Light-induced EPR study of charge transfer in poly(3-hexylthiophene)/fullerene bulk heterojunction.

The first results of the light-induced EPR study of magnetic, relaxation, and dynamic parameters of charge carriers background photoinduced by optical photons (1.7-3.4 eV) in poly(3-hexylthiophene)/fullerene bulk heterojunctions are described. All magnetic resonance parameters for positively charged polaron and negatively charged fullerene ion-radical in radical pairs photoinduced in the composite were determined separately by the steady-state microwave saturation method. Paramagnetic susceptibility of charge carriers reflects their activation dynamics and exchange interaction. A decay of long-living radical pairs depends on the spatial distance between photoinduced charge carriers. The one-dimensional polaron diffusion along the polymer chain and fullerene rotation near the main molecular axis was shown to follow activation Elliot hopping model and to be governed by photon energy. The difference in activation energies of the charge carriers' dynamics and in their dependence on the exciting photon energy proves their noninteracting character in the polymer/fullerene composite. Main magnetic, relaxation and dynamics parameters of charge carriers are governed by the photon energy band due to inhomogeneity of distribution of polymer and fullerene domains in the composite.