Solution Aggregate Structures of Donor Polymers Determine the Morphology and Processing Resiliency of Non-Fullerene Organic Solar Cells

The solution-state aggregation of conjugated polymers is critical to the morphology and device performance of bulk heterojunction (BHJ) organic solar cells (OSCs). However, the detailed structures of polymer solution-state aggregates and their impact on the morphology and device performance of OSCs remain largely unexplored. Herein, we utilize a benzodithiophenebased donor polymer (PM7) and its ester-functionalized derivatives (PM7 D1 and D2) with reduced backbone rigidity as our model systems to demonstrate how a polymer solution-state aggregate structure impacts the morphology and processing resiliency of OSCs. Using X-ray scattering and microscopic imaging techniques, we ascertain that PM7 solution forms a combination of semi-crystalline fiber aggregates and amorphous polymer chain network aggregates, whereas PM7 D1 and D2 solutions primarily form amorphous network aggregates through sidechain associations. Interestingly, when the solution temperature is increased, the fiber aggregates of PM7 break down while the polymer network aggregates remain stable. Due to this temperature-dependent behavior of the fiber aggregates, blade-coated devices fabricated from the PM7 donor polymer and non-fullerene acceptor, ITIC-4F, lead to highly processing temperature-sensitive performance, whereas PM7 D1 and D2 polymers exhibit improved processing temperature resiliency. More importantly, we report that amorphous, network-like aggregates are conducive to superior device performance in blade-coated OSCs owing to the formation of blend films with short pi-pi stacking distance, small domain spacing, and face-on preferred molecular orientation. In contrast, we find that fiber-like aggregates lead to large pi-pi stacking distance, large domain spacing, and isotropic molecular orientation in the blend film, which deteriorate the device performance.