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Research Article

Halogenated thiophene substitutions on quinoxaline unit to achieve morphology optimization in efficient organic solar cells

Dingding Qiu1,2,3, Jianqi Zhang1, Kun Lu1,3( ), Zhixiang Wei1,3( )
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing 100190, China
Sino-Danish Center for Education and Research, Sino-Danish College, University of Chinese Academy of Sciences, Beijing 100049, China
University of Chinese Academy of Sciences, Beijing 100049, China
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Graphical Abstract

Halogenated thiophene units were introduced into the quinoxaline-based acceptors. Qx-Br showed the most favorable film morphology and efficient carrier generation/transport, leading to an outstanding power conversion efficiency (PCE) of 17.42%. Ternary blends of PM6:Qx-Br:Y6 can further optimize light utilization, reaching a high PCE of 18.36% with an open-circuit voltage (VOC) of 0.87 V.

Abstract

Halogenated thiophenes are generally used units for constructing organic semiconductor materials for photovoltaic applications. Here, we introduced thiophene, 2-bromothiophene, and 2-chlorothiophene units to the central core of quinoxaline-based acceptors and obtained three acceptors, Qx-H, Qx-Br, and Qx-Cl, respectively. Compared with Qx-H, Qx-Br and Qx-Cl showed enhanced absorption, down-shifted energy levels, improved crystallinity, and reduced energy disorder. The improved crystallinity significantly optimized the blend morphology, leading to efficient charge generation and transport and, therefore, less bimolecular recombination. Eventually, PM6:Qx-Br-based devices exhibited an outstanding power conversion efficiency of 17.42% with a high open-circuit voltage (VOC) of 0.915 V. Furthermore, Y6 was introduced into the PM6:Qx-Br binary system to improve the light utilization, and the resulting ternary devices delivered a high PCE of 18.36%. This study demonstrated the great potential of halogenated thiophene substitution in quinoxaline-based acceptors for building high-performance organic solar cell acceptor materials.

Keywords

halogenated thiophene unitsnon-fullerene acceptorsorganic solar cellsquinoxaline acceptorsmorphology optimization

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References

[1]

Shen, Y. F.; Zhang, H.; Zhang, J. Q.; Tian, C. Y.; Shi, Y. N.; Qiu, D. D.; Zhang, Z. Q.; Lu, K.; Wei, Z. X. In situ absorption characterization guided slot-die-coated high-performance large-area flexible organic solar cells and modules. Adv. Mater. 2023, 35, 2209030.
Crossref Google Scholar
[2]

Chang, Y. L.; Zhu, X. W.; Zhu, L. Y.; Wang, Y. H.; Yang, C.; Gu, X. R.; Zhang, Y. X.; Zhang, J. Q.; Lu, K.; Sun, X. N. et al. Regioregular narrow bandgap copolymer with strong aggregation ability for high-performance semitransparent photovoltaics. Nano Energy 2021, 86, 106098.
Crossref Google Scholar
[3]

Ma, L. J.; Zhang, S. Q.; Ren, J. Z.; Wang, G. L.; Li, J. Y.; Chen, Z. H.; Yao, H. F.; Hou, J. H. Design of a fully non-fused bulk heterojunction toward efficient and low-cost organic photovoltaics. Angew. Chem., Int. Ed. 2023, 62, e202214088.
Crossref Google Scholar
[4]

Chen, T.; Wang, S. T.; Yang, Z. B.; Feng, Q. Y.; Sun, X. M.; Li, L.; Wang, Z. S.; Peng, H. S. Flexible, light-weight, ultrastrong, and semiconductive carbon nanotube fibers for a highly efficient solar cell. Angew. Chem., Int. Ed. 2011, 50, 1815–1819.
Crossref Google Scholar
[5]

Chen, H.; Jeong, S. Y.; Tian, J. F.; Zhang, Y. D.; Naphade, D. R.; Alsufyani, M.; Zhang, W. M.; Griggs, S.; Hu, H. L.; Barlow S. et al. A 19% efficient and stable organic photovoltaic device enabled by a guest nonfullerene acceptor with fibril-like morphology. Energy Environ. Sci. 2023, 16, 1062–1070.
Crossref Google Scholar
[6]

