Halogenation Strategy of Thiophene Derived Solvent Additives Enables Optimized Morphology for Organic Solar Cells with 19.17% Efficiency

Abstract As simple and versatile tools, additives have been widely used to refine active layer morphology and have played a crucial role in boosting the power conversion efficiency (PCE) of organic solar cells (OSCs). Herein, three novel solvent additives named Th‐FSi, Th‐ClSi, and Th‐BrSi with the same backbone of 2,5‐bis(trimethylsilyl)thiophene are designed and synthesized by substituting different halogens of fluorine, chlorine, and bromine, respectively. Notably, Th‐ClSi exhibits the more significant dipole moment and engages in non‐covalent interactions with a small‐molecule acceptor (SMA) L8‐BO, which slight adjustments in intermolecular interaction, crystallinity, and molecular packing in the PM6:L8‐BO active layer. Consequently, the OSCs incorporating Th‐ClSi outperform their Th‐FSi and Th‐BrSi counterparts in photo‐capturing, reduced energy loss, superior exciton dissociation, and charge transfer properties, out‐coming yields in an enhanced PCE of 18.29%. Moreover, by integrating a near‐infrared absorbing SMA (BTP‐eC9) guest into the PM6:L8‐BO matrix, the absorption spectrum to span 880–930 nm, and the resultant ternary OSCs achieve a commendable PCE of 19.17%, ranking among the highest efficiencies reported to date is expanded. These findings underscore the promise of halogenated thiophene‐based solvent additives as a potent avenue for morphological fine‐tuning and consequent PCE enhancement in OSCs.