Balancing Crystal Size in Small-Molecule Nonfullerene Solar Cells through Fine-Tuning the Film-Forming Kinetics to Fabricate Interpenetrating Network

[Image: see text] The nanoscale interpenetrating network of active layer plays a key role in determining the exciton dissociation and charge transport in all small-molecule nonfullerene solar cells (AS-NFSCs). However, fabricating interpenetrating networks in all small-molecule blends remains a critical hurdle due to the uncontrolled crystallization behavior of small molecules. In this study, we proposed that the balanced crystal size between the donor and the acceptor is an essential prerequisite to construct optimal interpenetrating networks. We also provided a solvent additive strategy to reduce the gap of crystal size between the donor and the acceptor in S-TR:ITIC all small-molecule blend system through manipulating the solution state and film-forming kinetics. As a result, the crystal size of S-TR decreased and the crystal size of ITIC increased, leading to nanoscale interpenetrating networks. This optimized morphology improved the exciton dissociation efficiency and suppressed the bimolecular recombination, achieving almost double power conversion efficiency compared to the reference device. This work demonstrates that manipulation of the balanced crystal size of donor and acceptor may be a key to further boost the efficiency of AS-NFSCs.