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Modified optical absorption of molecules on metallic nanoparticles at sub-monolayer coverage

Nature Photonics volume 10, pages 40–45 (2016)Cite this article

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Abstract

Enhanced optical absorption of molecules in the vicinity of metallic nanostructures is key to a number of surface-enhanced spectroscopies and of great general interest to the fields of plasmonics and nano-optics. However, experimental access to this absorbance has long proven elusive. Here, we present direct measurements of the surface absorbance of dye molecules adsorbed onto silver nanospheres and, crucially, at sub-monolayer concentrations where dye–dye interactions become negligible. With a large detuning from the plasmon resonance, distinct shifts and broadening of the molecular resonances reveal the intrinsic properties of the dye in contact with the metal colloid, in contrast to the often studied strong-coupling regime where the optical properties of the dye molecules cannot be isolated. The observation of these shifts together with the ability to routinely measure them has broad implications in the interpretation of experiments involving resonant molecules on metallic surfaces, such as surface-enhanced spectroscopies and many aspects of molecular plasmonics.

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Figure 1: Mie theory simulations of dye-coated spheres.
Figure 2: Differential absorbance measurements.
Figure 3: Differential absorbance spectra of common dyes adsorbed on silver nanoparticles.

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Acknowledgements

E.C.L.R. acknowledges the Royal Society of New Zealand (RSNZ) for support via a Rutherford Discovery Fellowship. The authors thank A. Edgar, P. Northcote and M. Lein from Victoria University of Wellington for discussions.

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Authors and Affiliations

  1. The MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Chemical and Physical Sciences, Victoria University of Wellington, PO Box 600, Wellington, 6140, New Zealand

    Brendan L. Darby, Baptiste Auguié, Matthias Meyer, Andres E. Pantoja & Eric C. Le Ru

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  1. Brendan L. Darby
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  2. Baptiste Auguié
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Contributions

B.L.D. and E.C.L.R. designed the original ideas presented in this work and built the experimental set-up with A.E.P. B.L.D. carried out most of the experiments. M.M. optimized various aspects of the experimental set-up, carried out extensive calibration, and performed the DFT calculations. B.A., B.L.D. and E.C.L.R. developed and performed the electromagnetic theory and calculations. The manuscript was jointly written by B.L.D., B.A. and E.C.L.R. All authors discussed the results and the manuscript.

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Correspondence to Eric C. Le Ru.

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Darby, B., Auguié, B., Meyer, M. et al. Modified optical absorption of molecules on metallic nanoparticles at sub-monolayer coverage. Nature Photon 10, 40–45 (2016). https://doi.org/10.1038/nphoton.2015.205

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