Skip to main content
SpringerLink
Log in

Slight Structural Disorder in Bithiophene-based Random Terpolymers with Improved Power Conversion Efficiency for Polymer Solar Cells

  • Article
  • Published:
Chinese Journal of Polymer Science Aims and scope Submit manuscript

Abstract

A series of random terpolymers P2−P5 were designed and synthesized by randomly embedding 5 mol%, 10 mol%, 15 mol% and 25 mol% feed ratios of low cost 2,2-bithiophene as the third monomer to the famous donor-acceptor (D-A) type copolymer PTB7-Th (P1). All polymers showed similar molecular weight with number-average molecular weight (Mn) and weight-average molecular weight (Mw) in the range of (59−74) and (93−114) kg·mol−1, respectively, to ensure a fair comparison on the structure-property relationships. Compared with the control copolymer PTB7-Th, the random terpolymers exhibited enhanced absorption intensity in a wide range from 400 nm to 650 nm in both solution and film as well as in polymer/PC71BM blends. From grazing incident wide-angle X-ray diffraction (GIWAXS), compared with the regularly alternated copolymer PTB7-Th, the random terpolymers demonstrated mild structural disorder with reduced (100) lamellar stacking and slightly weakened (010) π-π stacking for the polymers as well as slightly reduced PC71BM aggregation in polymer/PC71BM blends. However, the measured hole mobility for terpolymers ((1.20−3.73) × 10−4 cm2·V−1·s−1) was evaluated to be comparable or even higher than 1.35 × 10−4 cm2·V−1·s−1 of the alternative copolymer. Enhanced average power conversion efficiency (PCE) from 7.35% to 8.11% and 7.79% to 8.37% was observed in both conventional and inverted device architectures from copolymer P1 to terpolymers P4, while further increasing the 2,2-bithiophene feed ratio decreased the PCE.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Cheng, Y. J.; Yang, S. H.; Hsu, C. S. Synthesis of conjugated polymers for organic solar cell applications. Chem. Rev. 2009, 109(11), 5868–5923.

    Article  CAS  PubMed  Google Scholar 

  2. Brabec, C. J.; Heeney, M.; McCulloch, I.; Nelson, J. Influence of blend microstructure on bulk heterojunction organic photovoltaic performance. Chem. Soc. Rev. 2011, 40(3), 1185–1199.

    Article  CAS  PubMed  Google Scholar 

  3. Wang, S.; Huang W. Orthogonal solubility in fully conjugated donor-acceptor block copolymers: compatibilizers for polymer/fullerene bulk-heterojunction solar cells. Chinese J. Polym. Sci. 2017, 35(2), 207–218.

    Article  CAS  Google Scholar 

  4. Wu, Z.; Sun, C.; Dong, S.; Jiang, X. F.; Wu, S.; Wu, H.; Yip, H. L.; Huang, F.; Cao, Y. nType water/alcohol-soluble naphthalene diimide-based conjugated polymers for high-performance polymer solar cells. J. Am. Chem. Soc. 2016, 138(6), 2004–2013.

    Article  CAS  PubMed  Google Scholar 

  5. Zheng, Z.; Zhang, S.; Zhang, J.; Qin, Y.; Li, W.; Yu, R.; Wei, Z.; Hou, J. Over 11% efficiency in tandem polymer solar cells featured by a low-band-gap polymer with fine-tuned properties. Adv. Mater. 2016, 28(25), 5133–5138.

    Article  CAS  PubMed  Google Scholar 

  6. Cui, Y.; Yao, H.; Yang, C.; Zhang, S.; Hou, J. Organic solar cells with an efficiency approaching 15%. Acta Polymerica Sinica (in Chinese) 2018, (2), 223–230.

    Google Scholar 

  7. Duan, Y.; Xu, X.; Yan, H.; Wu, W.; Li, Z.; Peng, Q. Pronounced effects of a triazine core on photovoltaic performance-efficient organic solar cells enabled by a PDI trimer-based small molecular acceptor. Adv. Mater. 2017, 29(7), 1605115.