Zhou, M. W.; Liao, C. T.; Duan, Y. W.; Xu, X. P.; Yu, L. Y.; Li, R. P.; Peng, Q. 19.10% efficiency and 80.5% fill factor layer-by-layer organic solar cells realized by 4-bis(2-thienyl)pyrrole-2,5-dione based polymer additives for inducing vertical segregation morphology. Adv. Mater. 2023, 35, 2208279.
Crossref Google Scholar
[7]

Li, D. H.; Deng, N.; Fu, Y. W.; Guo, C. H.; Zhou, B. J.; Wang, L.; Zhou, J.; Liu, D.; Li, W.; Wang, K. et al. Fibrillization of non-fullerene acceptors enables 19% efficiency pseudo-bulk heterojunction organic solar cells. Adv. Mater. 2023, 35, 2208211.
Crossref Google Scholar
[8]

Xiao, C.; Wang, X. C.; Zhong, T.; Zhou, R. X.; Zheng, X. F.; Liu, Y. R.; Hu, T. Y.; Luo, Y. X.; Sun, F. B.; Xiao, B. et al. Hybrid cycloalkyl-alkyl chain-based symmetric/asymmetric acceptors with optimized crystal packing and interfacial exciton properties for efficient organic solar cells. Adv. Sci. 2023, 10, 2206580.
Crossref Google Scholar
[9]

Li, C.; Zhou, J. D.; Song, J. L.; Xu, J. Q.; Zhang, H. T.; Zhang, X. N.; Guo, J.; Zhu, L.; Wei, D. H.; Han, G. C. et al. Non-fullerene acceptors with branched side chains and improved molecular packing to exceed 18% efficiency in organic solar cells. Nat. Energy 2021, 6, 605–613.
Crossref Google Scholar
[10]

Kong, X. L.; Zhu, C.; Zhang, J. Y.; Meng, L.; Qin, S. C.; Zhang, J. Q.; Li, J.; Wei, Z. X.; Li, Y. F. The effect of alkyl substitution position of thienyl outer side chains on photovoltaic performance of A-DA’D-A type acceptors. Energy Environ. Sci. 2022, 15, 2011–2020.
Crossref Google Scholar
[11]

Shi, Y. N.; Chang, Y. L.; Lu, K.; Chen, Z. H.; Zhang, J. Q.; Yan, Y. J.; Qiu, D. D.; Liu, Y. N.; Adil, M. A.; Ma, W. et al. Small reorganization energy acceptors enable low energy losses in non-fullerene organic solar cells. Nat. Commun. 2022, 13, 3256.
Crossref Google Scholar
[12]

Zhao, X.; An, Q. S.; Zhang, H.; Yang, C.; Mahmood, A.; Jiang, M. Y.; Jee, M. H.; Fu, B.; Tian, S. Y.; Woo, H. Y. et al. Double asymmetric core optimizes crystal packing to enable selenophene-based acceptor with over 18% efficiency in binary organic solar cells. Angew. Chem., Int. Ed. 2023, 62, e202216340.
Crossref Google Scholar
[13]

Meng, F.; Qin, Y.; Zheng, Y. T.; Zhao, Z. H.; Sun, Y. N.; Yang, Y. G.; Gao, K.; Zhao, D. B. Structural fusion yields guest acceptors that enable Ternary organic solar cells with 18.77% efficiency. Angew. Chem., Int. Ed. 2023, 62, e202217173.
Crossref Google Scholar
[14]

Shang, A.; Luo, S. W.; Zhang, J. Q.; Zhao, H.; Xia, X. X.; Pan, M. G.; Li, C.; Chen, Y. Z.; Yi, J. C.; Lu, X. H. et al. Over 18% binary organic solar cells enabled by isomerization of non-fullerene acceptors with alkylthiophene side chains. Sci. China: Chem. 2022, 65, 1758–1766.
Crossref Google Scholar
[15]

