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Syntheses and Photovoltaic Properties of Narrow Band Gap Donor–Acceptor Copolymers with Carboxylate-Substituted Benzodithiophene as Electron Acceptor Unit

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Institute of Materials Science, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan
Tsukuba Research Center for Interdisciplinary Materials Science, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan
Division of Materials Science, Faculty of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan
§ Photovoltaic Materials Unit, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba 305-0047, Japan
*(M.K.) E-mail: [email protected]
Cite this: Macromolecules 2014, 47, 15, 4987–4993
Publication Date (Web):July 31, 2014
https://doi.org/10.1021/ma501078e
Copyright © 2014 American Chemical Society
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Abstract

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Stille-coupling of carboxylate-substituted dibrominated benzodithiophene (BDTC) with 2,5-distannylthieno[3,4-b]thiophene gave novel donor–acceptor type alternating copolymers, PBDTC-TT, where BDTC works as an electron-accepting unit in the polymers. They showed broad absorption bands from 500 nm to the near-infrared region, optical band gap (Eg) about 1.5 eV, small π-stacking distance (3.6 Å), and good thermal stability. The hole mobilities of PBDTC-TT determined from performance of their organic field-effect transistors were 3.1–6.9 × 10–4 (cm2 V–1 s–1). The bulk heterojunction (BHJ) solar cells were fabricated with configuration of ITO/PEDOT:PSS/polymer:PC70BM/LiF/Al. A PBDTC-TT device exhibited photocurrent response upon exposure to light with wavelength of 300–900 nm and incident photon to current conversion efficiency over 40% in the range of 400–750 nm. The power conversion efficiency of the best-performed device reached 3.03% with short-circuit current density of 12.54 mA cm–2, fill factor of 0.48, and open circuit voltage of 0.51 V under illumination of AM 1.5 G/100 mW cm–2. These results show that the BDTC unit can behave as an electron accepting building block for donor–acceptor type narrow band gap polymers, and these types of polymers can be used as a donor material in the active layer for BHJ photovoltaic cells.

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Synthetic procedures of TT-Br and BDTC, NMR spectra of all compounds and polymers, thermogravimetric analysis charts, photoemission yield spectra in the atmosphere, AFM images of PBDTC-TT2:PC70BM, and FET characteristics of the PBDTC-TT1 and PBDTC-TT2. This material is available free of charge via the Internet at http://pubs.acs.org.

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