We investigate the photostability of a set of organic semiconductor blends comprising a conjugated polymer as the donor and a fullerene as the acceptor using electron spin resonance (ESR). In the absence of oxygen, all blends show excellent stability. Even after several hundred hours of exposure to solar or UV radiation, the ESR spectra and the recombination of photoinduced charges recorded at low temperature are found to be unchanged. By contrast, the presence of oxygen leads to a fast light-induced degradation rendering the ability of the donor/acceptor system to form photoinduced charge carriers. Our findings suggest that conjugated polymer–fullerene blends exhibit very good photostability and that oxygen needs to be excluded in optoelectronic applications. Our findings also suggest that at low temperature, a universal recombination process of long-lived photoinduced charges is active, which does not depend on the electronic structure or the morphology of the investigated materials.

Regioregular polythiophenes baring 3-(p-methoxyethoxyethoxy)-phenyl substituents (PEOPT) show high photoluminescence efficiencies. Exposing thin films of this polymer to vapors of chloroform or annealing them by heat treatment results in a red shift of the absorption maximum due to solvent or heat induced ordering which gives rise to more planar conformations. The fact, that annealed thin films of PEOPT exhibit absorption edges at relatively low energies and thus have an enhanced spectral range makes them suitable for use in photodiodes / solar cells. The photoinduced charge generation efficiency in PEOPT is significantly enhanced by the addition of a strong electron acceptor like fullerene, as observed by quenching of the luminescence and by photoinduced absorption measurements in the infrared and UV-Vis regime. The efficiency of the photoinduced charge transfer from PEOPT to a methanofullerene is found to depend on the ordering of PEOPT in thin films.