The intrinsic intrachain photoluminescence ͑PL͒ dynamics of conjugated polymers in the solid state is investigated. We focus on the PL properties of long ␤-substituted oligothiophenes ͑8-mer, 12-mer, and 16-mer͒ and regio-regular ͑RR͒ and regio-random poly͑3-octylthiophenes͒ ͑P3OTs͒ diluted in the inactive solid matrix polypropylene ͑PP͒. The oligothiophenes have well-resolved 0-0 PL and absorption peaks at 4 K and show a good linear relationship with the reciprocal of the ring number. Franck-Condon analyses on the PL spectra reveal that the strength of the electron-phonon coupling represented by the Huang-Rhys factor becomes weak with increasing chain length in the oligomers. In contrast, the presence of stronger electron-phonon coupling is confirmed in RR P3OT despite it being of a much longer chain length than oligomers. This is probably due to its stereoregular chain conformation. The materials used in this work diluted in PP exhibit single-exponential PL decays with lifetimes that decrease with increases in the chain length. The presence of intrachain exciton migration is shown by the time-resolved PL measurements, except for the case of RR P3OT. The energy shifts attributed to intrachain migration are much smaller than those ascribed to interchain migration. We conclude that a change in the torsion angle around the thiophene ring bonds occurs within 50 ps following the absorption transition in thiophene derivatives and that the torsional change gives rise to a constant Stokes shift ͑60-70 meV͒, regardless of the chain length. We propose that the Stokes shift can be utilized for estimating the magnitude of exciton migration in thiophene derivatives, even in the case of undiluted films.

Bleaching probe spectroscopy performed for regioregular poly(3-hexylthiophene) diodes reveals that coexistent morphological phases determine the conducting and optical properties of conjugated polymer films. Photoinduced absorption measurements demonstrate that exciton migration occurs from lamella aggregates to morphological sites consisting of quasiuncoupled chains and that the latter sites determine steady-state photophysical properties. Spectroscopy synchronized with diode operation reveals that the morphological locations of injected carriers in polymer diodes vary with the applied bias.

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