Charge pair dissociation and recombination dynamics in a P3HT–PC₆₀BM bulk heterojunction

The mechanism by which Coulombically bound charge pairs dissociate into free carriers in photovoltaic donor–acceptor blends is of great interest. Here, we use polarization-sensitive transient absorption (TA) to study the diffusion of photogenerated holes in a polythiophene (P3HT)–fullerene (PC₆₀BM) blend. We observe an initial anisotropy value of 0.4 for the absorption of photogenerated holes, indicating that holes generated on a 100 fs time scale are localized on the same polymer chain as their precursor excitons. Depolarization dynamics indicate fast initial hole motion on a 0.3 ps time scale and slower migration up to 100 ps. Charge pair recombination is found to occur on a much longer time scale of 10–1000 ns via a purely bimolecular process independent of excess energy. Our results show that nearly all charge pairs get separated by at least 7 nm in the absence of an external field and indicate that high charge mobility is crucial for charge separation.