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Differential stress induced by thiol adsorption on facetted nanocrystals

Nature Materials volume 10, pages 862–866 (2011)Cite this article

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Abstract

Polycrystalline gold films coated with thiol-based self-assembled monolayers (SAM) form the basis of a wide range of nanomechanical sensor platforms1. The detection of adsorbates with such devices relies on the transmission of mechanical forces, which is mediated by chemically derived stress at the organic–inorganic interface. Here, we show that the structure of a single 300-nm-diameter facetted gold nanocrystal, measured with coherent X-ray diffraction, changes profoundly after the adsorption of one of the simplest SAM-forming organic molecules. On self-assembly of propane thiol, the crystal’s flat facets contract radially inwards relative to its spherical regions. Finite-element modelling indicates that this geometry change requires large stresses that are comparable to those observed in cantilever measurements. The large magnitude and slow kinetics of the contraction can be explained by an intermixed gold–sulphur layer that has recently been identified crystallographically2. Our results illustrate the importance of crystal edges and grain boundaries in interface chemistry and have broad implications for the application of thiol-based SAMs, ranging from nanomechanical sensors to coating technologies.

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Figure 1: CXD data.
Figure 2: Difference Fourier analysis showing the location of the crystal distortions due to thiol binding.
Figure 3: Measured strain and FEA simulation of the effect of surface stress.

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Acknowledgements

Work supported by the ‘nanosculpture’ Advanced Grant from the European Research Council, a Science and Innovation Award for Nanometrology and a Nanotechnology ‘Grand Challenge in Healthcare’ award from the UK Engineering and Physical Sciences Research Council. Measurements were carried out at APS, which is operated by the US Department of Energy.

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Authors and Affiliations

  1. London Centre for Nanotechnology, University College London, London WC1E 6BT, UK

    Moyu Watari, Rachel A. McKendry, Manuel Vögtli, Gabriel Aeppli, Xiaowen Shi, Gang Xiong, Xiaojing Huang & Ian K. Robinson

  2. London Centre for Nanotechnology, Imperial College, London SW7 2AZ, UK

    Yeong-Ah Soh

  3. Advanced Photon Source, Argonne, Illinois 60439, USA

    Ross Harder

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Contributions

Project was conceived by M.W., R.A.M., G.A., Y-A.S. and I.K.R. M.W., R.H. and I.K.R. carried out the X-ray measurements, M.W. and M.V. the cantilever measurements, X.S. and G.X. the FEA analysis and M.W., X.H., R.H. and I.K.R. the DFM analysis. All authors contributed to interpreting the results and writing the manuscript.

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Correspondence to Ian K. Robinson.

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The authors declare no competing financial interests.

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Watari, M., McKendry, R., Vögtli, M. et al. Differential stress induced by thiol adsorption on facetted nanocrystals. Nature Mater 10, 862–866 (2011). https://doi.org/10.1038/nmat3124

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