Volatile Solid-Assisted Molecular Assembly Enables Eco-Friendly Processed Organic Photovoltaic Cells with High Efficiency and Photostability

Achieving environmentally friendly solvent-processed high-performance organic photovoltaic cells (OPVs) is a crucial step toward their commercialization. Currently, OPVs with competitive efficiencies rely heavily on harmful halogenated solvent additives. Herein, the green and low-cost 9-fluorenone (9-FL) is employed as a solid additive. By using the o-xylene/9-FL solvent system, the PM6:BTP-eC9-based devices deliver power-conversion efficiencies of 18.6% and 17.9% via spin-coating and blade-coating respectively, outperforming all PM6:Y-series binary devices with green solvents. It is found that the addition of 9-FL can regulate the molecular assembly of both PM6 and BTP-eC9 in film-formation (molecule-level mixing) and post-annealing (thermal-assisted molecular reorganization with additive volatilization) stages, so as to optimize the blend morphology. As a result, the charge transport ability of donor and acceptor phases are simultaneously enhanced, and the trap-assisted recombination is reduced, which contributes to the higher short-circuit current density and fill factor. Moreover, the generation of photo-induced traps is significantly suppressed, resulting in improved stability under illumination. It is further demonstrated the excellent universality of 9-FL in various photoactive systems, making it a promising strategy to advance the development of eco-friendly OPVs.