Murugan, P.; Hu, T.; Hu, X. T.; Chen, Y. W. Fused ring A-DA’D-A (Y-series) non-fullerene acceptors: Recent developments and design strategies for organic photovoltaics. J. Mater. Chem. A 2022, 10, 17968–17987.
Crossref Google Scholar
[16]

Chen, Y. Z.; Ma, R. J.; Liu, T.; Xiao, Y. Q.; Kim, H. K.; Zhang, J. Q.; Ma, C.; Sun, H. L.; Bai, F. J.; Guo, X. G. et al. Side-chain engineering on Y-series acceptors with chlorinated end groups enables high-performance organic solar cells. Adv. Energy Mater. 2021, 11, 2003777.
Crossref Google Scholar
[17]

Xie, L.; Lan, A.; Gu, Q.; Yang, S. C.; Song, W.; Ge, J. F.; Zhou, R.; Chen, Z. Y.; Zhang, J. Q.; Zhang, X. L. et al. Alkoxy substitution on asymmetric conjugated molecule enabling over 18% efficiency in ternary organic solar cells by reducing nonradiative voltage loss. ACS Energy Lett. 2023, 8, 361–371.
Crossref Google Scholar
[18]

Xie, L.; Zhang, J. S.; Song, W.; Ge, J. F.; Li, D. D.; Zhou, R.; Zhang, J. Q.; Zhang, X. L.; Yan, D. B.; Tang, B. C. et al. Rational tuning of intermolecular and intramolecular interactions enabling high-efficiency indoor organic photovoltaics. Nano Energy 2022, 99, 107414.
Crossref Google Scholar
[19]

Xia, Z. H.; Zhang, J. S.; Gao, X.; Song, W.; Ge, J. F.; Xie, L.; Zhang, X. L.; Liu, Z. T.; Ge, Z. Y. Fine-tuning the dipole moment of asymmetric non-fullerene acceptors enabling efficient and stable organic solar cells. ACS Appl. Mater. Interfaces 2021, 13, 23983–23992.
Crossref Google Scholar
[20]

Zhang, S. P.; Ma, X. L.; Niu, L. B.; Jeong, S. Y.; Woo, H. Y.; Zhou, Z. J.; Zhang, F. J. 18.66% Efficiency of polymer solar cells employing two nonfullerene acceptors with fluorine or chlorine substitution. Sol. RRL 2023, 7, 2200957.
Crossref Google Scholar
[21]

Zhou, Z. C.; Liu, W. R.; Zhou, G. Q.; Zhang, M.; Qian, D. P.; Zhang, J. Y.; Chen, S. S.; Xu, S. J.; Yang, C.; Gao, F. et al. Subtle molecular tailoring induces significant morphology optimization enabling over 16% efficiency organic solar cells with efficient charge generation. Adv. Mater. 2020, 32, 1906324.
Crossref Google Scholar
[22]

Liu, F.; Zhou, L.; Liu, W. R.; Zhou, Z. C.; Yue, Q. H.; Zheng, W. Y.; Sun, R.; Liu, W. Y.; Xu, S. J.; Fan, H. J. et al. Organic solar cells with 18% efficiency enabled by an alloy acceptor: A two-in-one strategy. Adv. Mater. 2021, 33, 2100830.
Crossref Google Scholar
[23]

Liu, W. R.; Zhang, J. Y.; Xu, S. J.; Zhu, X. Z. Efficient organic solar cells achieved at a low energy loss. Sci. Bull. 2019, 64, 1144–1147.
Crossref Google Scholar
[24]

Chen, Z. Y.; Ge, J. F.; Guo, Y. T.; Zhao, M. Y.; Shi, J. Y.; Qiu, Y.; Zhou, E. J.; Ge, Z. Y. Modification on the quinoxaline unit to achieve high open-circuit voltage and morphology optimization for organic solar cells. ACS Energy Lett. 2022, 7, 3432–3438.
Crossref Google Scholar
[25]

Chen, H. B.; Liang, H. Z.; Guo, Z. Q.; Zhu, Y.; Zhang, Z.; Li, Z. X.; Cao, X. J.; Wang, H. H.; Feng, W. Y.; Zou, Y. L. et al. Central unit fluorination of non-fullerene acceptors enables highly efficient organic solar cells with over 18% efficiency. Angew. Chem., Int. Ed. 2022, 61, e202209580.
Crossref Google Scholar
[26]

