binary images from discrete x-rays. J. Math. Imaging Vision 27, 175–191 (2007)

    MathSciNet  Article  Google Scholar 

  11. Jinschek, J. R. et al. 3-D reconstruction of the atomic positions in a simulated gold nanocrystal based on discrete tomography: Prospects of atomic resolution electron tomography. Ultramicroscopy 108, 589–604 (2008)

    CAS  Article  Google Scholar 

  12. Crewe, A. V., Wall, J. & Welter, L. M. A high-resolution scanning transmission electron microscope. J. Appl. Phys. 39, 5861–5868 (1968)

    ADS  Article  Google Scholar 

  13. Hartel, P., Rose, H. & Dinges, C. Conditions and reasons for incoherent imaging in STEM. Ultramicroscopy 63, 93–114 (1996)

    CAS  Article  Google Scholar 

  14. Nellist, P. D. & Pennycook, S. J. The principles and interpretation of annular dark-field Z-contrast imaging. Adv. Imaging Electron Phys. 113, 147–203 (2000)

    Article  Google Scholar 

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

    ADS  CAS  Article  Google Scholar 

  16. Erni, R., Rossell, M. D., Kisielowski, C. & Dahmen, U. Atomic-resolution imaging with a sub-50-pm electron probe. Phys. Rev. Lett. 102, 096101 (2009)

    ADS  Article  Google Scholar 

  17. Pennycook, S. J., Lupini, A. R., Borisevich, A. Y., Peng, Y. & Shibata, N. 3D atomic resolution imaging through aberration-corrected STEM. Microsc. Microanal. 10, (Suppl. 1.2)1172–1173 (2004)

    ADS  Article  Google Scholar 

  18. van Benthem, K. et al. Three-dimensional ADF imaging of individual atoms by through-focal series scanning transmission electron microscopy. Ultramicroscopy 106, 1062–1068 (2006)

    CAS  Article  Google Scholar 

  19. Li, Z. Y. et al. Three-dimensional atomic-scale structure of size-selected gold nanoclusters. Nature 451, 46–48 (2008)

    CAS  Article  Google Scholar 

  20. Hillyard, S. & Silcox, J. Detector geometry, thermal diffuse-scattering and strain effects in ADF STEM imaging. Ultramicroscopy 58, 6–17 (1995)

    CAS  Article  Google Scholar 

  21. Klenov, D. O., Zide, J. M., Zimmerman, J. D., Gossard, A. C. & Stemmer, S. Interface atomic structure of epitaxial ErAs layers on (001)In0. 53Ga0. 47As and GaAs. Appl. Phys. Lett. 86, 241901 (2005)

    ADS  Article  Google Scholar 

  22. Dwyer, C., Erni, R. & Etheridge, J. Measurement of effective source distribution and its importance for quantitative interpretation of STEM images. Ultramicroscopy 110, 952–957 (2010)

    CAS  Article  Google Scholar 

  23. Dubey, Ph. A., Schönfeld, B. & Kostorz, G. Shape and internal structure of Guinier-Preston zones in Al-Ag. Acta Metall. Mater. 39, 1161–1170 (1991)

    CAS  Article  Google Scholar 

  24. Malik, A., Schonfeld, B., Kostorz, G. & Pedersen, J. S. Microstructure of Guinier-Preston zones in Al-Ag. Acta Mater. 44, 4845–4852 (1996)

    CAS  Article  Google Scholar 

  25. Kisielowski, C. et al. Detection of single atoms and buried defects in three dimensions by aberration-corrected electron microscope with 0.5-angstrom information limit. Microsc. Microanal. 14, 469–477 (2008)

    ADS  CAS  Article  Google Scholar 

  26. Erni, R., Heinrich, H. & Kostorz, G. On the internal structure of Guinier-Preston zones in Al-3 at.% Ag. Phil. Mag. Lett. 83, 599–609 (2003)

    ADS  CAS  Article  Google Scholar 

  27. Xin, H. L. & Muller, D. A. Aberration-corrected ADF-STEM depth sectioning and prospects for reliable 3D imaging in S/TEM. J. Electron Microsc. 58, 157–165 (2009)

    CAS  Article  Google Scholar 

  28. McLachlan, G. & Peel, D. Finite Mixture Models (eds Shewhart, W. A. & Wilks, S. S. ) (Wiley Series in Probability and Statistics, John Wiley & Sons, 2000)

    Book  Google Scholar 

  29. Kirkpatrick, S., Gelatt, C. D. & Vecchi, M. P. Optimization by simulated annealing. Science 220, 671–680 (1983)

    ADS  MathSciNet  CAS  Article  Google Scholar 

  30. Malis, T., Cheng, S. C. & Egerton, R. F. EELS log-ratio technique for specimen-thickness measurement in the TEM. J. Electron Microsc. Tech. 8, 193–200 (1988)

    CAS  Article  Google Scholar 

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Acknowledgements

Part of this work was performed at the National Center for Electron Microscopy (LBNL) which is supported by the Office of Science, Office of Basic Energy Sciences of the US Department of Energy under contract number DE-AC02-05CH11231. Financial support from the European Union for the Framework 6 programme under a contract for an Integrated Infrastructure Initiative (reference 026019 ESTEEM) is acknowledged.

Author information

Authors and Affiliations

Authors

Contributions

S.V.A. developed and applied a method of counting the number of atoms. K.J.B. reconstructed the nanoparticle in three dimensions. M.D.R. and R.E. prepared the sample and recorded the experimental images. G.V.T. advised on the methodology, the interpretation and on the paper. All the authors read and commented on the paper.

Corresponding author

Correspondence to Sandra Van Aert.

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Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

The file contains Supplementary Methods, Supplementary Table 1, Supplementary Figures 1-6 with legends and additional references. (PDF 572 kb)

Supplementary Movie 1

The movie shows the computed 3D reconstruction of a Ag nanocluster showing the 3D position of all 784 atoms. (MOV 16227 kb)

Supplementary Movie 2

The movie shows the computed 3D reconstruction in which the Ag nanocluster is tilted from the [101] zone-axis toward [100], [41 1], [21 1] , and back. (MOV 8517 kb)

Supplementary Movie 3

The movie shows the computed 3D reconstruction in which the Ag nanocluster is tilted from the [101] zone-axis toward [100], [41 1], [21 1], and back. This movie includes a confidence estimate for each atom position. The radius of the bright shell around the atoms represents the confidence that can be associated with a particular atom. Absence of the shell represents high confidence, while a large shell represents high uncertainty. (MOV 7998 kb)

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Van Aert, S., Batenburg, K., Rossell, M. et al. Three-dimensional atomic imaging of crystalline nanoparticles. Nature 470, 374–377 (2011). https://doi.org/10.1038/nature09741

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