Comparison between J-aggregates in a self-assembled multilayer and polymer-bound J-aggregates in solution: a steady-state and time-resolved spectroscopic study

The self-assembly of a thiacarbocyanine dye on a charged substrate via the layer-by-layer alternate adsorption technique was studied in detail. The influence of the chemical structure of the oppositely charged polyelectrolyte (PEL) in the multilayer on J-aggregate formation was investigated by means of absorption spectroscopy and steady-state and time-resolved fluorescence spectroscopy. J-Aggregates were formed yielding a bathochromic narrow absorption band. Fine tuning of the position of the absorption band is possible by incorporating other polyelectrolytes in the multilayer. The results obtained for the dye–polyelectrolyte multilayers were compared with measurements made on the aqueous dye–polyelectrolyte mixtures. The parameters obtained by fitting the fluorescence decays to several different models allowed us to suggest a mechanism for the non-radiative decay channel. The low fluorescence quantum yields and fast non-exponential fluorescence decays obtained for both the dye–polyelectrolyte multilayers and the aqueous dye–polyelectrolyte mixtures were attributed to the trapping of a fast migrating exciton by a non-luminescent trap. The results related to J-aggregate formation, decay time and dimensionality of the aggregates were compared in solution and in a self-assembled multilayer.