Busireddy, M. R.; Chen, T. W.; Huang, S. C.; Su, Y. J.; Wang, Y. M.; Chuang, W. T.; Chen, J. T.; Hsu, C. S. PBDB-T-based binary-OSCs achieving over 15. 83% efficiency via end-group functionalization and alkyl-chain engineering of quinoxaline-containing non-fullerene acceptors. ACS Appl. Mater. Interfaces 2022, 14, 41264–41274.
Crossref Google Scholar
[27]

Huang, J. F.; Li, S. S.; Qin, J. Z.; Xu, L.; Zhu, X. Z.; Yang, L. M. Facile modification of a noncovalently fused-ring electron acceptor enables efficient organic solar cells. ACS Appl. Mater. Interfaces 2021, 13, 45806–45814.
Crossref Google Scholar
[28]

Guo, L. Z.; Li, Q. D.; Ren, J. X.; Xu, Y. J.; Zhang, J. B.; Zhang, K.; Cai, Y. P.; Liu, S. J; Huang, F. Halogenated thiophenes serve as solvent additives in mediating morphology and achieving efficient organic solar cells. Energy Environ. Sci. 2022, 15, 5137–5148.
Crossref Google Scholar
[29]

Yuan, G. Z.; Fan, H. J.; Wan, S. S.; Jiang, Z.; Liu, Y. Q.; Liu, K. K.; Bai, H. R.; Zhu, X. Z.; Wang, J. L. A two-dimensional halogenated thiophene side-chain strategy for balancing Voc and Jsc and improving efficiency of non-fullerene small molecule acceptor-based organic solar cells. J. Mater. Chem. A 2019, 7, 20274–20284.
Crossref Google Scholar
[30]

Zhang, J. Q.; Li, Y. K.; Hu, H. W.; Zhang, G. Y.; Ade, H.; Yan, H. Chlorinated thiophene end groups for highly crystalline alkylated non-fullerene acceptors toward efficient organic solar cells. Chem. Mater. 2019, 31, 6672–6676.
Crossref Google Scholar
[31]

Wang, H.; Lu, H.; Chen, Y. N.; Ran, G. L.; Zhang, A. D.; Li, D. W.; Yu, N.; Zhang, Z.; Liu, Y. H.; Xu, X. J. et al. Chlorination enabling a low-cost benzodithiophene-based wide-bandgap donor polymer with an efficiency of over 17%. Adv. Mater. 2022, 34, 2105483.
Crossref Google Scholar
[32]

Lu, H.; Li, D. W.; Ran, G. L.; Chen, Y. N.; Liu, W. L.; Wang, H.; Li, S.; Wang, X. D.; Zhang, W. K.; Liu, Y. H. et al. Designing high-performance wide bandgap polymer donors by the synergistic effect of introducing carboxylate and fluoro substituents. ACS Energy Lett. 2022, 7, 3927–3935.
Crossref Google Scholar
[33]

Wang, H.; Lu, H.; Chen, Y. N.; Zhang, A. D.; Liu, Y. Q.; Li, D. W.; Liu, Y. H.; Xu, X. J.; Bo, Z. S. A versatile planar building block with C2V symmetry for high-performance non-halogenated solvent processable polymer donors. Adv. Energy Mater. 2022, 12, 2104028.
Crossref Google Scholar
[34]

Wang, H.; Lu, H.; Chen, Y. N.; Zhang, A. D.; Liu, Y. Q.; Zhang, C. E.; Liu, Y. H.; Xu, X. J.; Bo, Z. S. Effect of polymer chain regularity on the photovoltaic performance of organic solar cells. Chin. J. Polym. Sci. 2022, 40, 996–1002.
Crossref Google Scholar
[35]

