Insights into Excitonic Dynamics of Terpolymer-Based High-Efficiency Nonfullerene Polymer Solar Cells: Enhancing the Yield of Charge Separation States

Ternary copolymerization strategy is considered an effective method to achieve high-performance photovoltaic conjugated polymers. Herein, a donor–acceptor1–donor–acceptor2-type random copolymer, named PBDTNS-TZ-BDD (T1), containing one electron-rich unit alkylthionaphthyl-flanked benzo[1,2-b/4,5-b′] di-thiophene (BDTNS) as D and two electron-deficient moieties benzo[1,2-c/4,5-c′]dithiophene-4,8-dione (BDD) and fluorinated benzotriazole as A, was synthesized to investigate the excitonic dynamic effect. Also, the D–A-type alternating copolymer PBDTNS-BDD (P1) was also prepared for a clear comparison. Although the UV–Vis spectra and energy levels of P1 and T1 are similar, the power conversion efficiencies (PCEs) of the related devices are 11.50% (T1/ITIC) and 8.89% (P1/ITIC), respectively. The reason for this is systematically investigated and analyzed by theoretical calculation, photoluminescence, and pump-probe transient absorption spectroscopy. The density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculation results show that the terpolymer T1 with a lower exciton binding energy and a longer lifetime of spontaneous luminescence can synergistically increase the number of excitons reaching the donor/acceptor interface. The results of the pump-probe transient absorption spectroscopy show that the yield of charge separation of T1/ITIC is higher than that of the P1/ITIC blend film, and improved PCE could be achieved via copolymerization strategies. Moreover, the fabrication of the T1-based device is also simple without any additive or postprocessing. Therefore, it provides a promising and innovative method to design high-performance terpolymer materials.