Plasticizer Enhanced Chain Orientation and Dynamics for Printed Stretchable Conjugated Polymer Films

Fei-Yan Zhang; Zhao-Min Gao; Yu Chen; Jia-Yi Hua; Yu-Lin Han; Ning-Xin Wang; Ming-Hui Wang; Bi-Ying Wang; Guang-Tao Zhao; Kui Zhao; Zi-Cheng Ding; Yan-Chun Han

doi:10.1007/s10118-025-3526-0

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Plasticizer Enhanced Chain Orientation and Dynamics for Printed Stretchable Conjugated Polymer Films

RESEARCH ARTICLE | Updated：2026-03-26

- Plasticizer Enhanced Chain Orientation and Dynamics for Printed Stretchable Conjugated Polymer Films
- Plasticizer Enhanced Chain Orientation and Dynamics for Printed Stretchable Conjugated Polymer Films
- Chinese Journal of Polymer Science 2026年44卷第4期页码：959-969
- Affiliations：
  
  a.Shaanxi Key Laboratory for Advanced Energy Devices, Shaanxi Engineering Laboratory for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119, China
  b.State Key Laboratory of Polymer Science and Technology, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  c.Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China
- Author bio：
  
  zcding@snnu.edu.cn (Z.C.D.)
  ychan@ciac.ac.cn (Y.C.H.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 52433009), the Fundamental Research Funds for the Central Universities (No. GK202501005), and the State Key Laboratory of Polymer Science and Technology (No. PST-KF2025-07). We thank the 1W1A-Diffuse X-ray Scattering Beamline of Beijing Synchrotron Radiation Facility (https://cstr.cn/31109.02.BSRF.1W1A) for providing technical support and assistance in GIWAXS data collection.;Yan-Chun Han is an editorial board member for Chinese Journal of Polymer Science and was not involved in the editorial review or the decision to publish this article. The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3526-0.The data that support the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-025-3526-0
  中图分类号：
- 收稿：2025-10-27，
  
  修回：2025-12-02，
  
  录用：2025-12-03，
  
  网络首发：2026-02-06，
  
  纸质出版：2026-04-05
- Accepted：
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Zhang, F. Y.; Gao, Z. M.; Chen, Y.; Hua, J. Y.; Han, Y. L.; Wang, N. X.; Wang, M. H.; Wang, B. Y.; Zhao, G. T.; Zhao, K.; Ding, Z. C.; Han, Y. C. Plasticizer enhanced chain orientation and dynamics for printed stretchable conjugated polymer films. Chinese J. Polym. Sci. 2026, 44, 959–969

Fei-Yan Zhang, Zhao-Min Gao, Yu Chen, et al. Plasticizer Enhanced Chain Orientation and Dynamics for Printed Stretchable Conjugated Polymer Films[J]. Chinese Journal of Polymer Science, 2026, 44(4): 959-969.
Zhang, F. Y.; Gao, Z. M.; Chen, Y.; Hua, J. Y.; Han, Y. L.; Wang, N. X.; Wang, M. H.; Wang, B. Y.; Zhao, G. T.; Zhao, K.; Ding, Z. C.; Han, Y. C. Plasticizer enhanced chain orientation and dynamics for printed stretchable conjugated polymer films. Chinese J. Polym. Sci. 2026, 44, 959–969 DOI： 10.1007/s10118-025-3526-0.

Fei-Yan Zhang, Zhao-Min Gao, Yu Chen, et al. Plasticizer Enhanced Chain Orientation and Dynamics for Printed Stretchable Conjugated Polymer Films[J]. Chinese Journal of Polymer Science, 2026, 44(4): 959-969. DOI： 10.1007/s10118-025-3526-0.

摘要

This study introduces a plasticizer-assisted bar coating strategy for the scalable fabrication of high-performance stretchable conjugated polymer film. With reduced crystallinity

enhanced edge-on orientation and promoted chain alignment

the plasticizer-processed film shows significantly improved stretchability and charge mobilities under varying strains compared to the neat film.

Abstract

The scalable fabrication of stretchable conjugated polymer films

via

solution printing is essential for their practical application in large-area wearable electronics. However

the printed conj

ugated polymer films typically exhibit high crystallinity

limiting their mechanical deformability. Herein

we propose a plasticizer-assisted printing strategy to simultaneously enhance the stretchability and electrical performance of films based on the conjugated polymer poly(3-(5-(5-methylselenophen-2-yl)thiophen-2-yl)-6-(5-methylthiophen-2-yl)-2

5-bis(4-octyltetradecyl)-2

5-dihydropyrrolo[3

4-c

]

pyrrole-1

4-dione) (P(TDPP-Se)). The incorporation of a plasticizer trioctyl trimellitate (TOTM) promotes P(TDPP-Se) aggregation in initial solution

facilitates chain alignment under flow field

and shorten solidification process

thereby restricting randomly polymer crystallization. Consequently

a low-crystallinity film with favorable edge-on orientation

strong chain alignment and improved chain dynamics is realized

which effectively alleviates crystallites fragmentation and crack propagation under large strain. The TOTM-plasticized film exhibits approximately 2-fold improvements in fracture strain and charge mobility

along with superior mobility retention under 100% strain in comparison to the neat film. This study provides a feasible approach for microstructure control in printed stretchable conjugated polymer film.