    Article  CAS  Google Scholar 

  8. Hendriks, K. H.; Heintges, G. H.; Gevaerts, V. S.; Wienk, M. M.; Janssen, R. A. High-molecular-weight regular alternating diketopyrrolopyrrole-based terpolymers for efficient organic solar cells. Angew. Chem. Int. Ed. 2013, 52(32), 8341–8344.

    Article  CAS  Google Scholar 

  9. Lu, L.; Zheng, T.; Wu, Q.; Schneider, A. M.; Zhao, D.; Yu, L. Recent advances in bulk heterojunction polymer solar cells. Chem. Rev. 2015, 115(23), 12666–12731.

    Article  CAS  PubMed  Google Scholar 

  10. Lee, J. W.; Ahn, H.; Jo, W. H. Conjugated random copolymers consisting of pyridine-and thiophene-capped diketopyrrolopyrrole as co-electron accepting units to enhance both JSC and VOC of polymer solar cells. Macromolecules 2015, 48(21), 7836–7842.

    Article  CAS  Google Scholar 

  11. Subbiah, J.; Purushothaman, B.; Chen, M.; Qin, T.; Gao, M.; Vak, D.; Scholes, F. H.; Chen, X.; Watkins, S. E.; Wilson, G. J.; Holmes, A. B.; Wong, W. W.; Jones, D. J. Organic solar cells using a high-molecular-weight benzodithiophenebenzothiadiazole copolymer with an efficiency of 9.4%. Adv. Mater. 2015, 27(4), 702–705.

    Article  CAS  PubMed  Google Scholar 

  12. Liu, Y.; Zhao, J.; Li, Z.; Mu, C.; Ma, W.; Hu, H.; Jiang, K.; Lin, H.; Ade, H.; Yan, H. Aggregation and morphology control enables multiple cases of high-efficiency polymer solar cells. Nat. Commun. 2014, 5, 5293.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  13. Liu, P.; Zhang, K.; Liu, F.; Jin, Y.; Liu, S.; Russell, T. P; Yip, H. L.; Huang, F.; Cao, Y. Effect of fluorine content in thienothiophene-benzodithiophene copolymers on the morphology and performance of polymer solar cells. Chem. Mater. 2014, 26(9), 3009–3017.

    Article  CAS  Google Scholar 

  14. Ye, L.; Jiao, X.; Zhang, S.; Yao, H.; Qin, Y.; Ade, H.; Hou, J. Control of mesoscale morphology and photovoltaic performance in diketopyrrolopyrrole-based small band gap terpolymers. Adv. Energy Mater. 2017, 7(3), 1601138.

    Article  CAS  Google Scholar 

  15. 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. Terthiophene-based D-A polymer with an asymmetric arrangement of alkyl chains that enables efficient polymer solar cells. J. Am. Chem. Soc. 2015, 137(44), 14149–14157.

    Article  CAS  PubMed  Google Scholar 

  16. Huo, L.; Liu, T.; Sun, X.; Cai, Y.; Heeger, A. J.; Sun, Y. Single-junction organic solar cells based on a novel widebandgap polymer with efficiency of 9.7%. Adv. Mater. 2015, 27(18), 2938–2944.

    Article  CAS  PubMed  Google Scholar 

  17. Wang, M.; Cai, D.; Xin, J.; Ma, W.; Tu, Q.; Zheng, Q. A ternary conjugated D-A copolymer yields over 9.0% efficiency in organic solar cells. J. Mater. Chem. A 2017, 5(24), 12015–12021.

    Article  CAS  Google Scholar 

  18. Ko, S. J.; Hoang, Q. V.; Song, C. E.; Uddin, M. A.; Lim, E.; Park, S. Y.; Lee, B. H.; Song, S.; Moon, S. J.; Hwang, S.; Morin, P.-O.; Leclerc, M.; Su, G. M.; Chabinyc, M. L.; Woo, H. Y.; Shin, W. S.; Kim, J. Y. High-efficiency photovoltaic cells with wide optical band gap polymers based on fluorinated phenylene-alkoxybenzothiadiazole. Energy Environ. Sci. 2017, 10(6), 1443–1455.

    Article  CAS  Google Scholar 

  19. Fan, B.; Xue, X.; Meng, X.; Sun, X.; Huo, L.; Ma, W.; Sun, Y. High-performance conjugated terpolymer-based organic bulk heterojunction solar cells. J. Mater. Chem. A 2016, 4(36), 13930–13937.

