Fluorinated polythiophenes with ester side chains for boosting the Voc and efficiency in non-fullerene polymer solar cells

As the power conversion efficiency (PCE) of organic photovoltaics (OPVs) approximates the 19 % threshold, wide bandgap (WBG) polythiophenes (PTs) have gained increasing attention due to their simple chemical structures and ease of synthesis, making them promising candidates for large-scale production. However, the benchmark polymer poly(3-hexylthiophene) (P3HT) is limited by its high-lying HOMO energy level, which restricts the open-circuit voltage (V_OC) in solar cells. In this study, we introduce a novel series of PT derivatives (PDC8-T, PDC8-3T, PDC16-3T, and PDC16-3T-2F) featuring ester side chains designed to fine-tune electronic properties through a streamlined three-step synthesis. Additionally, we incorporated a π-spacer to reduce steric hindrance and elongated alkyl side chains to improve solubility and processability. Compared to P3HT, these PT derivatives demonstrate a significant reduction in HOMO energy levels, lowering by approximately 0.3–0.4 eV. Among them, PDC16-3T-2F—with fluorine atom substitution—achieves the lowest HOMO energy level, induces a coplanar molecular conformation, and enhances polymer aggregation behavior.

We evaluated these PT derivatives in inverted non-fullerene bulk-heterojunction (NFA BHJ) OPVs. The PDC8-3T device showed a relatively low PCE of 0.69 %, with a V_OC of 0.76 V, a short-circuit current density (J_SC) of 3.32 mA/cm², and a fill factor (FF) of 27.3 %. In contrast, the PDC16-3T-2F device achieved an impressive PCE of 7.21 %, with a V_OC of 0.85 V, a J_SC of 14.60 mA/cm², and an FF of 58.4 %. This remarkable improvement is attributed to the fluorine substitution, which not only enhances molecular orientation but also downshifts the HOMO energy level and further boosts the V_OC. Hence, these molecular design strategies have led to a fibrillar bicontinuous interpenetrating network with optimal nanoscale phase separation within the active layer.