关键词

Keywords

references

Li, N.; Li, Y.; Cheng, Z.; Liu, Y.; Dai, Y.; Kang, S.; Li, S.; Shan, N.; Wai, S.; Ziaja, A.; Wang, Y.; Strzalka, J.; Liu, W.; Zhang, C.; Gu, X.; Hubbell, J. A.; Tian, B.; Wang, S. Bioadhesive polymer semiconductors and transistors for intimate biointerfaces. Science 2023 , 381 , 686−693..

Jiang, Y.; Ji, S.; Sun, J.; Huang, J.; Li, Y.; Zou, G.; Salim, T.; Wang, C.; Li, W.; Jin, H.; Xu, J.; Wang, S.; Lei, T.; Yan, X.; Peh, W. Y. X.; Yen, S. C.; Liu, Z.; Yu, M.; Zhao, H.; Lu, Z.; Li, G.; Gao, H.; Liu, Z.; Bao, Z.; Chen, X. A universal interface for plug-and-play assembly of stretchable devices. Nature 2023 , 614 , 456−462..

Wang, Z.; Zhang, D.; Yang, L.; Allam, O.; Gao, Y.; Su, Y.; Xu, M.; Mo, S.; Wu, Q.; Wang, Z.; Liu, J.; He, J.; Li, R.; Jia, X.; Li, Z.; Yang, L.; Weber, M. D.; Yu, Y.; Zhang, X.; Marks, T. J.; Stingelin, N.; Kacher, J.; Jang, S. S.; Facchetti, A.; Shao, M. Mechanically robust and stretchable organic solar cells plasticized by smal l-molecule acceptors. Science 2025 , 387 , 381−387..

[Liu, K.; Wang, J.; Pan, X.; Tian, S Y.; Liu, Y.; Zhang, Z.; Di, Y.; Chen, J.; Wu, C.; Deng, X. Y.; Wang, D.; Li, P.; Pan, C. K.; Qi, F.; Liu, J.; Hua, J.; Pei, J.; Di, C. A.; Guo, Y.; Liu, Y.; Lei, T. n-Type thermoelectric elastomers. Nature 2025 , 644 , 920−926..

Roth, B.; Savagatrup, S.; de los Santos, N. V.; Hagemann, O.; Carle, J. E.; Helgesen, M.; Livi, F.; Bundgaard, E.; Sondergaard, R. R.; Krebs, F. C.; Lipomi, D. J. Mechanical properties of a library of low-band-gap polymers. Chem. Mater. 2016 , 28 , 2363−2373..

Pei, D.; Wang, Z.; Peng, Z.; Zhang, J.; Deng, Y.; Han, Y.; Ye, L.; Geng, Y. Impact of molecular weight on the mechanical and electrical properties of a high-mobility diketopyrrolopyrrole-based conjugated polymer. Macromolecules 2020 , 50 , 4490−4500..

Zhao, K.; Zhang, T.; Zhang, L.; Li, J.; Li, H.; Wu, F.; Chen, Y.; Zhang, Q.; Han, Y. Role of molecular weight in microstructural transition and its correlation to the mechanical and electrical properties of P(NDI2OD-T2) thin films. Macromolecules 2021 , 54 , 10203−10215..

Li, J.; Zhang, C.; Zhang, Q.; Wang, S.; Zhang, R.; Ding, Z.; Han, Y. Revealing the role of polydispersity in multilevel assembly structures and its correlation with the mechanical and electrical properties of IDTBT thin films. Macromolecules 2025 , 58 , 3208−3220..

Mun, J.; Ochiai, Y.; Wang, W.; Zheng, Y.; Zheng, Y. Q.; Wu, H. C.; Matsuhisa, N.; Higashihara, T.; Tok, J. B.; Yun, Y.; Bao, Z. A design strategy for high mobility stretchable polymer semiconductors. Nat. Commun. 2021 , 12 , 3572..

Wang, S.; Wang, L.; Ren, S.; Li, W.; Wang, Z.; Yi, Z.; Liu, Y. Intrinsically stretchable polymer semiconductor with regional conjugation for stretchable electronics. Adv. Electro. Mater. 2024 , 10 , 2300816..