    Article  CAS  Google Scholar 

  20. Wan, Z.; Yang, J.; Liu, Y.; Wang, S.; Zhong, Y.; Li, C.; Zhang, Z.; Xing, G.; Huettner, S.; Tao, Y.; Li, Y.; Huang, W. Cyclometalated Pt complex-based random terpolymers for efficient polymer solar cells. Polym. Chem. 2017, 8(32), 4729–4737.

    Article  CAS  Google Scholar 

  21. Park, G. E.; Kim, H. J.; Lee, D. H.; Cho, M. J.; Choi, D. H. Regular terpolymers with fluorinated bithiophene units for high-performing photovoltaic cells. Polym. Chem. 2016, 7(31), 5069–5978.

    Article  CAS  Google Scholar 

  22. Jiang, T.; Yang, J.; Tao, Y.; Fan, C.; Xue, L.; Zhang, Z.; Li, H.; Li, Y.; Huang, W. Random terpolymer with a cost-effective monomer and comparable efficiency to PTB7-Th for bulkheterojunction polymer solar cells. Polym. Chem. 2016, 7(4), 926–932.

    Article  CAS  Google Scholar 

  23. Qian, M.; Zhang, R.; Hao, J.; Zhang, W.; Zhang, Q.; Wang, J.; Tao, Y.; Chen, S.; Fang, J.; Huang, W. Dramatic enhancement of power conversion efficiency in polymer solar cells by conjugating very low ratio of triplet iridium complexes to PTB7. Adv. Mater. 2015, 27(23), 3546–3552.

    Article  CAS  PubMed  Google Scholar 

  24. Keshtov, M. L.; Khokhlov, A. R.; Kuklin, S. A.; Chen, F. C.; Nikolaev, A. Y.; Koukaras, E. N.; Sharma, G. D. Synthesis of alternating D-A1-D-A2 terpolymers comprising two electrondeficient moieties, quinoxaline and benzothiadiazole units for photovoltaic applications. Polym. Chem. 2016, 7(24), 4025–4035.

    Article  CAS  Google Scholar 

  25. Duan, C.; Gao, K.; van Franeker J. J.; Liu, F.; Wienk, M. M.; Janssen, R. A. Toward practical useful polymers for highly efficient solar cells via a random copolymer approach. J. Am. Chem. Soc. 2016, 138(34), 10782–10785.

    Article  CAS  PubMed  Google Scholar 

  26. Wang, W. Development of spiro [cyclopenta [1,2-b:5,4-b′] dithiophene-4,9′-fluorene]-based A-π-D-π-A small molecules with different acceptor units for efficient organic solar cells. ACS Appl. Mater. Interfaces 2017, 9(5), 4614–4625.

    Article  CAS  PubMed  Google Scholar 

  27. Xu, X.; Zhang, G.; Zhao, Y.; Liu, J.; Li, Y.; Peng, Q. Highly efficient random terpolymers for photovoltaic applications with enhanced absorption and molecular aggregation. Chinese J. Polym. Sci. 2017, 35(2), 249–260.

    Article  CAS  Google Scholar 

  28. Tan, Z.; Li, S.; Wang, F.; Qian, D.; Lin, J.; Hou, J.; Li, Y. High performance polymer solar cells with as-prepared zirconium acetylacetonate film as cathode buffer layer. Sci. Rep. 2014, 4, 4691.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  29. Sun, Y.; Seo, J. H.; Takacs, C. J.; Seifter, J.; Heeger, A. J. Inverted polymer solar cells integrated with a low-temperature-annealed sol-gel-derived ZnO film as an electron transport layer. Adv. Mater. 2011, 23(14), 1679–1683.

    Article  CAS  PubMed  Google Scholar 

  30. Xue, Z.; Wang, S.; Yang, J.; Zhong, Y.; Qian, M.; Li, C.; Zhang, Z.; Xing, G.; Huettner, S.; Tao, Y.; Li, Y.; Huang, W. Enhanced power conversion efficiency in iridium complex based terpolymers for polymer solar cells. npj Flex. Electron. 2018, 2, 1.

