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Plasmonic quantum size effects in silver nanoparticles are dominated by interfaces and local environments

Nature Physics volume 15, pages 275–280 (2019)Cite this article

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Abstract

The physical properties of metals change when their dimensions are reduced to the nano-scale and new phenomena such as the localized surface-plasmon resonance (LSPR) appear. This collective electronic excitation can be tuned over a large spectral range by adapting the material, size and shape. The existing literature is as rich as it is controversial—for example, size-dependent spectral shifts of the LSPR in small metal nanoparticles, induced by quantum effects, are reported to the red, to the blue or entirely absent. Here we report how complementary experiments on size-selected small silver nanoparticles embedded in silica can yield inconsistent results on the same system: whereas optical absorption shows no size effect in the range between only a few atoms and ~10 nm, a clear spectral shift is observed in single-particle electron spectroscopy. Our quantitative interpretation, based on a mixed classical/quantum model, resolves the apparent contradictions, not only within our experimental data, but also in the literature. Our comprehensive model describes how the local environment is the crucial parameter controlling the manifestation or absence of quantum size effects.

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Fig. 1: Optical spectroscopy.
Fig. 2: Electron spectroscopy.
Fig. 3: Electron-beam-induced interface reduction.
Fig. 4: Electron-dose-dependent LSPR shift.
Fig. 5: Theoretical and experimental size dependencies.
Fig. 6: Plasmon peak shift.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

We acknowledge financial support from the French National Research Agency (Agence Nationale de Recherche, ANR) in the frame of the project ‘FIT SPRINGS’, ANR-14-CE08-0009. This work has received support from the National Agency for Research under the programme of future investment TEMPOSCHROMATEM with the Reference Number ANR-10-EQPX-50. This work was performed using the Lyon Cluster Research Platform PLYRA. M.H. acknowledges support from the Brazilian Science Without Borders ‘Special Visiting Scientist’ programme (88881.030488/2013-01), and from the São Paulo Research Foundation (FAPESP, 16/12807-4). We gratefully acknowledge technical support from O. Boisron, C. Albin and C. Clavier and fruitful discussions with D. Ugarte.

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Authors and Affiliations

  1. Laboratoire de Physique des Solides, UMR 8502 CNRS and Université Paris-Sud, Orsay, France

    Alfredo Campos & Mathieu Kociak

  2. Institut Lumière Matière, Université de Lyon, Université Claude Bernard Lyon 1, CNRS, UMR5306, Villeurbanne, France

    Nicolas Troc, Emmanuel Cottancin, Michel Pellarin, Jean Lermé & Matthias Hillenkamp

  3. Aix Marseille University, CNRS, CINaM UMR 7325, Marseille, France

    Hans-Christian Weissker

  4. European Theoretical Spectroscopy Facility https://www.etsf.eu

    Hans-Christian Weissker

  5. Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas, R. Sergio B. de Holanda 777, Campinas-SP, Brazil

    Matthias Hillenkamp

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Contributions

H.-C.W., M.K. and M.H. designed the project; N.T., E.C., M.P. and M.H. fabricated the samples and performed optical spectroscopy; A.C. and M.K. performed STEM-EELS experiments, treated the data and developed the corresponding theoretical description; J.L. developed the theoretical model of the optical response and its equivalence to EELS and performed the calculations; M.H. coordinated the data interpretation and wrote the manuscript; all authors participated in the discussion.

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Correspondence to Matthias Hillenkamp.

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3 chapters, 19 figures, 64 references, 64 equations

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Campos, A., Troc, N., Cottancin, E. et al. Plasmonic quantum size effects in silver nanoparticles are dominated by interfaces and local environments. Nat. Phys. 15, 275–280 (2019). https://doi.org/10.1038/s41567-018-0345-z

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