Skip to main content
SpringerLink
Log in

Improving photovoltaic performance of benzothiadiazole-based small molecules: A synergistic effect of non-covalent interaction and aryl terminal group

  • Published:
Journal of Materials Research Aims and scope Submit manuscript

Abstract

A–Ar–A-type small molecule (SM) of Py-2DTOBT and Py-2DTOBTPh with an Ar(A–D)2 framework were synthesized, in which 2,7-pyrene (Py) and alkoxyl-substituted benzothiadiazole (OBT) were, respectively, used as the central aryl (Ar) and arm acceptor (A), while 3-phenanthrene (Ph) was used as a terminal donor (D) in Py-2DTOBTPh. By comparison with the parent SM of Py-2DTBT, where 2,7-pyrene (Py) and benzothiadiazole (BT) were used as the central aryl (Ar) and arm acceptor (A), the effects of non-covalent interactions and the terminal group on optical, electrochemical, and photovoltaic properties were investigated. The gradually improved photovoltaic performances were observed among Py-2DTBT, Py-2DTOBT, and Py-2DTOBTPh based organic solar cells. A power conversion efficiency (PCE) of 2.83% was obtained in the Py-2DTOBTPh/PC71BM-based device, which is a 53% improvement related to that of Py-2DTOBT and three times enhanced related to that of Py-2DTBT(Py-2DTOBT:PCE of 1.86%, Py-2DTBT:PCE of 0.74%).

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

Figure 1
Figure 2
Figure 3
Table 1
Figure 4
Figure 5
Figure 6
Table 2
Figure 7
Scheme 1

Similar content being viewed by others

References

  1. L. Yuan, K. Lu, B.-Z. Xia, J.-Q. Zhang, Z. Wang, Z.-Y. Wang, D. Deng, J. Fang, L.-Y. Zhu, and Z.-X. We: Acceptor end-capped oligomeric conjugated molecules with broadened absorption and enhanced extinction coefficients for high-efficiency organic solar cells. Adv. Mater. 28, 5980 (2016).

    Article  CAS  Google Scholar 

  2. K. Cnops, B.P. Rand, D. Cheyns, B. Verreet, M.A. Empl, and P. Heremans: 8.4% efficient fullerene-free organic solar cells exploiting long-range exciton energy transfer. Nat. Commun. 5, 3406 (2014).

    Article  CAS  Google Scholar 

  3. K. Sun, Z. Xiao, S. Lu, W. Zajaczkowski, W. Pisula, E. Hanssen, J.M. White, R.M. Williamson, J. Subbiah, J. Ouyang, A.B. Holmes, W. Wong, and D.J. Jones: A molecular nematic liquid crystalline material for high-performance organic photovoltaics. Nat. Commun. 6, 6013 (2015).

    Article  CAS  Google Scholar 

  4. Q. Zhang, B. Kan, F. Liu, G. Long, X. Wan, X. Chen, Y. Zuo, W. Ni, H. Zhang, M. Li, Z. Hu, F. Huang, Y. Cao, Z. Liang, M. Zhang, T.P. Russell, and Y. Chen: Small-molecule solar cells with efficiency over 9%. Nat. Photon 9, 35 (2015).

    Article  CAS  Google Scholar 

  5. B. Kan, M. Li, Q. Zhang, F. Liu, X. Wan, Y. Wang, W. Ni, G. Long, X. Yang, H. Feng, Y. Zuo, M. Zhang, F. Huang, Y. Cao, T.P. Russell, and Y. Chen: Small-molecule solar cells with efficiency over 9%. J. Am. Chem. Soc. 137, 3886 (2015).

    Article  CAS  Google Scholar 

  6. D. Deng, Y. Zhang, J. Zhang, Z. Wang, L. Zhu, J. Fang, B. Xia, Z. Wang, K. Lu, W. Ma, and Z. Wei: Fluorination-enabled optimal morphology leads to over 11% efficiency for inverted small-molecule organic solar cells. Nat. Commun. 7, 13740 (2016).

    Article  CAS  Google Scholar 

  7. S. Zhang, Y. Qin, J. Zhu, and J. Hou: Over 14% efficiency in polymer solar cells enabled by a chlorinated polymer donor. Adv. Mater. 20, 1800868 (2018).

