• charge transfer;
  • photovoltaic effects;
  • pi interactions;
  • polymerization;
  • thin layers


We have synthesized four types of cyclopentadithiophene (CDT)-based low-bandgap copolymers, poly[{4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl}-alt-(2,2′-bithiazole-5,5′-diyl)] (PehCDT-BT), poly[(4,4-dioctyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl)-alt-(2,2′-bithiazole-5,5′-diyl)] (PocCDT-BT), poly[{4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl}-alt-{2,5-di(thiophen-2-yl)thiazolo[5,4-d]thiazole-5,5′-diyl}] (PehCDT-TZ), and poly[(4,4-dioctyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl)-alt-{2,5-di(thiophen-2-yl)thiazolo[5,4-d]thiazole-5,5′-diyl}] (PocCDT-TZ), for use in photovoltaic applications. The intramolecular charge-transfer interaction between the electron-sufficient CDT unit and electron-deficient bithiazole (BT) or thiazolothiazole (TZ) units in the polymeric backbone induced a low bandgap and broad absorption that covered 300 nm to 700–800 nm. The optical bandgap was measured to be around 1.9 eV for PehCDT-BT and PocCDT-BT, and around 1.8 eV for PehCDT-TZ and PocCDT-TZ. Gel permeation chromatography showed that number-average molecular weights ranged from 8000 to 14 000 g mol−1. Field-effect mobility measurements showed hole mobility of 10−6–10−4 cm2 V−1 s−1 for the copolymers. The film morphology of the bulk heterojunction mixtures with [6,6]phenyl-C61-butyric acid methyl ester (PCBM) was also examined by atomic force microscopy before and after heat treatment. When the polymers were blended with PCBM, PehCDT-TZ exhibited the best performance with an open circuit voltage of 0.69 V, short-circuit current of 7.14 mA cm−2, and power conversion efficiency of 2.23 % under air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm−2).