Manipulating Alkyl Inner Side Chain of Acceptor for Efficient As-Cast Organic Solar Cells.

As-cast organic solar cells (OSCs) possess tremendous potential for low-cost commercial applications. Herein, five small-molecule acceptors (A1-A5) are designed and synthesized by selectively and elaborately extending the alkyl inner side chain flanking on the pyrrole motif to prepare efficient as-cast devices. As the extension of the alkyl chain, the absorption spectra of the films are gradually blue-shifted from A1 to A5 along with slightly uplifted lowest unoccupied molecular orbital energy levels, which is conducive for optimizing the trade-off between short-circuit current density and open-circuit voltage of the devices. Moreover, a longer alkyl chain improves compatibility between the acceptor and donor. The in situ technique clarifies that good compatibility will prolong molecular assembly time and assist in the preferential formation of the donor phase, where the acceptor precipitates in the framework formed by the donor. The corresponding film-formation dynamics facilitate the realization of favorable film morphology with a suitable fibrillar structure, molecular stacking, and vertical phase separation, resulting in an incremental fill factor from A1 to A5-based devices. Consequently, the A3-based as-cast OSCs achieve a top-ranked efficiency of 18.29%. This work proposes an ingenious strategy to manipulate intermolecular interactions and control the film-formation process for constructing high-performance as-cast devices.