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Atom-resolved imaging of ordered defect superstructures at individual grain boundaries


The ability to resolve spatially and identify chemically atoms in defects would greatly advance our understanding of the correlation between structure and property in materials1. This is particularly important in polycrystalline materials, in which the grain boundaries have profound implications for the properties and applications of the final material2. However, such atomic resolution is still extremely difficult to achieve, partly because grain boundaries are effective sinks for atomic defects and impurities3,4,5, which may drive structural transformation of grain boundaries and consequently modify material properties6,7. Regardless of the origin of these sinks, the interplay between defects and grain boundaries complicates our efforts to pinpoint the exact sites and chemistries of the entities present in the defective regions, thereby limiting our understanding of how specific defects mediate property changes. Here we show that the combination of advanced electron microscopy, spectroscopy and first-principles calculations can provide three-dimensional images of complex, multicomponent grain boundaries with both atomic resolution and chemical sensitivity. The high resolution of these techniques allows us to demonstrate that even for magnesium oxide, which has a simple rock-salt structure, grain boundaries can accommodate complex ordered defect superstructures that induce significant electron trapping in the bandgap of the oxide. These results offer insights into interactions between defects and grain boundaries in ceramics and demonstrate that atomic-scale analysis of complex multicomponent structures in materials is now becoming possible.

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Figure 1: Chemical and structural analysis of a Σ = 5, (310)[001] grain boundary.
Figure 2: Atomic-column imaging of the Σ = 5 grain boundary.
Figure 3: Formation of an ordered defect superstructure at the grain boundary.
Figure 4: Calculated free energy of grain boundary as a function of the chemical potential of oxygen ( μO).


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

    Article  CAS  Google Scholar 

  2. Buban, J. P. et al. Grain boundary strengthening in alumina by rare earth impurities. Science 311, 212–215 (2006)

    Article  ADS  CAS  Google Scholar 

  3. Kingery, W. D. Plausible concepts necessary and sufficient for interpretation of ceramic grain-boundary phenomena: I, grain-boundary characteristics, structure, and electrostatic potential. J. Am. Ceram. Soc. 57, 1–8 (1974)

    Article  CAS  Google Scholar 

  4. Bai, X. M. et al. Efficient annealing of radiation damage near grain boundaries via interstitial emission. Science 327, 1631–1634 (2010)

    Article  ADS  CAS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

  6. Lartigue-Korinek, S., Bouchet, D., Bleloch, A. & Colliex, C. HAADF study of the relationship between intergranular defect structure and yttrium segregation in an alumina grain boundary. Acta Mater. 59, 3519–3527 (2011)

    Article  CAS  Google Scholar 

  7. Maiti, A. et al. Dopant segregation at semiconductor grain boundaries through cooperative chemical rebonding. Phys. Rev. Lett. 77, 1306–1309 (1996)

    Article  ADS  CAS  Google Scholar 

  8. Kaiser, U. et al. Direct observation of defect-mediated cluster nucleation. Nature Mater. 1, 102–105 (2002)

    Article  ADS  CAS  Google Scholar 

  9. Barth, C. et al. Recent trends in surface characterization and chemistry with high-resolution scanning force methods. Adv. Mater. 23, 477–501 (2011)

    Article  CAS  Google Scholar 

  10. Muller, D. A. Structure and bonding at the atomic scale by scanning transmission electron microscopy. Nature Mater. 8, 263–270 (2009)

    Article  ADS  CAS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

  12. Huang, P. Y. et al. Grains and grain boundaries in single-layer graphene atomic patchwork quilts. Nature 469, 389–392 (2011)

    Article  ADS  CAS  Google Scholar 

  13. Klie, R. F. et al. Enhanced current transport at grain boundaries in high-T c superconductors. Nature 435, 475–478 (2005)

    Article  ADS  CAS  Google Scholar 

  14. McKenna, K. P. & Shluger, A. L. First-principles calculations of defects near a grain boundary in MgO. Phys. Rev. B 79, 224116 (2009)

    Article  ADS  Google Scholar 

  15. Chiang, Y. M., Henriksen, A. F. & Kingery, W. D. Characterization of grain-boundary segregation in MgO. J. Am. Ceram. Soc. 64, 385–389 (1981)

