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Electromagnetic and chemical interaction between Ag nanoparticles and adsorbed rhodamine molecules in surface-enhanced Raman scattering

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Abstract

The critical importance of the junction between touching or closely adjacent Ag nanoparticles associated with single-molecule sensitivity (SMS) in surface-enhanced Raman scattering (SERS) was confirmed via the following observations: (1) an additional peak is observed in elastic scattering only for the SERS-active state, which originated from absorption of adsorbates, (2) local- and far-field evaluation using a finite difference time domain method could reproduce this extra peak and anticipate the significantly enhanced field even inside the adsorbates sitting at the junction through an increased coupling of the localized surface plasmons, and (3) in addition to enhanced fluorescence of adsorbed dye, an inelastic scattering peak was observed and attributed to the metal surface electron. Concerning the chemical enhancement in SERS, Cl− anions activate the Ag-Cl-R6G (rhodamine) samples by inducing intrinsic electronic interaction between Ag and R6G molecules. This electronic interaction is irreversibly quenched by the addition of thiosulfate anions which dissolve Ag+ cations while the electromagnetic (EM) effect remains intact.

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Acknowledgments

This research was financially supported in part by Grant-in-Aid for Scientific Research (B) 17350013 by Japan Society for the Promotion of Science (JSPS) and by Core Research for Evolutional Science and Technology (CREST) project in the Japan Science and Technology Agency (JST). We thank Dr. Mitsuru Ishikawa (AIST) for collaboration.

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Authors and Affiliations

  1. Nanoarchitectonics Research Center, National Institute of Advanced Industrial Science and Technology, 1-1-1 Higashi, Tsukuba, 305-8562, Japan

    M. Futamata

  2. Tsukuba Research Laboratory, Hamamatsu Photonics K.K., Tsukuba, 300-2635, Japan

    Y. Maruyama

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  1. M. Futamata
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  2. Y. Maruyama
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Correspondence to M. Futamata.

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Futamata, M., Maruyama, Y. Electromagnetic and chemical interaction between Ag nanoparticles and adsorbed rhodamine molecules in surface-enhanced Raman scattering. Anal Bioanal Chem 388, 89–102 (2007). https://doi.org/10.1007/s00216-007-1183-5

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  • DOI: https://doi.org/10.1007/s00216-007-1183-5

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