Ding, Y.; Zhu, Y.; Wang, X.; Wang, Y.; Zhang, S.; Zhang, G.; Gu, X.; Qiu, L. Side chain engineering: achieving stretch-induced molecular orientation and enhanced mobility in polymer semiconductors. Chem. Mater. 2022 , 34 , 2696−2707..

Galuska, L. A.; Ocheje, M. U.; Ahmad, Z. C.; Rondeau-Gagné, S.; Gu, X. Elucidating the role of hydrogen bonds for i mproved mechanical properties in a high-performance semiconducting polymer. Chem. Mater. 2022 , 34 , 2259−2267..

Xu, J.; Wang, S. H.; Wang, G. J. N.; Zhu, C. X.; Luo, S. C.; Jin, L. H.; Gu, X. D.; Chen, S. C.; Feig, V. R.; To, J. W. F.; Rondeau-Gagne, S.; Park, J.; Schroeder, B. C.; Lu, C.; Oh, J. Y.; Wang, Y. M.; Kim, Y. H.; Yan, H.; Sinclair, R.; Zhou, D. S.; Xue, G.; Murmann, B.; Linder, C.; Cai, W.; Tok, J. B. H.; Chung, J. W.; Bao, Z. N. Highlystretchable polymer semiconductor films through the nanoconfinement effect. Science 2017 , 355 , 59−64..

Wang, H.; Xiao, C.; Geng, H.; Liu, Y.; Xu, J.; Lu, Z.; Fan, H.; Zhen, Y.; Li, W. Noncovalent cross-linking of diketopyrrolopyrrole polymer via polyvinyl chloride for intrinsically stretchable organic field-effect transistors. Macromolecules 2025 , 58 , 9809−9818..

Yu, X.; Chen, L.; Li, C.; Gao, C.; Xue, X.; Zhang, X.; Zhang, G.; Zhang, D. Intrinsically stretchable polymer semiconductors with good ductility and high charge mobility through reducing the central symmetry of the conjugated backbone units. Adv. Mater. 2023 , 35 , 2209896..

Root, S. E.; Savagatrup, S.; Printz, A. D.; Rodriquez, D.; Lipomi, D. J. Mechanical properties of organic semiconductors for stretchable, highly flexible, and mechanically robust electronics. Chem. Rev. 2017 , 117 , 6467−6499..

Noriega, R. Efficient charge transport in disordered conjugated polymer microstructures. Macromol. Rapid Commun. 2018 , 39 , 1800096..

Cao, X.; Han, Y. Control over the aggregated structure of donor–acceptor conjugated polymer films for high-mobility organic field-effect transistors. Aggregate 2024 , 5 , e501..

Liu, D.; Li, J. H.; Wang, S. C.; Zhang, L.; Liu, X. Y.; Zhang, Q.; Han, Y.-C. Control aggregation of P3HT in solution for high efficiency doping: ensuring structural order and the distribution of dopants. Chinese J. Polym. Sci. 2023 , 41 , 811−823..

Ding, Z.; Liu, D.; Zhao, K.; Han, Y. Optimizing morphology to trade off charge transport and mechanical properties of stretchable conjugated polymer films. Macromolecules 2021 , 54 , 3907−3926..

Zhang, L.; Li, H.; Zhao, K.; Zhang, T.; Liu, D.; Wang, S.; Wu, F.; Zhang, Q.; Han, Y. Achieving the high charge mobility of conjugated polymers under cyclic stretching by changing the interaction parameter between solvent and sidechain. Polymer 2023 , 275 , 125912..

Zuo, J.; Jin, T.; Li, H.; Li, J.; Liu, X.; Yu, X.; Han, Y.; Han, Y. Continuous conjugated polymer network in elastomer matrix arising from solution-state aggregation and film-forming dynamics favoring mechanical and electrical properties. Adv. Funct. Mater. 2025 , 35 , 2424785..

Liu, D.; Ding, Z.; Wu, Y.; Liu, S. F.; Han, Y.; Zhao, K. In situ study of molecular aggregation in conjugated polymer/elastomer blends toward stretchable electronics. Macromolecules 2022 , 55 , 297−308..

Qu, G.; Kwok, J. J.; Diao, Y. Flow-directed crystallization for printed electronics. Acc. Chem. Res. 2016 , 49 , 2756−2764..

Shin, J.; Hong, T. R.; Lee, T. W.; Kim, A.; Kim, Y. H.; Cho, M. J.; Choi, D. H. Template-guided solution-shearing method for enhanced charge carrier mobility in diketopyrrolopyrrole-based polymer field-effect transistors. Adv. Mater. 2014 , 26 , 6031−6035..

