A novel electron acceptor, BTP-H2, demonstrates a high efficiency of 18.5% with a high V _oc of 0.932 V. It also enables the ternary device to yield an efficiency of 19.2%, ranking the highest among single-junction organic photovoltaics.

Enhancing the luminescence property without sacrificing the charge collection is one key to high-performance organic solar cells (OSCs), while limited by the severe non-radiative charge recombination. Here, we demonstrate efficient OSCs with high luminescence via the design and synthesis of an asymmetric non-fullerene acceptor, BO-5Cl. Blending BO-5Cl with the PM6 donor leads to a record-high electroluminescence external quantum efficiency of 0.1%, which results in a low non-radiative voltage loss of 0.178 eV and a power conversion efficiency (PCE) over 15%. Importantly, incorporating BO-5Cl as the third component into a widely-studied donor:acceptor (D:A) blend, PM6:BO-4Cl, allows device displaying a high certified PCE of 18.2%. Our joint experimental and theoretical studies unveil that more diverse D:A interfacial conformations formed by asymmetric acceptor induce optimized blend interfacial energetics, which contributes to the improved device performance via balancing charge generation and recombination.

Unveiling the correlations among molecular structures, morphological characteristics, macroscopic properties and device performances is crucial for developing better photovoltaic materials and achieving higher efficiencies. To achieve this goal, a comprehensive study is performed based on four state-of-the-art non-fullerene acceptors (NFAs), which allows to systematically examine the above-mentioned correlations from different scales. It’s found that extending conjugation of NFA shows positive effects on charge separation promotion and non-radiative loss reduction, while asymmetric terminals can maximize benefits from both terminals. Another molecular optimization is from alkyl chain tuning. The shortened alkyl side chain results in strengthened terminal packing and decreased π-π distance, which contribute high carrier mobility and finally the high charge collection efficiency. With the most-acquired benefits from molecular structure and macroscopic factors, PM6:BTP-S9-based organic photovoltaics (OPVs) exhibit the optimal efficiency of 17.56% (certified: 17.4%) with a high fill factor of 78.44%, representing the best among asymmetric acceptor based OPVs. This work provides insight into the structure-performance relationships, and paves the way toward high-performance OPVs via molecular design.