Exciton formation, relaxation, and decay in PCDTBT

The nature and time evolution of the primary excitations in the pristine conjugated polymer, PCDTBT, are investigated by femtosecond-resolved fluorescence up-conversion spectroscopy. The extensive study includes data from PCDTBT thin film and from PCDTBT in chlorobenzene solution, compares the fluorescence dynamics for several excitation and emission wavelengths, and is complemented by polarization-sensitive measurements. The results are consistent with the photogeneration of mobile electrons and holes by interband π-π* transitions, which then self-localize within about 100 fs and evolve to a bound singlet exciton state in less than 1 ps. The excitons subsequently undergo successive migrations to lower energy localized states, which exist as a result of disorder. In parallel, there is also slow conformational relaxation of the polymer backbone. While the initial self-localization occurs faster than the time resolution of our experiment, the exciton formation, exciton migration, and conformational changes lead to a progressive relaxation of the inhomogeneously broadened emission spectrum with time constants ranging from about 500 fs to tens of picoseconds. The time scales found here for the relaxation processes in pristine PCDTBT are compared to the time scale (<0.2 ps) previously reported for photoinduced charge transfer in phase-separated PCDTBT:fullerene blends (Phys. Rev. B 2010, 81, 125210). We point out that exciton formation and migration in PCDTBT occur at times much longer than the ultrafast photoinduced electron transfer time in PCDTBT:fullerene blends. This disparity in time scales is not consistent with the commonly proposed idea that photoinduced charge separation occurs after diffusion of the polymer exciton to a fullerene interface. We therefore discuss alternative mechanisms that are consistent with ultrafast charge separation before localization of the primary excitation to form a bound exciton.