Introducing Siloxane-Terminated Side Chains in Small Molecular Donors for All-Small-Molecule Organic Solar Cells: Modulated Molecular Orientation and Enhanced Efficiency.

In this work, three small molecular donors (SMDs) S35, S35-1Si, and S35-2Si, with 3,5-difluorophenyl-substituted benzodithiophene as the central 2-dimensional unit to combine different numbers of siloxane-terminated side chain, were synthesized for all-small-molecule organic solar cells (ASM-OSCs). The three SMDs showed comparable film absorption peaks at 570 nm and optical band gaps of 1.8 eV. Relative to S35 and S35-1Si with symmetric alkyl side chains and asymmetric side chains on the central unit, respectively, the S35-2Si carrying two symmetric siloxane-terminated side chains displayed largely elevated melting and crystalline temperatures, lowered surface energy, and modulated molecular orientation. The three SMDs possessed edge-on dominated molecular orientations of their neat films; however, a big difference was found for their blend films with nonfullerene acceptor Y6. The S35:Y6 and S35-1Si:Y6 blends exhibited edge-on and face-on bimodal orientations but the S35-2Si:Y6 blend showed pure face-on orientation, indicating quite different donor:acceptor intermolecular interactions. Some large domains existed in the S35:Y6 and S35-1Si:Y6 blends, but could be suppressed by the S35-2Si:Y6 blend, leading to a more balanced charge transport. In ASM-OSCs, the two S35:Y6 and S35-1Si:Y6 active layers showed comparable power conversion efficiencies (PCE) of ∼12% but a much higher efficiency of 13.50% could be achieved with the S35-2Si:Y6 active layer. Our results suggest that the siloxane-terminated side chain is promising to regulate crystalline ability of a SMD, paving a way for high performance ASM-OSCs.