Citation: Zhi-ming Hu, Hui Chen, Xiao-wei Zhong, Jian-fei Qu, Wei Chen, An-hua Liu, Feng He. Design and Synthesis of Halogen Atom Substituted Benzothiadiazole-based Donor Polymers for Efficient Solar Energy Conversion[J]. Acta Polymerica Sinica, ;2018, (2): 273-283. doi: 10.11777/j.issn1000-3304.2018.17243 shu

Design and Synthesis of Halogen Atom Substituted Benzothiadiazole-based Donor Polymers for Efficient Solar Energy Conversion

Zhi-ming Hu ^1,2 ,
Hui Chen ¹ ,
Xiao-wei Zhong ¹ ,
Jian-fei Qu ¹ ,
Wei Chen ^3,4,, ,
An-hua Liu ^2,, ,
Feng He ^1,,

1.
Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055
2.
College of Materials, Xiamen University, Xiamen 361005
3.
Institute for Molecular Engineering and Materials Science Division, Argonne National Laboratory, Lemont 60439, USA
4.
Institute for Molecular Engineering, The University of Chicago, Chicago 60637, USA

Corresponding author: Wei Chen, wchen@anl.gov An-hua Liu, ahliu@xmu.edu.cn Feng He, hef@sustc.edu.cn
Received Date: 28 August 2017
Revised Date: 25 September 2017

