Simultaneously Achieving Highly Efficient and Stable Polymer:Non‐Fullerene Solar Cells Enabled By Molecular Structure Optimization and Surface Passivation

Abstract Despite the tremendous efforts in developing non‐fullerene acceptor (NFA) for polymer solar cells (PSCs), only few researches are done on studying the NFA molecular structure dependent stability of PSCs, and long‐term stable PSCs are only reported for the cells with low efficiency. Herein, the authors compare the stability of inverted PM6:NFA solar cells using ITIC, IT‐4F, Y6, and N3 as the NFA, and a decay rate order of IT‐4F > Y6 ≈ N3 > ITIC is measured. Quantum chemical calculations reveal that fluorine substitution weakens the C═C bond and enhances the interaction between NFA and ZnO, whereas the β‐alkyl chains on the thiophene unit next to the C═C linker blocks the attacking of hydroxyl radicals onto the C═C bonds. Knowing this, the authors choose a bulky alkyl side chain containing molecule (named L8‐BO) as the acceptor, which shows slower photo bleaching and performance decay rates. A combination of ZnO surface passivation with phenylethanethiol (PET) yields a high efficiency of 17% and an estimated long T80 and Ts80 of 5140 and 6170 h, respectively. The results indicate functionalization of the β‐position of the thiophene unit is an effective way to improve device stability of the NFA.