Bihalogenated Thiophene-Based Terpolymers for High-Performance Semitransparent Organic Solar Cells Processed by an Eco-Friendly Solvent and Layer-by-Layer Deposition

The development of photoactive materials simultaneously satisfying high performance, low cost, and eco-friendly processability remains challenging in organic solar cells (OSCs). Herein, a synergistic strategy is proposed to design three terpolymers (PM7(ClCl = 0.2), PM7(ClBr = 0.2), and PM7(BrBr = 0.2)) based on bihalogenated thiophenes with relatively low cost, for improving the optical and electrochemical properties, solubility in nontoxic solvents, and crystallinity and miscibility balance. In summary, a bulk-heterojunction (BHJ)-processed device based on PM7(ClCl = 0.2) with 20% dichlorinated thiophene achieves the highest power conversion efficiency (PCE) of 15.2% using toluene (best PCE ≈ 15.8% on the ternary blend). Moreover, high-performance semitransparent OSCs (ST-OSCs) were fabricated by a combination of layer-by-layer (LBL) and sequential dynamic and static spin-coating techniques according to the molecular weight of PM7(ClCl = 0.2). Using this unique LBL strategy, the PM7(ClCl = 0.2)-MW (H; high molecular weight)-processed ST-OSCs yield a high PCE of 11.5% and an average visible transmittance (AVT) of 27.1% with outstanding tolerance to device reproducibility. By optimizing ST-OSCs with tungsten trioxide as a distributed Bragg reflector, a light utilization efficiency (LUE) of 3.61% is realized with a PCE of 10.8% and an AVT of 33.4% (certified PCE ≈ 11.157%; LUE ≈ 3.73%). This study provides a novel perspective for designing and developing actual photoactive materials for OSC commercialization.