    Article  CAS  Google Scholar 

  8. H. Bin, Y. Yang, Z.-G. Zhang, L. Ye, M. Ghasemi, S. Chen, Y. Zhang, C. Zhang, C. Sun, L. Xue, C. Yang, H. Ade, and Y. Li: Over 14% efficiency in organic solar cells enabled by chlorinated nonfullerene small-molecule acceptors. J. Am. Chem. Soc. 139, 5085 (2017).

    Article  CAS  Google Scholar 

  9. B. Kan, Q. Zhang, M. Li, X. Wan, W. Ni, G. Long, Y. Wang, X. Yang, H. Feng, and Y.-S. Chen: Solution-processed organic solar cells based on dialkylthiol-substituted benzodithiophene unit with efficiency near 10%. J. Am. Chem. Soc. 44, 15529 (2014).

    Article  CAS  Google Scholar 

  10. H. Tan, Y. Long, J. Zhang, J. Zhu, J. Yang, J. Yu, and W. Zhu: Spirobifluorene-cored wide bandgap non-fullerene small molecular acceptor with 3D structure for organic solar cells. Dyes Pigm. 162, 797 (2019).

    Article  CAS  Google Scholar 

  11. J. Yu, W. Zhu, H. Tan, and Q. Peng: A novel D2-A-D1-A-D2-type donor–acceptor conjugated small molecule based on a benzo[1,2-b:4,5-b′]dithiophene core for solution processed organic photovoltaic cells. Chem. Phys. Lett. 667, 254 (2017).

    Article  CAS  Google Scholar 

  12. L. Meng, Y. Zhang, X. Wan, C. Li, X. Zhang, Y. Wang, X. Ke, Z. Xiao, L. Ding, R. Xia, H.-L. Yip, Y. Cao, and Y. Chen: Organic and solution-processed tandem solar cells with 17.3% efficiency. Science 361, 1094 (2018).

    Article  CAS  Google Scholar 

  13. B. Fan, D. Zhang, M. Li, W. Zhong, Z. Zeng, L. Ying, F. Huang, and Y. Cao: Achieving over 16% efficiency for single-junction organic solar cells. Sci. China Chem. 62, 746 (2019).

    Article  CAS  Google Scholar 

  14. J. Yuan, Y. Zhang, L. Zhou, G. Zhang, H.-L. Yip, T.-K. Lau, X. Lu, C. Zhu, H. Peng, P.A. Johnson, M. Leclerc, Y. Cao, J. Ulanski, Y.-F. Li, and Y.-P. Zou: Single-junction organic solar cell with over 15% efficiency using fused-ring acceptor with electron-deficient core. Joule 3, 1140 (2019).

    Article  CAS  Google Scholar 

  15. Y.-H. Lin, S.B. Darling, M.P. Nikiforov, J. Strzalka, and R. Verduzco: Supramolecular conjugated block copolymers. Macromolecules 45, 6571 (2012).

    Article  CAS  Google Scholar 

  16. K. Osowska and O.S. Miljanic: Supramolecular organization of extended benzobisoxazole cruciforms. Chem. Commun. 46, 4276 (2010).

    Article  CAS  Google Scholar 

  17. N.E. Jackson, B.M. Savoie, K.L. Kohlstedt, M. Olvera de la Cruz, G.C. Schatz, L.-X. Chen, and M.A. Ratner: Controlling conformations of conjugated polymers and small molecules: The role of nonbonding interactions. J. Am. Chem. Soc. 135, 10475 (2013).

    Article  CAS  Google Scholar 

  18. G. Conboy, R.G.D. Taylor, N.J. Findlay, A.L. Kanibolotsky, A.R. Inigo, S.S. Ghosh, B. Ebenhoch, L.K. Jagadamma, G.K.V.V. Thalluri, M.T. Sajjad, I.D.W. Samuel, and P.J. Skabara: Novel 4,8-benzobisthiazole (BBT) copolymers and their application in OFET and OPV devices. J. Mater. Chem. C 5, 11927 (2017).

