Time-resolved charge carrier generation from higher lying excited states in conjugated polymers

Sub-ps three-pulse transient differential transmission spectroscopy using two excitation pulses is used to directly investigate the generation of charge carriers in ladder-type poly(para)phenyl in bulk film. The role of higher excited singlet states of both even and odd symmetry is examined and the dynamics of the major processes involved is described quantitatively. The charge generation efficiency is found to depend strongly on the delay between the two excitation pulses. This is explained by the interplay between internal conversion, excitation energy migration, and on-site vibronic relaxation.