Conjugated polymers having good electrochemical and thermal stability are highly desired in optoelectronics. We report a new polythiophene consisting of alternating 4,4′-didodecyl-2,2′-bithiophene and terthiophene units (HPL1) synthesized via Stille coupling reaction. The optical band gap of HPL1 (1.92 eV) is similar to that of regioregular poly(3-hexylthiophene) (rr-P3HT, 1.89 eV). In comparison to rr-P3HT, the HPL1 when subjected to the cyclic voltammetry as thin film shows much superior electrochemical stability and a lower highest occupied molecular orbital energy level (−4.87 eV for rr-P3HT and −4.95 eV for HPL1). The transient photoluminescence study of HPL1 and rr-P3HT shows that both materials have two exciton decay processes, and the excitons of rr-P3HT are quenched more quickly. The onset decomposition, Td for rr-P3HT (465°C) is 4°C lower than HPL1 (469°C). Preliminary photovoltaic study disclosed that the polymer solar cell based on HPL1:[6,6]-phenyl-C61-butyric acid methyl ester blend showed a power conversion efficiency of 0.63%, with a Voc of 0.6 V, and a short circuit current (Jsc) of 2.79 mA cm−2 under AM 1.5 illumination (100 mW cm−2). The whole study provided an important example to design new electrochemically and thermally stable polymers with longer exciton life time for application in bulk heterojunction polymer solar cells. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
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