Metal-Enhanced Fluorescence: Wavelength-Dependent Ultrafast Energy Transfer

Abstract

The fluorescence of dye molecules often shows a strong increase in intensity near metal surfaces or nanoparticles. The excited-state dynamics of 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM) in the presence of a silver island film (SIF) were explored by femtosecond transient absorption spectroscopy. Under 403 nm excitation, we found clear differences in the excited-state spectra and kinetics of DCM with the SIF. From the analysis of the emission kinetics of DCM, an additional process with a 40-60 ps time constant was distinguished, which was hypothesized to be surface plasmon-coupled fluorescence. This ultrafast process for 403 nm excitation was confirmed as ultrafast energy transfer directly from the surface plasmon of the SIF to DCM. Under 480 nm excitation, no such ultrafast process was observed, but a constant increase in the emission intensity by similar to 10% due to the increased electric field of the silver nanoparticles occurred.