Recently, non-fullerene n-type organic semiconductors have attracted significant attention as acceptors in organic photovoltaics (OPVs) due to their great potential to realize high-power conversion efficiencies. The rational design of the central fused ring unit of these acceptor molecules is crucial to maximize device performance. Here, we report a new class of non-fullerene acceptor, Y6, that employs a ladder-type electron-deficient-core-based central fused ring (dithienothiophen[3.2-b]-pyrrolobenzothiadiazole) with a benzothiadiazole (BT) core to fine-tune its absorption and electron affinity. OPVs made from Y6 in conventional and inverted architectures each exhibited a high efficiency of 15.7%, measured in two separate labs. Inverted device structures were certified at Enli Tech Laboratory demonstrated an efficiency of 14.9%. We further observed that the Y6-based devices maintain a high efficiency of 13.6% with an active layer thickness of 300 nm. The electron-deficient-core-based fused ring reported in this work opens a new door in the molecular design of high-performance acceptors for OPVs.

We design and synthesize four fused-ring electron acceptors based on 6,6,12,12-tetrakis(4-hexylphenyl)-indacenobis(dithieno[3,2-b;2',3'-d]thiophene) as the electron-rich unit and 1,1-dicyanomethylene-3-indanones with 0-2 fluorine substituents as the electron-deficient units. These four molecules exhibit broad (550-850 nm) and strong absorption with high extinction coefficients of (2.1-2.5) × 10 M cm. Fluorine substitution downshifts the LUMO energy level, red-shifts the absorption spectrum, and enhances electron mobility. The polymer solar cells based on the fluorinated electron acceptors exhibit power conversion efficiencies as high as 11.5%, much higher than that of their nonfluorinated counterpart (7.7%). We investigate the effects of the fluorine atom number and position on electronic properties, charge transport, film morphology, and photovoltaic properties.

A planar fused-ring electron acceptor (IC-C6IDT-IC) based on indacenodithiophene is designed and synthesized. IC-C6IDT-IC shows strong absorption in 500-800 nm with extinction coefficient of up to 2.4 × 10(5) M(-1) cm(-1) and high electron mobility of 1.1 × 10(-3) cm(2) V(-1) s(-1). The as-cast polymer solar cells based on IC-C6IDT-IC without additional treatments exhibit power conversion efficiencies of up to 8.71%.

An alloy-like model based on Y6 and its derivative BTP-M is constructed to fabricate ternary organic solar cells, leading to a best efficiency of 17.03%.