A Simple Dithienopyrrol‐Rhodanine Molecular Third Component Enables Over 16.7% Efficiency and Stable Organic Solar Cells

Organic solar cells (OSCs) can achieve greatly improved power conversion efficiency (PCE) by incorporating suitable additives in active layers. Their structure design often faces the challenge of operation generality for more binary blends. Herein, a simple dithieno[3,2‐b:2′,3′‐d]pyrrole‐rhodanine molecule (DR8) featuring high compatibility with polymer donor PM6 is developed as a cost‐effective third component. By employing classic ITIC‐like ITC6‐4Cl and Y6 as model nonfullerene acceptors (NFAs) in PM6‐based binary blends, DR8 added PM6:ITC6‐4Cl blends exhibit significantly promoted energy transfer and exciton dissociation. The PM6:ITC6‐4Cl:DR8 (1:1:0.1, weight ratio) OSCs contribute an exciting PCE of 14.94% in comparison to host binary devices (13.52%), while PM6:Y6:DR8 (1:1.2:0.1) blends enable 16.73% PCE with all simultaneously improved photovoltaic parameters. To the best of the knowledge, this performance is among the best for ternary OSCs with simple small molecular third components in the literature. More importantly, DR8‐added ternary OSCs exhibit much improved device stability against thermal aging and light soaking over binary ones. This work provides new insight on the design of efficient third components for OSCs.