Achieving 19.5% Efficiency via Modulating Electronic Properties of Peripheral Aryl-Substituted Small-Molecule...

The advancement of acceptors plays a pivotal role in determining photovoltaic performance. While previous efforts have focused on optimizing acceptor-donor-acceptor₁-donor-acceptor (A-DA₁-D-A)-typed acceptors by adjusting side chains, end groups, and conjugated extension of the electron-deficient central A₁ unit, the systematic exploration of the impact of peripheral aryl substitutions, particularly with different electron groups, on the A₁ unit and its influence on device performance is still lacking. In this study, three novel acceptors - QxTh, QxPh, and QxPy - with distinct substitutions on the quinoxaline (Qx) are designed and synthesized. Density functional theory (DFT) analyses reveal that QxPh, featuring a phenyl-substituted Qx, exhibits the smallest molecular binding energies and a tightest π···π stacking distance. Consequently, the PM6:QxPh device demonstrates a better power conversion efficiency (PCE) of 17.1% compared to the blends incorporating QxTh (16.4%) and QxPy (15.7%). This enhancement is primarily attributed to suppressed charge recombination, improved charge extraction, and more favorable molecular stacking and morphology. Importantly, introducing QxPh as a guest acceptor into the PM6:BTP-eC9 binary system yields an outstanding PCE of 19.5%, indicating the substantial potential of QxPh in advancing ternary device performance. The work provides deep insights into the expansion of high-performance organic photovoltaic materials through peripheral aryl substitution strategy.