Competition between morphological attributes in the thermal annealing and additive processing of polymer solar cells

Thermal annealing and additive processing are employed and compared using alkoxy substituted (QxO) and extended π conjugated alkythienyl substituted (QxT) benzo[1,2-b:4,5 b′]dithiophene based heterojunction (BHJ) solar cells. The characteristic median length of the morphology, average composition fluctuations, interface structure, crystallinity and molecular miscibility are investigated based on these two processes. Our results suggest that focusing on single structural, morphological or thermodynamic measurements is not sufficient to explain differences in device performance. In the current work, no blends are close to the ideal morphology containing either domains that are too large, too mixed or too pure. An optimization strategy is proposed to improve those devices. Importantly, we find that domain size and relative domain purity are overall correlated with molecular miscibility, i.e. the more immiscible system induces larger and purer domains irrespective of the processing and even in non-equilibrium structures. This indicates that the relative domain size and purity, and device performance can be potentially predicted by the donor-acceptor molecular miscibility, a factor not yet widely considered when designing new materials for BHJ devices.