Five Orders-of-Magnitude Enhancement of Two-Photon Absorption for Dyes on Silver Nanoparticle Fractal Clusters

Strong enhancement of the two-photon absorption of organic molecules near silver nanoparticle fractal clusters has been observed and has been exploited to yield composite materials with very strong two-photon absorption and two-photon-excited fluorescence properties. Measurements on cluster films coated with chromophoric polymer or with thiol-bound chromophores give spatially-averaged enhancements of 1000 and 20 000, respectively. Two-photon fluorescence microscopy studies show that the enhancements are spatially inhomogeneous, with peak-enhancement factors of ≥ 10 000 (polymer/cluster) and ≥ 160 000 (thiol chromophore/cluster), and excitation frequency dependent. These results are in accord with theoretical predictions of local-field effects due to strong localization of collective plasmon modes in fractal metal clusters, and demonstrate an approach to ultrasensitive two-photon processes.