Fine Optimization of Morphology Evolution Kinetics with Binary Additives for Efficient Non‐Fullerene Organic Solar Cells.

The power conversion efficiency of polymer solar cells (PSCs) is strongly affected by active layer morphology. Here, two solvent additives (ODT: octance‐1,8‐dithiol; DIO: 1,8‐diiodooctane) are used to optimize the bulk heterojunction morphology of FTAZ:ITIC‐Th based PSCs and ≈11% efficiency is obtained, which is 10% higher than the untreated device. Based on the morphological characterizations, the influence of binary solvent additives on manipulating molecular packing and phase separation of blend films is successfully revealed. More importantly, in situ grazing incidence wide‐angle X‐ray scattering characterization is adopted to explore the crucial role played by these two solvent additives at different stages of the film‐forming process, that is, ODT influences the initial stage of the film‐forming process, while DIO later establishes the ultimate photoactive film formation. Due to the impacts of two additives at different film processing stages, an optimal ratio of ODT:DIO (0.375%:0.125%) is obtained, which helps in realizing the optimized morphology. The device with binary additive of octance‐1,8‐dithiol:1,8‐diiodooctane (ODT:DIO) (0.375%:0.125%) based on FTAZ:ITIC‐Th blends exhibits a higher power conversion efficiency of 10.93% than the devices processed with only 0.5% ODT, 0.5% DIO, or excess binary additive of ODT:DIO (0.5%:0.5%). The reason is that additives with different boiling point work in different stages during the whole filming process as in situ grazing incidence wide‐angle X‐ray scattering characterization indicates. [ABSTRACT FROM AUTHOR]