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Coordination-dependent surface atomic contraction in nanocrystals revealed by coherent diffraction

Nature Materials volume 7, pages 308–313 (2008)Cite this article

Abstract

Surface atoms have fewer interatomic bonds than those in the bulk that they often relax and reconstruct on extended two-dimensional surfaces. Far less is known about the surface structures of nanocrystals. Here, we show that coherent diffraction patterns recorded from individual nanocrystals are very sensitive to the atomic structure of nanocrystal surfaces. Nanocrystals of Au of 3–5 nm in diameter were studied by examining diffraction intensity oscillations around the Bragg peaks. Both results obtained from modelling the experimental data and molecular dynamics simulations strongly suggest inhomogeneous relaxations, involving large out-of-plane bond length contractions for the edge atoms (∼0.2 Å); a significant contraction (∼0.13 Å) for {100} surface atoms; and a much smaller contraction (∼0.05 Å) for atoms in the middle of the {111} facets. These results denote a coordination/facet dependence that markedly differentiates the structural dynamics of nanocrystals from bulk crystalline surfaces.

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Figure 1: Coherent electron diffraction pattern recorded from a single, faceted, Au nanocrystal (∼4 nm in size).
Figure 2: Experimental diffraction intensities of a Au nanocrystal and their modelling.
Figure 3: Bond length distributions in the Au nanocrystal obtained by modelling the experimental diffraction pattern.
Figure 4: Surface atom contraction obtained from the molecular dynamics simulation.

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Acknowledgements

The work was supported by NSF Career Award, DMR 0449790 (W.J.H., J.M.Z.), DOE DEFG02-01ER45923 (R.S., J.T., J.M.Z.) and DEFG02-03ER15476 (R.G.N., L.D.M.). The electron microscopy work was carried out in the Center for Microanalysis of Materials, University of Illinois, which is partially supported by the US Department of Energy under grant DEFG02-91-ER45439.

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  1. J. Tao

    Present address: Present address: Condensed Matter Physics and Materials Science Department, Brookhaven National Laboratory, Upton, New York 11973, USA,

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA

    W. J. Huang, R. Sun, J. Tao & J. M. Zuo

  2. Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA

    W. J. Huang, R. Sun, J. Tao, L. D. Menard, R. G. Nuzzo & J. M. Zuo

  3. Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA

    L. D. Menard & R. G. Nuzzo

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  1. W. J. Huang
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Contributions

W.J.H., R.S., J.T. and J.M.Z. carried out the diffraction experiment, modelling and analysis. L.D.M. and R.G.N. carried out particle synthesis.

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Correspondence to J. M. Zuo.

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Huang, W., Sun, R., Tao, J. et al. Coordination-dependent surface atomic contraction in nanocrystals revealed by coherent diffraction. Nature Mater 7, 308–313 (2008). https://doi.org/10.1038/nmat2132

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