Optimizing the Phase-Separated Domain Size of the Active Layer via Sequential Crystallization in All-Polymer Solar Cells

The proper domain size of the active layer plays a key role in determining the exciton dissociation and charge transport in all-polymer solar cells (all-PSCs). However, fine-tuning the domain size remains challenging due to low glass transition temperature and negligible mixing entropy in polymer blends. Herein, we systematically studied the influence of “crystallization kinetics” on the domain size and proposed that if the donor and acceptor crystallize simultaneously, they are prone to form a large domain, while if sequential crystallization of the donor and acceptor occurs, a fine phase separation structure with the proper domain size can be obtained. Taking PBDB-T/PNDI blends for instance, the domain size was decreased by using sequential crystallization; meanwhile, the crystallinity and molecular orientation were also optimized, boosting the power conversion efficiency from 6.55% to 7.78%. This work provides a novel way to finely tune the heterojunction phase separation structures.