Polarization anisotropy of charge transfer absorption and emission of aligned polymer: fullerene blend films

An improved understanding of the electronic structure of interfacial charge transfer (CT) states is of importance due to their crucial role in charge carrier generation and recombination in organic donor-acceptor (DA) solar cells. DA combinations with a small difference between the energy of the CT state (E-CT) and energy of the donor exciton (E-D*) are of special interest since energy losses due to electron transfer are minimized, resulting in an optimized open-circuit voltage. In that case, the CT state can be considered as a resonance mixture, containing character of a fully ionic state (D+ A(-)) and of the local polymer excited state (D* A). We show that the D* A contribution to the overall CT state wave function can be determined by measurements of the polarization anisotropy of CT absorption and emission of polymer: fullerene blends with aligned polymer chains. We study two donor polymers, P3HT and TQ1, blended with fullerene acceptors with different ionization potentials, allowing variation of the E-D* -E-CT difference. We find that, upon decreasing E-D* -E-CT, the local excitonic D* A character of the CT state increases, resulting in a decreased fraction of charge transferred and an increased transition dipole moment. For typical polymer: fullerene systems, this effect is expected to become detrimental for device performance if E-D* - E-CT < 0.1 eV. This however, depends on the electronic coupling between D* A and D+ A(-), which we experimentally estimate to be similar to 6 meV for the TQ1: PCBM system.