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High-speed imaging of surface-enhanced Raman scattering fluctuations from individual nanoparticles

Nature Nanotechnology volume 14, pages 981–987 (2019)Cite this article

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Abstract

The concept of plasmonic hotspots is central to the interpretation of the surface-enhanced Raman scattering (SERS) effect. Although plasmonic hotspots are generally portrayed as static features, single-molecule SERS (SM-SERS) is marked by characteristic time-dependent fluctuations in signal intensity. The origin of those fluctuations can be assigned to a variety of dynamic and complex processes, including molecular adsorption or desorption, surface diffusion, molecular reorientation and metal surface reconstruction. Since each of these mechanisms simultaneously contributes to a fluctuating SERS signal, probing their relative impact in SM-SERS remains an experimental challenge. Here, we introduce a super-resolution imaging technique with an acquisition rate of 800,000 frames per second to probe the spatial and temporal features of the SM-SERS fluctuations from single silver nanoshells. The technique has a spatial resolution of ~7 nm. The images reveal short ~10 µs scattering events localized in various regions on a single nanoparticle. Remarkably, even a fully functionalized nanoparticle was ‘dark’ more than 98% of the time. The sporadic SERS emission suggests a transient hotspot formation mechanism driven by a random reconstruction of the metallic surface, an effect that dominates over any plasmonic resonance of the particle itself. Our results provide the SERS community with a high-speed experimental approach to study the fast dynamic properties of SM-SERS hotspots in typical room-temperature experimental conditions, with possible implications in catalysis and sensing.

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Fig. 1: Experimental overview.
Fig. 2: High-speed SERS signal acquisition and super-resolution imaging.
Fig. 3: Time statistics and spatial locations of single-molecule SIFs.
Fig. 4: Wavelength, temperature and power dependence of SIFs.

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Data availability

The data that support the conclusions of this study are available from the corresponding author upon request.

Code availability

The MATLAB codes used in this study are available from the corresponding author upon request.

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Acknowledgements

This work was supported by an operating grant from NSERC Discovery Grant programme and by the National Science Foundation through CAREER grant no. 1552642. We also thank Compute Canada for access to computational resources. Instrument grants were provided by the Canada Foundation for Innovation, the British Columbia knowledge and Development fund (BCKDF) and by the University of Victoria. We also thank C. Bohne for access to the temperature-controlled stage.

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Author notes

  1. These authors contributed equally: Nathan C. Lindquist, Carlos Diego L. de Albuquerque.

Authors and Affiliations

  1. Department of Physics and Engineering, Bethel University, St Paul, MN, USA

    Nathan C. Lindquist

  2. Department of Chemistry, University of Victoria, Victoria, British Columbia, Canada

    Carlos Diego L. de Albuquerque, Regivaldo G. Sobral-Filho, Irina Paci & Alexandre G. Brolo

  3. Centre for Advanced Materials and Related Technologies (CAMTEC), University of Victoria, Victoria, British Columbia, Canada

    Carlos Diego L. de Albuquerque, Regivaldo G. Sobral-Filho, Irina Paci & Alexandre G. Brolo

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Contributions

R.G.S.-F. synthesized and characterized the nanoparticles. I.P. performed the computational work. N.C.L. and C.D.L.d.A. contributed equally to all other experiments. A.G.B., N.C.L. and C.D.L.d.A. wrote the paper together.

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Correspondence to Alexandre G. Brolo.

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Peer review information: Nature Nanotechnology thanks Francois Lagugné-Labarthet and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

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Supplementary Figs. 1–8.

Supplementary Movie 1

Atomic fluctuations in a metal cluster.

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Lindquist, N.C., de Albuquerque, C.D.L., Sobral-Filho, R.G. et al. High-speed imaging of surface-enhanced Raman scattering fluctuations from individual nanoparticles. Nat. Nanotechnol. 14, 981–987 (2019). https://doi.org/10.1038/s41565-019-0535-6

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