Abstract
Energy transfer in spin-coated films and solutions of poly(dioctylphenylthiophene) with bulky side chains has been studied by femtosecond pump-probe spectroscopy, polarisation anisotropy and excitation annihilation. A red shift of stimulated emission spectra with time and a gradual decay of anisotropy are observed in film and solution and attributed to excitation migration towards lower-energy sites. At high-excitation intensities singlet-singlet annihilation with time-independent rate dominates the decay of excited-state population in the film for short times. It is concluded that energy migration in film, which results in effective excitation trapping and nonradiative decay, is a three-dimensional process, while in solution a one-dimensional intra-chain energy migration is much more limited.
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