    Article  Google Scholar 

  31. Wan, Q.; Guo, X.; Wang, Z.; Li, W.; Guo, B.; Ma, W.; Zhang, M.; Li, Y. 10.8% Efficiency polymer solar cells based on PTB7-Th and PC71BM via binary solvent additives treatment. Adv. Funct. Mater. 2016, 26(36), 6635–6640.

    Article  CAS  Google Scholar 

  32. Zhang, J.; Zhang, Y.; Fang, J.; Lu, K.; Wang, Z.; Ma, W.; Wei, Z. Conjugated polymer-small molecule alloy leads to high efficient ternary organic solar cells. J. Am. Chem. Soc. 2015, 137(25), 8176–8183.

    Article  CAS  PubMed  Google Scholar 

  33. Liang, Y.; Xu, Z.; Xia, J.; Tsai, S. T.; Wu, Y.; Li, G.; Ray, C.; Yu, L. For the bright future-bulk heterojunction polymer solar cells with power conversion efficiency of 7.4%. Adv. Mater. 2010, 22(20), E135–E138.

    Article  CAS  PubMed  Google Scholar 

  34. Bin, H.; Zhang, Z. G.; Gao, L.; Chen, S.; Zhong, L.; Xue, L.; Yang, C.; Li, Y. Non-fullerene polymer solar cells based on alkylthio and fluorine substituted 2D-conjugated polymers reach 9.5% efficiency. J. Am. Chem. Soc. 2016, 138(13), 4657–4664.

    Article  CAS  PubMed  Google Scholar 

  35. Li, Y. Molecular design of photovoltaic materials for polymer solar cells: toward suitable electronic energy levels and broad absorption. Acc. Chem. Res. 2012, 45(5), 723–733.

    Article  CAS  PubMed  Google Scholar 

  36. Prasad, S. K. K.; Gallaher, J. K.; Barker, A. J.; Woo, H. Y.; Abbas, M.; Hirsch, L.; Hodgkiss, J. M. Prof. SPIE 9926, 99231, 99231F-1.

    Google Scholar 

  37. Zusan, A.; Gieseking, B.; Zerson, M.; Dyakonov, V.; Magerle, R.; Deibel, C. The effect of diiodooctane on the charge carrier generation in organic solar cells based on the copolymer PBDTTT-C. Sci. Rep. 2015, 5, 8286.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

Download references

Acknowledgments

This work was financially supported by the the National Natural Science Foundation of China (No. 61761136013) and the Natural Science Foundation of Jiangsu Province (Nos. BK20160042 and BK20160990). S.H. is thankful to DFG (392306670) and Y.Z. is thankful to the CSC for financial support. Parts of this research were undertaken at the SAXS/WAXS beamline of the Australian Synchrotron.

Author information

Authors and Affiliations

  1. Key Lab for Flexible Electronics & Institute of Advanced Materials, Jiangsu National Synergistic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University, Nanjing, 211816, China

    Meng-Han Wang, Zhong-Yuan Xue, Wei-Hua Ning, Ya-Nan Liu & You-Tian Tao

  2. National Laboratory of Solid State Microstructures, School of Physics, and Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, 210093, China

    Zhi-Wei Wang & Chun-Feng Zhang

  3. Macromolecular Chemistry I, Universität Bayreuth, 30 Universitätsstr, 95447, Bayreuth, Germany

    Yu Zhong & Sven Huettner

Authors
  1. Meng-Han Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zhong-Yuan Xue
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhi-Wei Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Wei-Hua Ning
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yu Zhong
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ya-Nan Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Chun-Feng Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Sven Huettner
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. You-Tian Tao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to You-Tian Tao.

Electronic supplementary material

10118_2018_2128_MOESM1_ESM.pdf

Slight Structural Disorder in Bithiophene-based Random Terpolymers with Improved Power Conversion Efficiency for Polymer Solar Cells

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, MH., Xue, ZY., Wang, ZW. et al. Slight Structural Disorder in Bithiophene-based Random Terpolymers with Improved Power Conversion Efficiency for Polymer Solar Cells. Chin J Polym Sci 36, 1129–1138 (2018). https://doi.org/10.1007/s10118-018-2128-5

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10118-018-2128-5

Keywords

Search

Navigation