Unraveling the Solution Aggregation Structures and Processing Resiliency of High‐Efficiency Organic Photovoltaic Blends

The solution aggregation structure of conjugated polymers is crucial to the morphology and resultant optoelectronic properties of organic electronics and is of considerable interest in the field. Precise characterizations of the solution aggregation structures of organic photovoltaic (OPV) blends and their temperature‐dependent variations remain challenging. In this work, the temperature‐dependent solution aggregation structures of three representative high‐efficiency OPV blends using small‐angle X‐ray/neutron scattering are systematically probed. Three cases of solution processing resiliency are elucidated in state‐of‐the‐art OPV blends. The exceptional processing resiliency of high‐efficiency PBQx‐TF blends can be attributed to the minimal changes in the multiscale solution aggregation structure at elevated temperatures. Importantly, a new parameter, the percentage of acceptors distributed within polymer aggregates (Ф), for the first time in OPV blend solution, establishes a direct correlation between Ф and performance is quantified. The device performance is well correlated with the Kuhn length of the cylinder related to polymer aggregates L1 at the small scale and the Ф at the large scale. Optimal device performance is achieved with L1 at ≈30 nm and Ф within the range of 60 ± 5%. This study represents a significant advancement in the aggregation structure research of organic electronics. The temperature‐dependent solution aggregation behavior of high‐efficiency organic photovoltaic blends is thoroughly investigated by complementary scattering techniques. The direct quantitative relationships established between multiscale solution structural parameters (Kuhn length of polymer aggregates, L1, and the percentage of acceptors distributed within polymer aggregates, Ф) and device performance provide valuable optimization guidelines for the preparation of high‐performance organic electronic devices.