    Article  CAS  Google Scholar 

  19. S. Yu, Y. Chen, L. Yang, P. Ye, J. Wu, J. Yu, S. Zhang, Y. Gao, and H. Huang: Significant enhancement of photovoltaic performance through introducing S/N conformational locks. J. Mater. Chem. A 5, 21674 (2017).

    Article  CAS  Google Scholar 

  20. J. Yu, Y. Zheng, and J. Huang: Towards High performance organic photovoltaic cells: A review of recent development in organic photovoltaics. Polymers 6, 2473 (2014).

    Article  CAS  Google Scholar 

  21. H. Huang, Z. Chen, R.P. Ortiz, C. Newman, H. Usta, S. Lou, J. Youn, Y. Noh, K. Baeg, L.-X. Chen, A. Facchetti, and T. Marks: Erratum: Combining electron-neutral building blocks with intramolecular ‘Conformational Locks’ affords stable, high-mobility P- and N-channel polymer semiconductors. J. Am. Chem. Soc. 134, 10966 (2012).

    Article  CAS  Google Scholar 

  22. H. Huang, L. Yang, A. Facchetti, and T.J. Marks: Organic and polymeric semiconductors enhanced by noncovalent conformational locks. Chem. Rev. 117, 10291 (2017).

    Article  CAS  Google Scholar 

  23. Q. Tao, M. Xiao, M. Zhu, L. Shao, Z. Sui, P. Wang, G. Huang, Y. Pei, W. Zhu, and F. Huang: Improving self-assembly behavior and photovoltaic performance of the indacenodithiophene-based small molecules via increasing dipole moment of the terminal group. Dyes Pigm. 144, 142 (2017).

    Article  CAS  Google Scholar 

  24. C. Duan, F. Alice, J.J. van Franeker, R.E.M. Willems, M.M. Wienk, and R.A.J. Janssen: Wide-bandgap benzodithiophene-benzothiadiazole copolymers for highly efficient multi-junction polymer solar cells. Adv. Mater. 27, 4461 (2015).

    Article  CAS  Google Scholar 

  25. J.W. Jo, W. Jung, E.H. Jung, H. Ahn, T.J. Shin, and W.H. Jo: Fluorination on both D and A units in D-A type conjugated copolymers based on difluorobithiophene and benzothiadiazole for highly efficient polymer solar cells. Energy Environ. Sci. 8, 2427 (2015).

    Article  CAS  Google Scholar 

  26. Z. Chen, P. Cai, J. Chen, X. Liu, L. Zhang, L. Lan, J. Peng, Y. Ma, and Y. Cao: Low band-gap conjugated polymers with strong interchain aggregation and very high hole mobility towards highly efficient thick-film polymer solar cells. Adv. Mater. 26, 2586 (2014).

    Article  CAS  Google Scholar 

  27. Q. Tao, D. Yan, Y. Liao, X. Huang, J. Deng, and D. Yu: Synthesis and photovoltaic performance of anthracene-based small molecules for solution-processed organic solar cells. ChemistrySelect 4, 752 (2019).

    Article  CAS  Google Scholar 

  28. W. Lee, G.H. Kim, S.J. Ko, S. Yum, S. Hwang, S. Cho, Y.H. Shin, J.Y. Kim, and H.Y. Woo: Semicrystalline D-A copolymers with different chain curvature for applications in polymer optoelectronic devices. Macromolecules 47, 1604 (2014).

    Article  CAS  Google Scholar 

  29. S. Yum, T.K. An, X. Wang, W. Lee, M.A. Uddin, Y.J. Kim, T.L. Nguyen, S. Xu, S. Hwang, C.E. Park, and H.Y. Woo: Benzotriazole-containing planar conjugated polymers with noncovalent conformational locks for thermally stable and efficient polymer field-effect transistors. Chem. Mater. 26, 2147 (2014).

    Article  CAS  Google Scholar 

  30. T. Lei, X. Xia, J.Y. Wang, C. Liu, and J. Pei: ‘Conformation locked’ strong electron-deficient poly(p-phenylene vinylene) derivatives for ambient-stable n-type field-effect transistors: Synthesis, properties, and effects of fluorine substitution position. J. Am. Chem. Soc. 136, 2135 (2014).

