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Energy-resolved plasmonic chemistry in individual nanoreactors

Nature Nanotechnology volume 16, pages 1378–1385 (2021)Cite this article

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Abstract

Plasmonic resonances can concentrate light into exceptionally small volumes, which approach the molecular scale. The extreme light confinement provides an advantageous pathway to probe molecules at the surface of plasmonic nanostructures with highly sensitive spectroscopies, such as surface-enhanced Raman scattering. Unavoidable energy losses associated with metals, which are usually seen as a nuisance, carry invaluable information on energy transfer to the adsorbed molecules through the resonance linewidth. We measured a thousand single nanocavities with sharp gap plasmon resonances spanning the red to near-infrared spectral range and used changes in their linewidth, peak energy and surface-enhanced Raman scattering spectra to monitor energy transfer and plasmon-driven chemical reactions at their surface. Using methylene blue as a model system, we measured shifts in the absorption spectrum of molecules following surface adsorption and revealed a rich plasmon-driven reactivity landscape that consists of distinct reaction pathways that occur in separate resonance energy windows.

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Fig. 1: NCoMs as energy-tunable nanoreactors.
Fig. 2: Forming an experimental resonance energy scale.
Fig. 3: CID and effective molecular absorption.
Fig. 4: MB blue plasmon-driven chemistry.

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Data availability

Datasets generated during and/or analysed during the current study are available online at https://doi.org/10.6084/m9.figshare.15051894.v1.

Code availability

All custom codes used in the current study are provided along with the relevant data online at https://doi.org/10.6084/m9.figshare.15051894.v1.

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Acknowledgements

We thank J. Kuster for software development and support, and L. Leppert and T. B. de Queiroz for helpful discussions. This work was supported by the Dutch Research Council (NWO). I.S., A.X., J.J.B. and A.F.K. acknowledge support from the European Research Council (ERC) under the Horizon 2020 Research and Innovation Programme THOR (grant agreement no. 829067), PICOFORCE (grant agreement no. 883703) and POSEIDON (grant agreement no. 861950). J.J.B. acknowledges funding from the EPSRC (Cambridge NanoDTC EP/L015978/1, EP/L027151/1, EP/S022953/1, EP/P029426/1 and EP/R020965/1). A.B. acknowledges support from the Dutch Research Council (NWO) via the Vidi award 680-47-550.

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Authors and Affiliations

  1. Center for Nanophotonics, AMOLF, Amsterdam, the Netherlands

    Eitan Oksenberg, Ilan Shlesinger, A. Femius Koenderink & Erik C. Garnett

  2. NanoPhotonics Centre, Cavendish Laboratory, Department of Physics, University of Cambridge, Cambridge, UK

    Angelos Xomalis & Jeremy J. Baumberg

  3. DIFFER—Dutch Institute for Fundamental Energy Research, Eindhoven, the Netherlands

    Andrea Baldi

  4. Department of Physics and Astronomy, Vrije Universiteit Amsterdam, Amsterdam, the Netherlands

    Andrea Baldi

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Contributions

E.C.G., E.O. and A.B. conceived the experiments. I.S., A.X., J.J.B. and A.F.K. performed the SERS measurements. E.O. fabricated the samples, performed the optical measurement, conducted the electromagnetic simulations, produced the electron microscopy images and analysed the data. E.C.G. and E.O. wrote the manuscript. All the authors discussed the results and commented on the manuscript.

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Correspondence to Erik C. Garnett.

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Peer review information Nature Nanotechnology thanks Suljo Linic and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Sections 1–7 and Figs. 1–14.

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Oksenberg, E., Shlesinger, I., Xomalis, A. et al. Energy-resolved plasmonic chemistry in individual nanoreactors. Nat. Nanotechnol. 16, 1378–1385 (2021). https://doi.org/10.1038/s41565-021-00973-6

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