Non‐Radiative Loss Suppression via a Novel Asymmetric Anthracene‐Diimide Additive: A Pathway to 20.56% Efficient Binary Organic Solar Cells

ABSTRACT Suppressing non‐radiative recombination energy loss (ΔEnr) is critical for efficient organic solar cells (OSCs) yet remains challenging. Herein, two asymmetric donor–acceptor type non‐volatile solid additives, a‐ADI and a‐ATI, are synthesized to simultaneously reduce ΔEnr and optimize morphology via dipole‐induced intermolecular interactions with active materials. The photoluminescence quantum yield (PLQY) of L8‐BO films increases from 2.24% to 3.88% (a‐ADI) and 3.14% (a‐ATI), while the electroluminescence quantum yield of D18:L8‐BO blends improves from 1.24 × 10 −4 to 2.85 × 10 −4 and 1.99 × 10 −4 , respectively, yielding minimized ΔE nr of 0.205 and 0.214 eV in corresponding OSCs. In addition, the donor‐acceptor structured additives facilitate the formation of a highly ordered interpenetrating network microstructure in the blend, which effectively enhances carrier mobility and interfacial charge extraction capabilities within the device. Consequently, a‐ADI‐ and a‐ATI‐modified D18:L8‐BO devices achieve power conversion efficiencies (PCEs) of 20.56% and 19.87%. Notably, a‐ADI enables 17.02% efficiency in layer‐by‐layer OSCs without a cathode interface layer, and 20.76% in ternary devices. Notably, the a‐ADI‐modified devices exhibited T 80 lifetimes exceeding 500 h under both continuous illumination and continuous heating condition. This work underscores the potential of asymmetric diimide‐based additives in suppressing non‐radiative recombination, offering deep insights into realizing organic photovoltaics with ultralow energy loss and high efficiency.