Backbone Engineering with Asymmetric Core to Finely Tune Phase Separation for High-Performance All-Small-Molecule Organic Solar Cells

In order to obtain high-performance all-small-molecule organic solar cells (ASM-OSCs), it is crucial to exploit the available strategy for molecular design and to further understand key structure–property relationship that can rationally control the blend nanomorphology and influence the physical process. In this work, we design two small molecule donors FBD-S1 and TBD-S2 with identical electron-withdrawing units but various asymmetric central cores, which exhibit differing phase separation in Y6-based blend films. It is found that TBD-S2 with increased phase separation between donor and acceptor can lead to more favorable interpenetrating networks, effective exciton dissociation, and enhanced and more balanced charge transport. Importantly, a remarkable PCE of 13.1% is obtained for TBD-S2:Y6 based ASM-OSCs, which is an attractive photovoltaic performance for ASM-OSCs. This result demonstrates that the central core modification at the atomic level for small molecule donors can delicately control the phase separation and optimize photophysical processes, and refines device performance, which facilitate development in the ASM-OSC research field.