Halogen‐Free Donor Polymers Based on Dicyanobenzotriazole with Low Energy Loss and High Efficiency in Organic Solar Cells

Abstract Halogenation of organic semiconductors is an efficient strategy for improving the performance of organic solar cells (OSCs), while the introduction of halogens usually involves complex synthetic process and serious environment pollution problems. Herein, three halogen‐free ternary copolymer donors (PCNx, x = 3, 4, 5) based on electron‐withdrawing dicyanobenzotriazole are reported. When blended with the Y6, PCN3 with strong interchain interactions results in appropriate crystallinity and thermodynamic miscibility of the blend film. Grazing‐incidence wide‐angle X‐ray scattering measurements indicate that PCN3 has more ordered arrangement and stronger π–π stacking than previous PCN2. Fourier‐transform photocurrent spectroscopy and external quantum efficiency of electroluminescence measurements show that PCN3‐based OSCs have lower energy loss than PCN2, which leads to their higher open‐circuit voltage (0.873 V). The device based on PCN3 reaches power conversion efficiency (PCE) of 15.33% in binary OSCs, one of the highest values for OSCs with halogen‐free donor polymers. The PCE of 17.80% and 18.10% are obtained in PM6:PCN3:Y6 and PM6:PCN3:BTP‐eC9 ternary devices, much higher than those of PM6:Y6 (16.31%) and PM6:BTP‐eC9 (17.33%) devices. Additionally, this ternary OSCs exhibit superior stability compared to binary host system. This work gives a promising path for halogen‐free donor polymers to achieve low energy loss and high PCE.