13.4 % Efficiency from All-Small-Molecule Organic Solar Cells Based on a Crystalline Donor with Chlorine and Trialkylsilyl Substitutions

How to simultaneously achieve both high open-circuit voltage (V_oc) and high short-circuit current density (J_sc) is a big challenge for realising high power conversion efficiency (PCE) in all-small-molecule organic solar cells (all-SM OSCs). Herein, a novel small molecule (SM)-donor, namely FYSM−SiCl, with trialkylsilyl and chlorine substitutions was designed and synthesized. Compared to the original SM-donor FYSM−H, FYSM−Si with trialkylsilyl substitution showed a decreased crystallinity and lower highest occupied molecular orbital (HOMO) level, while FYSM−SiCl had an improved crystallinity, more ordered packing arrangement, significantly lower HOMO level, and predominant “face-on” orientation. Matched with a SM-acceptor Y6, the FYSM−SiCl-based all-SM OSCs exhibited both high V_oc of 0.85 V and high J_sc of 23.7 mA cm⁻², which is rare for all-SM OSCs and could be attributed to the low HOMO level of FYSM−SiCl donor and the delicate balance between high crystallinity and suitable blend morphology. As a result, FYSM−SiCl achieved a high PCE of 13.4 % in all-SM OSCs, which was much higher than those of the FYSM−H- (10.9 %) and FYSM−Si-based devices (12.2 %). This work demonstrated a promising method for the design of efficient SM-donors by a side-chain engineering strategy via the introduction of trialkylsilyl and chlorine substitutions.