Halogen substituted benzothiadiazole polymers with different length of alkyl side chains were synthesized via Stille coupling and used as donor materials in polymer solar cells (PSC). These polymers exhibited good solubility in common organic solvents, excellent film forming ability, and broad absorption properly towards the sun light. By introducing the halogen atoms to the backbone, in particularly the large chlorine atoms, fullerene-based (PC₇₁BM) bulk heterojunction PSCs of these polymers could achieve enhanced open-circuit voltage and short-circuit current, and eventually the power conversion efficiency could be dramatically improved. It was found that the halogen substitution and various alkyl side chains could highly affect the polymers' band gaps and charge transport properties, through influencing the molecular orientation and crystallinity. With regard to tuning the energy levels, compared with fluorine atom, chlorine atom with a bigger atomic radius could reduce more efficiently the energy levels, thereby further improving the open-circuit voltage of the corresponding PSCs. In this study, the PSCs based on one-chlorine-and-one-fluorine-substituted PCFBT4T-2OD, with PC₇₁BM used as the acceptor, exhibited an open-circuit voltage of 0.72 V, a short-circuit current of 17.61 mA cm^-2, and the highest power conversion efficiency of 8.84%. From the grazing-incidence wide-angle X-ray scattering (GIWAXS) experiments, those polymers with the halogen atoms substitutions showed a mixed "face-on" and "edge-on" conformation in their blended films. The introduction of fluorine atoms in the polymer PCFBT4T-2OD further enhanced the π-π stacking, compared with the one-chlorine substituted PCBT4T-2BO, which was helpful for the charge transport in the active layer and to enhance the device performance in PSCs. Those results demonstrated that the halogen substitution was an effective molecular design strategy to modify the polymer aggregation and morphology for optimized polymer solar cell applications.
- Polymer solar cells,
- Donor materials,
- Halogen atom substitution,
- Open-circuit voltage
1. [1]
  Ashraf R S, Schroeder B C, Bronstein H A, Huang Z, Thomas S, Kline R J, Brabec C J, Rannou P, Anthopoulos T D, Durrant J R, McCulloch I. Adv Mater, 2013, 25(14):2029-2034 doi: 10.1002/adma.201300027
2. [2]
  Dkhil S B, Pfannmöller M, Bals S, Koganezawa T, Yoshimoto N, Hannani D, Gaceur M, Videlot-Ackermann C, Margeat O, Ackermann J. Adv Energy Mater, 2016, 13:290-300
3. [3]
  He F, Cheng G, Zhang H, Zheng Y, Xie Z, Yang B, Ma Y, Liu S, Shen J. Chem Commun, 2003, 17:2206-2207
4. [4]
  Fan B, Xue X, Meng X, Sun X, Huo L, Ma W, Sun Y. J Mater Chem A, 2016, 4:13930-13937 doi: 10.1039/C6TA05886H
5. [5]
  He F, Yu L. J Phys Chem Lett, 2011, 2(24):3102-3113 doi: 10.1021/jz201479b
6. [6]
  Lu L, Zheng T, Wu Q, Schneider A M, Zhao D, Yu L. Chem Rev, 2015, 115:12666-12731 doi: 10.1021/acs.chemrev.5b00098
7. [7]
  Liu X, Li X, Li Y, Song C, Zhu L, Zhang W, Wang H Q, Fang J. Adv Mater, 2016, 28(34):7405-7412 doi: 10.1002/adma.201601814
8. [8]
  Ma W, Yang G, Jiang K, Carpenter J H, Wu Y, Meng X, McAfee T, Zhao J, Zhu C, Wang C, Ade H, Yan H. Adv Energy Mater, 2015, 5(23):1501400 doi: 10.1002/aenm.201501400
9. [9]
  Li G, Shrotriya V, Huang J, Yao Y, Moriarty T, Emery K, Yang Y. Nat Mater, 2005, 4(11):864-868 doi: 10.1038/nmat1500
10. [10]
  Hu H, Jiang K, Yang G, Liu J, Li Z, Lin H, Liu Y, Zhao J, Zhang J, Huang F, Qu Y, Ma W, Yan H. J Am Chem Soc, 2015, 137(44):14149-14157 doi: 10.1021/jacs.5b08556
11. [11]
  Lin Y, Zhao F, Wu Y, Chen K, Xia Y, Li G, Prasad S K K, Zhu J, Huo L, Bin H, Zhang Z G, Guo X, Zhang M, Sun Y, Gao F, Wei Z, Ma W, Wang C, Hodgkiss J, Bo Z, Inganäs O, Li Y, Zhan X. Adv Mater, 2016, 3:1604155
12. [12]
  Yao J, Yu C, Liu Z, Luo H, Yang Y, Zhang G, Zhang D. J Am Chem Soc, 2016, 138(1):173-185 doi: 10.1021/jacs.5b09737
13. [13]
  Yang Shu, Zhang Wei, Shen Xingxing, Liu Ying, Du Xiaoyan, Chen Shan, Xiao Zuo, Yang Zhenyu, Zuo Qiqun, Ding Liming. Acta Polymerica Sinica, 2012, (8):838-845
14. [14]
  van Pham C, Mark H, Zimmer H. Synth Commun, 1986, 16(6):689-696 doi: 10.1080/00397918608057741
15. [15]
  Li M, Gao K, Wan X, Zhang Q, Kan B, Xia R, Liu F, Yang X, Feng H, Ni W, Wang Y, Peng J, Zhang H, Liang Z, Yip H L, Peng X, Cao Y, Chen Y. Nat Photon, 2016, 11(2):85-90
16. [16]
  Chen C C, Chang W H, Yoshimura K, Ohya K, You J, Gao J, Hong Z, Yang Y. Adv Mater, 2014, 26(32):5670-5677 doi: 10.1002/adma.201402072
17. [17]
  Yusoff A R b M, Kim D, Kim H P, Shneider F K, da Silva W J, Jang J. Energy Environ Sci, 2015, 8(1):303-316 doi: 10.1039/C4EE03048F
18. [18]
  Yu G, Gao J, Hummelen J C, Wudl F, Heeger A J. Science, 1995, 270:1789-1971 doi: 10.1126/science.270.5243.1789
19. [19]
  He Z, Xiao B, Liu F, Wu H, Yang Y, Xiao S, Wang C, Russell T P, Cao Y. Nat Photonics, 2015, 9(3):174-179 doi: 10.1038/nphoton.2015.6
20. [20]
  Wang Y, Parkin S R, Gierschner J, Watson M D. Org Lett, 2008, 10(15):3307-3310 doi: 10.1021/ol8003468
21. [21]
  Albrecht S, Janietz S, Schindler W, Frisch J, Kurpiers J, Kniepert J, Inal S, Pingel P, Fostiropoulos K, Koch N, Neher D. J Am Chem Soc, 2012, 134(36):14932-14944 doi: 10.1021/ja305039j
22. [22]
  Wang Y, Xin X, Lu Y, Xiao T, Xu X, Zhao N, Hu X, Ong B S, Ng S C. Macromolecules 2013, 46(24):9587-9592 doi: 10.1021/ma401709r
23. [23]
  Dang M. T, Hirsch L, Wantz G, Wuest J D. Chem Rev, 2013, 113(5):3734-65 doi: 10.1021/cr300005u
24. [24]
  Zhou H, Yang L, Xiao S, Liu S, You W. Macromolecules, 2010, 43(2):811-820 doi: 10.1021/ma902241b
25. [25]
  Zhang S, Qin Y, Uddin M A, Jang B, Zhao W, Liu D, Woo H Y, Hou J. Macromolecules, 2016, 49(8):2993-3000 doi: 10.1021/acs.macromol.6b00248
26. [26]
  Jo J W, Jung J W, Wang H W, Kim P, Russell T P, Jo W H. Chem Mater, 2014, 26(14):4214-4220 doi: 10.1021/cm502229k
27. [27]
  Wang E, Wang L, Lan L, Luo C, Zhuang W, Peng J, Cao Y. Appl Phys Lett, 2008, 92(3):033307 doi: 10.1063/1.2836266
28. [28]
  Allard N, Aïch R d B, Gendron D, Boudreault P L T, Tessier C, Alem S, Tse S C, Tao Y, Leclerc M. Macromolecules, 2010, 43(5):2328-2333 doi: 10.1021/ma9025866
29. [29]
  Hu Z M, Chen H, Qu J F, Zhong X W, Chao P J, Xie M, Lu W, Liu A H, Tian L L, Su Y A, Chen W, He F. ACS Energy Lett, 2017, 2:753-758 doi: 10.1021/acsenergylett.7b00092
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