Role of Aggregates in the Luminescence Decay Dynamics of Conjugated Polymers.

Fluorescence quantum yields of conjugated polymer films are systematically lower than their counterparts in dilute solution. Films also exhibit a long "temporal tail" in their fluorescence decay dynamics not present in solution. We study the spectroscopy, excitation wavelength dependence, temperature dependence, and electric field quenching of the temporal tail of the photoluminescence in MEH-PPV on a nanosecond time scale to elucidate the relationship between those observations. We conclude that the tail represents emission from H-like aggregated regions in the polymer. Using a simple model of the photophysics, we estimate the formation yield of the aggregates responsible for the tail emission to be <20% so that they cannot account for the large reduction in fluorescence observed in densely packed films relative to that in solution.