Ultrafast coherent vibronic oscillations in regioregular poly(3-alkylthiophene)

Ultrafast degenerate four-wave mixing (DFWM) signals of the regioregular (RR) poly(3-hexylthiophene) (P3HT) film have been investigated by the experiments using sub-20 fs pulses generated from a noncollinear optical parametric amplifier (NOPA) system. Strong DFWM signals were observed owing to a large third-order nonlinear susceptibility χ⁽³⁾ of the RR-P3HT film. The time profile of the DFWM signals exhibits clear coherent oscillation on a decaying signal. The oscillation turn out to be caused by the C=C stretching mode that gives strong Raman signal. The time profile of the DFWM signal is simulated by a numerical calculation. The result of simulation reveals that decay constants of electronic population and of vibronic oscillation are 200 fs and 210 fs, respectively. This is the first determination of the decay constants for the RR-P3HT film. The obtained result demonstrates that the χ⁽³⁾ signal of the RR-P3HT film decays very rapidly.