Fine-Tuning the Quasi-3D Geometry: Enabling Efficient Nonfullerene Organic Solar Cells Based on Perylene Diimides

The geometries of acceptors based on perylene diimides (PDIs) are important for improving the phase separation and charge transport in organic solar cells. To fine-tune the geometry, biphenyl, spiro-bifluorene, and benzene were used as the core moiety to construct quasi-three-dimensional nonfullerene acceptors based on PDI building blocks. The molecular geometries, energy levels, optical properties, photovoltaic properties, and exciton kinetics were systematically studied. The structure–performance relationship was discussed as well. Owing to the finest phase separation, the highest charge mobility and smallest nongeminate recombination, the power conversion efficiency of nonfullerene solar cells using PDI derivatives with biphenyl core (BP-PDI₄) as acceptor reached 7.3% when high-performance wide band gap donor material poly­[(2,6-(4,8-bis­(5-(2-ethylhexyl)­thiophen-2-yl)-benzo­[1,2-<i>b</i>:4,5-<i>b</i>′]­dithiophene))-<i>alt</i>-(5,5-(1′,3′-di-2-thienyl-5′,7′-bis­(2-ethylhexyl)­benzo­[1′,2′-<i>c</i>:4′,5′-<i>c</i>′]­dithiophene-4,8-dione))] was blended