Triggering the Donor-Acceptor Phase Segregation with Solid Additives Enables 16.5% Efficiency in All-Polymer Solar Cells.

All-polymer solar cells have attracted considerable research interest due to their superior morphological stabilities, stretchability, and mechanical durability. However, the morphology optimization of the all-polymer bulk heterojunctions remains challenging due to the two long conjugated polymer chains, limiting its power conversion efficiency. Herein, we focus on the donor-acceptor phase segregation of an all-polymer active layer composed of PM6/PY-IT, a state-of-the-art all-polymer combination, by the introduction of volatile solid additives. Especially with 1,3-dibromo-5-chlorobenzene (DBCl) as the processing additive, we could effectively tune the miscibility between PM6 and PY-IT and thus optimize the phase segregation of the polymer donor and acceptor. Due to the synergetic effects on the favorable phase segregation and desired donor-acceptor distribution, the DBCl-treated devices feature the evident improvement of charge transport and collection, accompanied by the suppressed trap-assisted charge recombination. We consequently achieved a champion device efficiency of 16.5% (16.4% averaged), which is a 13% improvement compared with the control device without DBCl (14.6%). Our results highlight the importance of altering the miscibility of the polymer donor-acceptor pairs for practical applications of high-performance all-polymer solar cells.