Sun, H. L.; Liu, T.; Yu, J. W.; Lau, T. K.; Zhang, G. Y.; Zhang, Y. J.; Su, M. Y.; Tang, Y. M.; Ma, R. J.; Liu, B. et al. A monothiophene unit incorporating both fluoro and ester substitution enabling high-performance donor polymers for non-fullerene solar cells with 16.4% efficiency. Energy Environ. Sci. 2019, 12, 3328–3337.
Crossref Google Scholar
[36]

Weng, K. K.; Ye, L. L ; Zhu, L.; Xu, J. Q.; Zhou, J. J.; Feng, X.; Lu, G. H.; Tan, S. T.; Liu, F.; Sun, Y. M. Optimized active layer morphology toward efficient and polymer batch insensitive organic solar cells. Nat. Commun. 2020, 11, 2855.
Crossref Google Scholar
[37]

Li, M. J.; Zeng, Z. M. Y.; Fan, B. B.; Zhong, W. K.; Zhang, D. F.; Zhang, X. N.; Zhang, Y.; Ying, L.; Huang, F.; Cao, Y. Tailoring the side chain of imide-functional benzotriazole based polymers to achieve internal quantum efficiency approaching 100%. J. Mater. Chem. A 2020, 8, 23519–23525.
Crossref Google Scholar
[38]

Liu, Q. S.; Jiang, Y. F.; Jin, K.; Qin, J. Q.; Xu, J. G.; Li, W. T.; Xiong, J.; Liu, J. F.; Xiao, Z.; Sun, K. et al. 18% efficiency organic solar cells. Sci. Bull. 2020, 65, 272–275.
Crossref Google Scholar
[39]

Zhang, M. J.; Guo, X.; Ma, W.; Ade, H.; Hou, J. H. A large-bandgap conjugated polymer for versatile photovoltaic applications with high performance. Adv. Mater. 2015, 27, 4655–4660.
Crossref Google Scholar
[40]

Zhu, C.; Meng, L.; Zhang, J. Y.; Qin, S. C.; Lai, W. B.; Qiu, B. B.; Yuan, J.; Wan, Y.; Huang, W. C.; Li, Y. F. A quinoxaline-based D-A copolymer donor achieving 17.62% efficiency of organic solar cells. Adv. Mater. 2021, 33, 2100474.
Crossref Google Scholar
[41]

Zhang, W. Q.; Sun, C. K.; Qin, S. C.; Shang, Z. Y.; Li, S. M.; Zhu, C.; Yang, G.; Meng, L.; Li, Y. F. A cost-effective alpha-fluorinated bithienyl benzodithiophene unit for high-performance polymer donor material. ACS Appl. Mater. Interfaces 2021, 13, 55403–55411.
Crossref Google Scholar
[42]

Duan, T. N.; Gao, J.; Xu, T. L.; Kan, Z. P.; Chen, W. J.; Singh, R.; Kini, G. P.; Zhong, C.; Yu, D. H.; Xiao, Z. G. et al. Simple organic donors based on halogenated oligothiophenes for all small molecule solar cells with efficiency over 11%. J. Mater. Chem. A 2020, 8, 5843–5847.
Crossref Google Scholar
[43]

Duan, T. N.; Yang, Q. G.; Sun, Z. Y.; Chen, Q. Q.; Zhang, G. Q.; Hu, D. Q.; Oh, J.; Yang, C.; Lv, J.; Feng, B. et al. Oligothiophene electron donor and electron acceptor for all small molecule organic solar cells with efficiency over 9%. Chem. Eng. J. 2023, 456, 141006.
Crossref Google Scholar
[44]

Jeong, D.; Kim, G. U.; Lee, D.; Seo, S.; Lee, S.; Han, D.; Park, H.; Ma, B. W.; Cho, S.; Kim, B. J. Sequentially fluorinated polythiophene donors for high-performance organic solar cells with 16.4% efficiency. Adv. Energy Mater. 2022, 12, 2201603.
Crossref Google Scholar
[45]

Liang, Z. Q.; Li, M. M.; Wang, Q.; Qin, Y. P.; Stuard, S. J.; Peng, Z. X.; Deng, Y. F.; Ade, H.; Ye, L.; Geng, Y. H. Optimization requirements of efficient polythiophene: Nonfullerene organic solar cells. Joule 2020, 4, 1278–1295.
Crossref Google Scholar
[46]

