In Situ Optical Spectroscopy Demonstrates the Effect of Solvent Additive in the Formation of All-Polymer Solar Cells

[Image: see text] 1-Chloronaphthalene (CN) has been a common solvent additive in both fullerene- and nonfullerene-based organic solar cells. In spite of this, its working mechanism is seldom investigated, in particular, during the drying process of bulk heterojunctions composed of a donor:acceptor mixture. In this work, the role of CN in all-polymer solar cells is investigated by in situ spectroscopies and ex situ characterization of blade-coated PBDB-T:PF5-Y5 blends. Our results suggest that the added CN promotes self-aggregation of polymer donor PBDB-T during the drying process of the blend film, resulting in enhanced crystallinity and hole mobility, which contribute to the increased fill factor and improved performance of PBDB-T:PF5-Y5 solar cells. Besides, the nonradiative energy loss of the corresponding device is also reduced by the addition of CN, corresponding to a slightly increased open-circuit voltage. Overall, our observations deepen our understanding of the drying dynamics, which may guide further development of all-polymer solar cells.