    Article  CAS  Google Scholar 

  31. C. Mallet, G. Savitha, M. Allain, V. Kozmík, J. Svoboda, P. Frère, and J. Roncali: Synthesis and electronic properties of D-A-D triads based on 3-alkoxy-4-cyanothiophene and benzothienothiophene blocks. J. Org. Chem. 77, 2041 (2012).

    Article  CAS  Google Scholar 

  32. W. Lee, H. Choi, S. Hwang, J.Y. Kim, and H.Y. Woo: Efficient conventional- and inverted-type photovoltaic cells using a planar alternating polythiophene copolymer. Chemistry 18, 2551 (2012).

    Article  CAS  Google Scholar 

  33. S.V. Meille, A. Farina, F. Bezziccheri, and M.C. Gallazzi: The influence of alkoxy side chains on the conformational flexibility of oligo- and polythiophenes. Adv. Mater. 6, 848 (1994).

    Article  CAS  Google Scholar 

  34. X. Guo, J. Quinn, Z. Chen, H. Usta, Y. Zheng, Y. Xia, J.W. Hennek, R.P. Ortiz, T.J. Marks, and A. Facchetti: Dialkoxybithiazole: A new building block for head-to-head polymer semiconductors. J. Am. Chem. Soc. 135, 1986 (2013).

    Article  CAS  Google Scholar 

  35. Y. Wang, S.R. Parkin, J. Gierschner, and M.D. Watson: Highly fluorinated benzobisbenzothiophenes. Org. Lett. 10, 3307 (2008).

    Article  CAS  Google Scholar 

  36. T.L. Nguyen, H. Choi, S.J. Ko, M.A. Uddin, B. Walker, S. Yum, J.E. Jeong, M.H. Yun, T.J. Shin, and S. Hwang: Semi-crystalline photovoltaic polymers with efficiency exceeding 9% in a ~300 nm thick conventional single-cell device. Energy Environ. Sci. 7, 3040 (2014).

    Article  CAS  Google Scholar 

  37. Y. Zhang, H. Tan, M. Xiao, X. Bao, Q. Tao, Y. Wang, Y. Liu, R. Yang, and W. Zhu: D–A–Ar-type small molecules with enlarged π-system of phenanthrene at terminal for high-performance solution processed organic solar cells. Org. Electron 15, 1173 (2014).

    Article  CAS  Google Scholar 

  38. Y. Zhang, X. Bao, M. Xiao, H. Tan, Q. Tao, Y. Wang, Y. Liu, R. Yang, and W. Zhu: Significantly improved photovoltaic performance of the triangular-spiral TPA(DPP-PN)3 by appending planar phenanthrene units into the molecular terminals. J. Mater. Chem. A 3, 886 (2015).

    Article  CAS  Google Scholar 

  39. Y. Zhang, M. Xiao, N. Su, J. Zhong, H. Tan, Y. Wang, Y. Liu, Y. Pei, R. Yang, and W. Zhu: Efficient strategies to improve photovoltaic performance of linear-shape molecules by introducing large planar aryls in molecular center and terminals. Org. Electron 17, 198 (2015).

    Article  CAS  Google Scholar 

  40. O.P. Lee, A.T. Yiu, P.M. Beaujuge, C.H. Woo, W.T. Holcombe, J.E. Millstone, J.D. Douglas, M.S. Chen, and J.M. Frechet: Efficient small molecule bulk heterojunction solar cells with high fill factors via pyrene-directed molecular self-assembly. Adv. Mater. 23, 5359 (2011).

    Article  CAS  Google Scholar 

  41. J. Deng, J. Chen, Q. Tao, D. Yan, Y. Fu, and H. Tan: Improved photovoltaic performance of 2,7-pyrene based small molecules via the use of 3-carbazole as terminal unit. Tetrahedron 74, 3989 (2018).

    Article  CAS  Google Scholar 

  42. D. Mi, J.B. Park, F. Xu, H.U. Kim, J.-H. Kim, and D.-H. Hwang: Synthesis and Characterization of Phenanthrene-substituted Fullerene Derivatives as Electron Acceptors for P3HT-based Polymer Solar Cells. Bull. Korean Chem. Soc. 35, 1647 (2014).

