Tuning of the spectroscopic properties of composite nanoparticles by the insertion of a spacer layer: effect of exciton-plasmon coupling.

Composite nanoparticles (NPs) having a double-shell structure, Au core, spacer layer (inner shell), and J-aggregate (JA) layer (outer shell) (Au/spacer/JA) have been synthesized. The spacer layer composed of N,N,N-trimethyl(11-mercaptoundecyl)ammonium chloride played an important role in promoting the J-aggregation of anionic cyanine dyes on the surface, as evidenced by the successful formation of the JA layers with four kinds of anionic cyanine dyes. It was found that the presence of a spacer layer causes a significant change in the line shape of the absorption spectrum, particularly near the J-band; there is the appearance of a peak type absorption for the composite NPs with the double-shell structure, while there is a dip type absorption for the ones without the spacer layer. The change from the peak type absorption to the dip type absorption in the Au/spacer/JA NPs occurs when the size of the Au core is varied from 5 to 15 nm. These observations would indicate that the strength of exciton-plasmon coupling between the Au core and the JA layer is enhanced with the increase in the core size or the decrease in the separation between the Au core and the JA shell. The photoluminescence arising from the JA can be detected for the composite NPs with the double-shell structure, showing that the quenching by the Au core is effectively suppressed by the spacer layer.