Design of Chlorinated Indaceno[1,2-b:5,6-b']dithiophene Acceptors toward Efficient Organic Photovoltaics

Chlorinated modifications have been extensively employed to modulate the optoelectronic properties of π-conjugated materials. Herein, the Cl substitution in designing nonfullerene acceptors (NFAs) with various bandgaps is studied. Four narrow-bandgap electron acceptors (GS-40, GS-41, GS-42, and GS-43) were synthesized by tuning the electrostatic potential distributions of the molecular conjugated backbones. The optical absorption onset of these NFAs ranges from 900 to 1030 nm. Compared to the nonchlorinated analogue, the introduction of Cl atoms on the core of indaceno[1,2-b:5,6-b'] dithiophene (IDT) and π spacer results in an upward shift of the lowest unoccupied molecular orbital levels and induces a blue shift in the absorption spectra of the NFAs. This alteration facilitates achieving appropriate energy-level alignment and favorable bulk heterojunction morphology when blended with the widely used donor PBDB-TF. The PBDB-TF:GS-43-based solar cells show an optimal power conversion efficiency of 13.3%. This work suggests the potential of employing chlorine-modified IDT and thiophene units as fundamental building blocks for developing high-performance photoactive materials.