Time-resolved spectroscopy of charge transfer phenomena in organic solar cells

Geminate recombination of photo-generated excitons represents a considerable loss mechanism in polymer solar cells. We apply time-resolved photoluminescence (TRPL) to study the radiative recombination which accompanies the process of charge generation. A streak camera is used, which is sensitive for both the photoluminescence (PL) from the initially excited singlet excitons and the weaker emission from charge transfer (CT) states. The latter are formed at internal interfaces when the polymer is blended with a fullerene acceptor. We draw a comparison between our results for two polymers, P3HT and PTB7, respectively, which were studied in blends with the fullerene derivative PCBM. In addition, pristine films were investigated, allowing for the identification of interfacial features in the blends. For both polymers, the PL of the singlet states was rapidly quenched in blends with PCBM. In P3HT, time constants of about 40 ps were recorded for the singlet exciton decay and related to exciton diffusion, whereas the PL of PTB7 was almost completely quenched within the first 3 ps. The decay rates of the emissive CT excitons were 2-3 orders of magnitude smaller than those of the singlet state. Yet, due to their slower dynamics (similar to 500 ps), they could be separated from the superimposed singlet emission. The CT decay times in blends with P3HT exhibited no significant temperature dependence, indicating that thermally driven dissociation of emissive excitons is unlikely. For blends with PTB7, however, a faster decay of the CT emission was obtained at room temperature.