    Article  CAS  Google Scholar 

  43. J. Chen, M. Xiao, L. Duan, Q. Wang, H. Tan, N. Su, Y. Liu, R. Yang, and W. Zhu: Benzodi(pyridothiophene): A novel acceptor unit for application in A1–A–A1 type photovoltaic small molecules. Phys. Chem. Chem. Phys. 18, 1507 (2016).

    Article  CAS  Google Scholar 

  44. P. Zhou, D. Dang, M. Xiao, Q. Wang, J. Zhong, H. Tan, Y. Pei, R. Yang, and W. Zhu: Improved photovoltaic performance of star-shaped molecules with a triphenylamine core by tuning the substituted position of the carbazolyl unit at the terminal. J. Mater. Chem. A 3, 10883 (2015).

    Article  CAS  Google Scholar 

  45. J. Chen, L. Duan, M. Xiao, Q. Wang, B. Liu, H. Xia, R. Yang, and W. Zhu: Tuning the central fused ring and terminal units to improve the photovoltaic performance of Ar(A–D)2 type small molecules in solution-processed organic solar cells. J. Mater. Chem. A 4, 4952 (2016).

    Article  CAS  Google Scholar 

  46. W. Su, M. Xiao, Q. Fan, J. Zhong, J. Chen, D. Dang, J. Shi, W. Xiong, X. Duan, H. Tan, Y. Liu, and W. Zhu: Significantly increasing open-circuit voltage of the benzo[1,2-b:4,5-b0]dithiophene-alt-5,8-dithienyl-quinoxaline copolymers based PSCs by appending dioctyloxy chains at 6,7-positions of quinoxaline. Org. Electron 17, 129 (2015).

    Article  CAS  Google Scholar 

  47. J. Lee, M. Kim, B. Kang, S.B. Jo, H.G. Kim, J. Shin, and K. Cho: Side-chain engineering for fine-tuning of energy levels and nanoscale morphology in polymer solar cells. Adv. Energy Mater. 4, 1400087 (2014).

    Article  CAS  Google Scholar 

  48. Q. Tao, T. Liu, L. Duan, Y. Cai, W. Xiong, P. Wang, H. Tan, G. Lei, Y. Pei, W. Zhu, R. Yang, and Y. Sun: Wide bandgap copolymers with vertical benzodithiophene dicarboxylate for high-performance polymer solar cells with an efficiency up to 7.49%. J. Mater. Chem. A 4, 18792 (2016).

    Article  CAS  Google Scholar 

  49. D. Yan, Y. Liao, X. Huang, Q. Tao, and J. Deng: Synthesis and photoelectric performance of D–A–A’ type small molecule based on triphenylamine. Mater. Res. Express 5, 075101 (2018).

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was supported by the Natural Science Foundation of Hunan Province (2015JJ2042, 2018JJ3098, 2019JJ40057), Open Foundation of Hunan Innovation Platform (18K091), and Foundation of Jiangsu Engineering Laboratory of Light-Electricity-Heat Energy-Converting Materials and Applications (GDRGCS2019005).

Author information

Authors and Affiliations

  1. Hunan Provincial Key Laboratory of Environmental Catalysis & Waste Recycling, School of Materials and Chemical Engineering, Hunan Institute of Engineering, Xiangtan, 411104, China

    Qian Liu, Jiyong Deng, Dong Yan, Xianwei Huang, Yunfeng Liao & Qiang Tao

Authors
  1. Qian Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jiyong Deng
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Dong Yan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xianwei Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yunfeng Liao
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Qiang Tao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Jiyong Deng or Qiang Tao.

Supplementary Material

Supplementary Material

To view supplementary material for this article, please visit https://doi.org/10.1557/jmr.2020.254.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, Q., Deng, J., Yan, D. et al. Improving photovoltaic performance of benzothiadiazole-based small molecules: A synergistic effect of non-covalent interaction and aryl terminal group. Journal of Materials Research 35, 2967–2975 (2020). https://doi.org/10.1557/jmr.2020.254

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1557/jmr.2020.254

Search

Navigation