Solution-processable tetrazine and oligothiophene based linear A-D-A small molecules: Synthesis, hierarchical structure and photovoltaic properties

A series of high coplanar alternative linear small molecules with acceptor-donor-acceptor (A-D-A) structure containing electron-accepting tetrazine (Tz) moiety and electron-donating oligothiophe nes (OTs) moiety, alkylated thiophene attached to both sides of the Tz moiety were designed and synthesized. The influences of varied oligothiophe ne length on small molecules' optical and electrochemical properties, crystallization, self assembling morphology in blend film with (6,6)-phenyl-C-61-butyric acid methyl ester (PC61BM), and photovoltai c properties for the application as donor materials in organic solar cells (OSCs) were studied. The optical and electrochemical properties of small molecules showed that the HOMO and LUMO energy levels were determined by the number of OTs moiety and electron-accepting ability of Tz in the alternative small molecules, respectively. Meanwhile, the varied OT moieties can significantly affect the hierarchical structures when mixed with PC61BM. The molecule with intermediate conjugate moity length showed the highest ordering in its crystalline state, as revealed by differential scannin gcalorimetry (DSC) and X-ray diffraction experiments, and best photovoltaic properties when blended together with PC61BM or (6,6)-phenyl-C-71-butyric acid methyl ester (PC71BM) as active layer in photovoltaic devices. The results indicate that hierarchical structures controlled by adjusting the conjugate moity length of small molecules is an effective way to improve the performance of OSCs. The photovoltaic device based on TT(HTTzHT)(2): PC71BM with 1% DIO additives showed the best performance, with a J(sc) of 7.87 mA/cm(2) and a PCE of 3.24%