Syntheses and Properties of Random Copolymers Using Thienyl-Thieno-Indole and Bithiophene-Dicarboximide with Different Ratios

Juae Kim; Ina Jeong; Jihoon Lee; Sung Heum Park; Hongsuk Suh

Macromolecular Research, Vol.27, No.5, 470-475, May, 2019

DOI10.1007/s13233-019-7067-7 Export Citation

Syntheses and Properties of Random Copolymers Using Thienyl-Thieno-Indole and Bithiophene-Dicarboximide with Different Ratios

Juae Kim, Ina Jeong, Jihoon Lee¹, Sung Heum Park^{1, †}, and Hongsuk Suh^†

Department of Chemistry and Chemistry Institute for Functional Materials, Pusan National University, Busan 46239, Korea
¹Department of Physics, Pukyong National University, Busan 48513, Korea

E-mail:,

We synthesized random copolymers using 6-(2-thienyl)-4H-thieno[3,2-b]indole (TTI) and N-alkyl-2,2′-bithiophene-3,3′-dicarboximide (BTI) as the electron-rich and deficient units for the polymer solar cells (PSCs). Herein, by using different feed ratios of electron-deficient unit, the push-pull type copolymers were synthesized by Stille polymerization of TTI, BTI and thiophene linkage. Out of the series PBTI3 with 7:3 ratio of TTI and BTI showed the highest molar absorption coefficient and mobility, which is favorable for efficiently harvesting solar photons and higher photo-induced carriers to improve the JSC. Among devices of synthesized copolymers, PBTI3/PC71BM (1:2) (with 3% DIO additive) blend-based PSCs showed the best performance with a JSC of 6.78 mA/cm2, a VOC of 0.72 V, a FF of 0.54 and a PCE of 2.64%.

Keywords:random polymer;photovoltaic cells;N-alkyl-2,2'-bithiophene-3,3'-dicarboximide unit (BTI);6-(2-thienyl)-4H-thieno[3,2-b]indole (TTI);random polymer

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[2] Liu W, Liu S, Zawacka NK, Andersen TR, Cheng P, Fu L, Chen M, Fu W, Bundgaard E, Jørgensen M, Zhan X, Krebs FC, Chen H, J. Mater. Chem. A, 2, 19809 (2014)

[3] Khan S, Lorenzelli L, Dahiya RS, IEEE Sens. J., 15, 3164 (2015)

[4] Zhuping F, Flurin DE, Xuechen J, Mohammed A, Jason AR, et al., Adv. Mater., 30, 170520 (2018)

[5] Nam S, Seo J, Woo S, Kim WH, Kim H, Bradley DDC, Kim Y, Nat. Commun., 6, 8929 (2015)

[6] Noh YJ, Na SI, Kim SS, Sol. Energy Mater. Sol. Cells, 117, 139 (2013)

[7] Beaujuge PM, Frechet JMJ, J. Am. Chem. Soc., 133(50), 20009 (2011)

[8] Yao HF, Ye L, Zhang H, Li SS, Zhang SQ, Hou JH, Chem. Rev., 116(12), 7397 (2016)

[9] Li Y, Accounts Chem. Res., 45, 723 (2012)

[10] Liu Y, Zhao J, Li Z, Mu C, Ma W, Hu H, Jiang K, Lin H, Ade H, Yan H, Nat. Commun., 5, 5293 (2014)

[11] Xiong J, Yang B, Cao C, Wu R, Huang Y, Sun J, Zhang J, Liu C, Tao S, Gao Y, Yang J, Org. Electron., 30, 30 (2016)

[12] Liao HC, Ho CC, Chang CY, Jao MH, Darling SB, Su WF, Mater. Today, 16, 326 (2013)

[13] Zhao F, Wang C, Zhan X, Adv. Eng. Mater., 8, 170314 (2018)

[14] Lee JY, Kim KS, Mhin BJ, J. Chem. Phys., 115(20), 9484 (2001)

[15] Duan C, Huang F, Cao Y, J. Mater. Chem., 22, 10416 (2012)

[16] Kim J, Kim NH, Song S, Park SY, Chae S, Bae E, Kim I, Kim HJ, Kim JY, Suh H, Polymer, 102, 84 (2016)

[17] Kim J, Shim JY, Lee J, Lee DY, Chae S, Kim J, Kim I, Kim HJ, Park SH, Suh H, J. Polym. Sci. A: Polym. Chem., 50, 1018 (2012)

[18] Kim J, Chae SM, Yi AR, Kim MJ, Kim HJ, Suh HS, Macromol. Res., 26(5), 438 (2018)

[19] Kim J, Park SY, Han G, Chae S, Song S, Shim JY, Bae E, Kim I, Kim HJ, Kim JY, Suh H, Polymer, 95, 36 (2016)

[20] Cho HJ, Kim YJ, Chen S, Lee J, Shin TJ, Park CE, Yang C, Nano Energy, 39, 229 (2017)

[21] Huo L, Xue X, Liu T, Xiong W, Qi F, Fan B, Xie D, Liu F, Yang C, Sun Y, Chem. Mater., 30, 3294 (2018)

[22] Jung JW, Liu F, Russell TP, Jo WH, Energy Environ. Sci., 6, 3301 (2013)

[23] Kim T, Lee JY, Heo J, Lim B, Kim JY, Polym. Chem, 9, 1216 (2018)

[24] Zhou NJ, Guo XG, Ortiz RP, Li SQ, Zhang SM, Chang RPH, Facchetti A, Marks TJ, Adv. Mater., 24(17), 2242 (2012)

[25] Kim J, Kim SH, Kim T, Shim JY, Park D, Kim J, Kim I, Kim JY, Suh H, Bull. Korean Chem. Soc., 36, 2238 (2015)

[26] (a)Blouin N, Michaud A, Leclerc M, Adv. Mater., 19, 2295 (2007) (b)Park SH, Roy A, Beaupre S, Cho S, Coates N, Moon JS, Moses D, Leclerc M, Lee K, Heeger AJ, Nat. Photonics, 3, 297 (2009).

[27] Shim JY, Baek J, Kim J, Park SY, Kim J, Kim I, Chun HH, Kim JY, Suh H, Polym. Chem., 6, 6011 (2015)

[28] Jeong I, Kim J, Kim J, Lee J, Lee DY, Kim I, Park SH, Suh H, Synth. Met., 213, 25 (2016)

[29] Kim J, Park SY, Han G, Chae S, Song S, Shim JY, Bae E, Kim I, Kim HJ, Kim JY, Suh H, Polymer, 95, 36 (2016)

[30] Jung JW, Liu F, Russell TP, Jo WH, Energy Environ. Sci., 6, 3301 (2013)

[31] Burkhart B, Khlyabich PP, Thompson BC, ACS Macro Lett., 1, 660 (2012)

[32] Zhang L, Pu M, Zhou W, Hu X, Zhang Y, Xie Y, Liu B, Chen Y, J. Phys. Chem. C, 119, 23310 (2015)