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Poly(2,5-thienylene vinylene), PTV, can be conveniently prepared via a precursor route to give coherent films suitable for optical measurements. Photoexcitation above the band gap at 1.8 eV gives rise to two transient absorption peaks at 0.44 eV and 1.0 eV that are associated with bipolarons that live for times of order a few ms at 80 K. Photoluminescence, comparable in intensity to the Raman scattering, is found at energies above the band edge, and we assign this to a hot recombination process. Pump and probe measurements of the induced bleaching at 2 eV show a very fast rise and initial fall time, which are within the 100 fsec resolution of the measurement.

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