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3-(2-Octyldodecyl)thieno[3,2- b ]thiophen was successfully synthesized as a new π-bridge with a long branched side alkyl chain. Two donor-π-bridge-acceptor type copolymers were designed and synthesized by combining this π-bridge structure, a fluorinated benzothiadiazole acceptor unit, and a thiophene or thienothiophene donor unit, ( PT-ODTTBT or PTT-ODTTBT respectively) through Stille polymerization. Inverted OPV devices with a structure of ITO/ZnO/polymer:PC 71 BM/MoO 3 /Ag were fabricated by spin-coating in ambient atmosphere or N 2 within a glovebox to evaluate the photovoltaic performance of the synthesized polymers (effective active area: 0.09 cm 2 ). The PTT-ODTTBT :PC 71 BM-based structure exhibited the highest organic photovoltaic (OPV) device performance, with a maximum power conversion efficiency (PCE) of 7.05 (6.88 ± 0.12)%, a high short-circuit current ( J  sc ) of 13.96 mA/cm 2 , and a fill factor ( FF ) of 66.94 (66.47 ± 0.63)%; whereas the PT-ODTTBT :PC 71 BM-based device achieved overall lower device performance. According to GIWAXS analysis, both neat and blend films of PTT-ODTTBT exhibited well-organized lamellar stacking, leading to a higher charge carrier mobility than that of PT-ODTTBT . Compared to PT-ODTTBT containing a thiophene donor unit, PTT-ODTTBT containing a thienothiophene donor unit exhibited higher crystallinity, preferential face-on orientation, and a bicontinuous interpenetrating network in the film, which are responsible for the improved OPV performance in terms of high J  sc , FF , and PCE.

Novel Conjugated Polymers Containing 3-(2-Octyldodecyl)thieno[3,2-b]thiophene as a π-Bridge for Organic Photovoltaic Applications