Excitation laser energy dependence of surface-enhanced fluorescence showing plasmon-induced ultrafast electronic dynamics in dye molecules

T Itoh, YS Yamamoto, H Tamaru, V Biju, N Murase… - Physical Review B …, 2013 - APS
T Itoh, YS Yamamoto, H Tamaru, V Biju, N Murase, Y Ozaki
Physical Review B—Condensed Matter and Materials Physics, 2013APS
We find unique properties accompanying surface-enhanced fluorescence (SEF) from dye
molecules adsorbed on Ag nanoparticle aggregates, which generate surface-enhanced
Raman scattering. The properties are observed in excitation laser energy dependence of
SEF after excluding plasmonic spectral modulation in SEF. The unique properties are large
blue shifts of fluorescence spectra, deviation of ratios between anti-Stokes SEF intensity and
Stokes from those of normal fluorescence, super-broadening of Stokes spectra, and …
We find unique properties accompanying surface-enhanced fluorescence (SEF) from dye molecules adsorbed on Ag nanoparticle aggregates, which generate surface-enhanced Raman scattering. The properties are observed in excitation laser energy dependence of SEF after excluding plasmonic spectral modulation in SEF. The unique properties are large blue shifts of fluorescence spectra, deviation of ratios between anti-Stokes SEF intensity and Stokes from those of normal fluorescence, super-broadening of Stokes spectra, and returning to original fluorescence by lower energy excitation. We elucidate that these properties are induced by electromagnetic enhancement of radiative decay rates exceeding the vibrational relaxation rates within an electronic excited state, which suggests that molecular electronic dynamics in strong plasmonic fields can be largely deviated from that in free space.
American Physical Society
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