Lin, Y. Z.; Zhao, F. W.; Prasad, S. K. K.; Chen, J. D.; Cai, W. Z.; Zhang, Q. Q.; Chen, K.; Wu, Y.; Ma, W.; Gao, F. et al. Balanced partnership between donor and acceptor components in nonfullerene organic solar cells with > 12% efficiency. Adv. Mater. 2018, 30, 1706363.
Crossref Google Scholar
[47]

Liu, J.; Chen, S. S.; Qian, D. P.; Gautam, B.; Yang, G. F.; Zhao, J. B.; Bergqvist, J.; Zhang, F. L.; Ma, W.; Ade, H. et al. Fast charge separation in a non-fullerene organic solar cell with a small driving force. Nat. Energy 2016, 1, 16089.
Crossref Google Scholar
[48]

Ye, Q. R.; Ge, J. F.; Li, D. D.; Chen, Z. Y.; Shi, J. Y.; Zhang, X. L.; Zhou, E. J.; Yang, D. B.; Ge, Z. Y. Modulation of the fluorination site on side-chain thiophene improved efficiency in all-small-molecule organic solar cells. ACS Appl. Mater. Interfaces 2022, 14, 33234–33241.
Crossref Google Scholar
[49]

Song, W.; Yu, K. B.; Ge, J. F.; Xie, L.; Zhou, R.; Peng, R. X.; Zhang, X. L.; Yang, M. J.; Wei, Z. X.; Ge, Z. Y. Entangled structure morphology by polymer guest enabling mechanically robust organic solar cells with efficiencies of over 16.5%. Matter 2022, 5, 1877–1889.
Crossref Google Scholar
[50]

Ge, J. F.; Hong, L.; Song, W.; Xie, L.; Zhang, J. S.; Chen, Z. Y.; Yu, K. B.; Peng, R. X.; Zhang, X. L.; Ge, Z. Y. Solvent annealing enables 15.39% efficiency all-small-molecule solar cells through improved molecule interconnection and reduced non-radiative loss. Adv. Energy Mater. 2021, 11, 2100800.
Crossref Google Scholar
[51]

Chen, H.; Zhao, T. X.; Li, L.; Tan, P.; Lai, H. J.; Zhu, Y. L.; Lai, X.; Han, L.; Zheng, N.; Guo, L. et al. 17.6%-efficient quasiplanar heterojunction organic solar cells from a chlorinated 3D network acceptor. Adv. Mater. 2021, 33, 2102778.
Crossref Google Scholar
[52]

Chen, H. B.; Zou, Y. L.; Liang, H. Z.; He, T. F.; Xu, X. Y.; Zhang, Y. X.; Ma, Z. F.; Wang, J.; Zhang, M. T.; Li, Q. W. et al. Lowing the energy loss of organic solar cells by molecular packing engineering via multiple molecular conjugation extension. Sci. China Chem. 2022, 65, 1362–1373.
Crossref Google Scholar
[53]

Zou, Y. L.; Chen, H. B.; Bi, X. Q.; Xu, X. Y.; Wang, H. B.; Lin, M. L.; Ma, Z. F.; Zhang, M. T.; Li, C. X.; Wan, X. J. et al. Peripheral halogenation engineering controls molecular stacking to enable highly efficient organic solar cells. Energy Environ. Sci. 2022, 15, 3519–3533.
Crossref Google Scholar
Nano Research
Volume 16 Issue 9,
September 2023
Pages 11630-11637
DOI: 10.1007/s12274-023-5723-x
Cite this article:
Qiu D, Zhang J, Lu K, et al. Halogenated thiophene substitutions on quinoxaline unit to achieve morphology optimization in efficient organic solar cells. Nano Research, 2023, 16(9): 11630-11637. https://doi.org/10.1007/s12274-023-5723-x
Topics:
Organic solar cells
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Received: 08 February 2023
Revised: 16 March 2023
Accepted: 10 April 2023
Published: 13 May 2023
© Tsinghua University Press 2023
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