    Article  CAS  Google Scholar 

  16. Browning, N. D. et al. Investigating the structure-property relationships at grain boundaries in MgO using bond-valence pair potentials and multiple scattering analysis. J. Am. Ceram. Soc. 82, 366–372 (1999)

    Article  CAS  Google Scholar 

  17. Yan, Y. et al. Impurity-induced structural transformation of a MgO grain boundary. Phys. Rev. Lett. 81, 3675–3678 (1998)

    Article  ADS  CAS  Google Scholar 

  18. Duffy, D. M. Grain boundaries in ionic crystals. J. Phys. C 19, 4393–4412 (1986)

    Article  ADS  CAS  Google Scholar 

  19. Yamakov, V. et al. Dislocation processes in the deformation of nanocrystalline aluminium by molecular-dynamics simulation. Nature Mater. 1, 45–49 (2002)

    Article  ADS  CAS  Google Scholar 

  20. Kizuka, T., Iijima, M. & Tanaka, N. Atomic process of electron-irradiation-induced grain-boundary migration in a MgO tilt boundary. Philos. Mag. A 77, 413–422 (1998)

    Article  ADS  CAS  Google Scholar 

  21. Ortalan, V. et al. Direct imaging of single metal atoms and clusters in the pores of dealuminated HY zeolite. Nature Nanotechnol. 5, 506–510 (2010)

    Article  ADS  CAS  Google Scholar 

  22. Colliex, C. Elementary resolution. Nature 450, 622–623 (2007)

    Article  ADS  CAS  Google Scholar 

  23. Findlay, S. et al. Robust atomic resolution imaging of light elements using scanning transmission electron microscopy. Appl. Phys. Lett. 95, 191913 (2009)

    Article  ADS  Google Scholar 

  24. Ishizuka, K. & Uyeda, N. A new theoretical and practical approach to the multislice methods. Acta Crystallogr. A 33, 740–749 (1977)

    Article  ADS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

  26. Davies, J. J. & Wertz, J. E. The EPR spectrum of trivalent titanium in orthorhombic symmetry in MgO. J. Phys. Chem. Solids 31, 2489–2494 (1970)

    Article  ADS  CAS  Google Scholar 

  27. Tanaka, I. et al. Identification of ultradilute dopants in ceramics. Nature Mater. 2, 541–545 (2003)

    Article  ADS  CAS  Google Scholar 

  28. Vitek, V. & Wang, G. J. Segregation and grain boundary structure. Surf. Sci. 144, 110–123 (1984)

    Article  ADS  CAS  Google Scholar 

  29. McKenna, K. P. & Shluger, A. L. Electron-trapping polycrystalline materials with negative electron affinity. Nature Mater. 7, 859–862 (2008)

    Article  ADS  CAS  Google Scholar 

  30. Harris, D. J., Watson, G. W. & Parker, S. C. Atomistic simulation of the effect of temperature and pressure on the [001] symmetric tilt grain boundaries of MgO. Phil. Mag. A 74, 407–418 (1996)

    Article  ADS  CAS  Google Scholar 

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This work was supported in part by a Grant-in-Aid for Scientific Research on Priority Area “Atomic Scale Modification (474)” from MEXT, Japan. We thank T. Mizoguchi for performing electron energy-loss near-edge structure simulations and for discussions, and T. Saito and W. Zeng for experimental assistance. Z.W. acknowledges support by a Grant-in-Aid for Young Scientists (B) (grant no. 22760500) and from IZUMI Science Foundation. M.S. is grateful for a Grant-in-Aid for Scientific Research (C) (grant no. 23560817) and to MURATA Science Foundation for financial support. K.P.M. acknowledges support by a Grant-in-Aid for Young Scientists (B) (grant no. 22740192). S.T. thanks supports from the Nippon Sheet Glass Foundation. Calculations were conducted at ISSP, University of Tokyo.

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Z.W. prepared specimens, carried out calculations and wrote the manuscript. M.S. made images and conducted image simulation and processing. K.P.M. and A.L.S. helped with the calculations and discussed the results. L.G. and S.T. helped with the experiments. Y.I. discussed the results and directed the entire study. All the authors read and commented on the manuscript.

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Correspondence to Zhongchang Wang.

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The authors declare no competing financial interests.

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Wang, Z., Saito, M., McKenna, K. et al. Atom-resolved imaging of ordered defect superstructures at individual grain boundaries. Nature 479, 380–383 (2011).

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