Zhu, S.-Y.; Peng, J. Meniscus-assisted solution printing enables cocrystallization in poly(3-alkylthiophene)-based blends for field-effect transistors. Chinese J. Polym. Sci. 2023 , 41 , 1269−1276..

Selivanova, M.; Zhang, S.; Billet, B.; Malik, A.; Prine, N.; Landry, E.; Gu, X.; Xiang, P.; Rondeau-Gagné, S. Branched polyethylene as a plasticizing additive to modulate the mechanical properties of π-conjugated polymers. Macromolecules 2019 , 52 , 7870−7877..

Xu, J.; Wu, H. C.; Mun, J.; Ning, R.; Wang, W.; Wang, G. N.; Nikzad, S.; Yan, H.; Gu, X.; Luo, S.; Zhou, D.; Tok, J. B.; Bao, Z. Tuning conjugated polymer chain packing for stretchable semiconductors. Adv. Mater. 2022 , 34 , 2104747..

Zhuo, Z.; Ni, M.; Yu, N.; Zheng, Y.; Lin, Y.; Yang, J.; Sun, L.; Wang, L.; Bai, L.; Chen, W.; Xu, M.; Huo, F.; Lin, J.; Feng, Q.; Huang, W. Intrinsically stretchable fully π-conjugated polymer film via fluid conjugated molecular external-plasticizing for flexible light-emitting diodes. Nat. Commun. 2024 , 15 , 7990..

Wang, X.; Huang, H.; Gu, K.; Wang, Y.; Zhu, C.; Gu, X.; Qiu, L. Modulating aggregation structure and properties of conjugated polymers via ester a dditives. Macromolecules 2024 , 57 , 7586−7596..

Chung, S.; Kim, S. H.; Kim, S.; Ok, E.; Kim, B. J.; Kim, J.; Shin, J.; Chung, T.; Jang, J. D.; Lee, S.; Kang, B.; Cho, K. Enhancing mechanical deformability of rigid conjugated polymers through functional additive-induced persistence length modulation. Adv. Funct. Mater. 2025 , 35 , 2511256..

Huang, W.; Liu, X.; Ding, Z.; Wang, Z.; Xu, C.; Li, R.; Wang, S.; Wu, Y.; Qin, R.; Han, Y.; Geng, Y.; Liu, S. F.; Han, Y.; Zhao, K. Aligned conjugated polymer nanofiber networks in an elastomer matrix for high-performance printed stretchable electronics. Nano Lett. 2024 , 24 , 441−449..

Gao, Z.; Huang, W.; Ding, Z.; Yang, Y.; Xu, C.; Chen, Y.; Qin, R.; Hua, J.; Weng, Q.; Han, Y.; Geng, Y.; Han, Y.; Zhao, K. Chain alignment and film crystallinity manipulation towards high-performance large-area printed stretchable electronics. Sci. China Mater. 2025 , 68 , 3995−4005..

Liu, Y.; Chen, R.; Jiang, Y.; Zhang, X.; Shen, Y.; Huang, S.; Li, H.; Peng, Z.; Zhang, Q.; Ding, Z.; Duan, X.; Han, Y. Spatial distribution regulated chemical doping towards high-performance stretchable conjugated polymer films. Macromolecules 2025 , 58 , 7802−7814..

Wood, S.; Wade, J.; Shahid, M.; Collado-Fregoso, E.; Bradley, D. D. C.; Durrant, J. R.; Heeney, M.; Kim, J. S. Natures of optical absorption transitions and excitation energy dependent photostability of diketopyrrolopyrrole (DPP)-based photovoltaic copolymers. Energy Environ. Sci. 2015 , 8 , 3222−3232..

Wang, Z.; Shi, Y.; Deng, Y.; Han, Y.; Geng, Y. Toward high mobility green solvent-processable conjugated polymers: a systematic study on chalcogen effect in poly(diketopyrrolopyrrole-alt-terchalcogenophene)s. Adv. Funct. Mater. 2021 , 31 , 2104881..

Yi, S.; Zheng, H.; Peng, J. Synergistic backbone and side chain engineering on crystalline orientation and charge transport of conjugated polymers in field-effect transistors. Polymer 2025 , 327 , 128391..

Xu, Y.; Liu, J.; Wang, H.; Yu, X.; Xing, R.; Han, Y. Formation of parallel aligned nano-fibrils of a donor–acceptor conjugated copolymer via controlling J-aggregates and post treatment. Soft Matter 2013 , 9 , 9849−9856..

Su, Y.; Zhang, L.; Ding, Z.; Z hang, Y.; Wu, Y.; Duan, Y.; Zhang, Q.; Zhang, J.; Han, Y.; Xu, Z.; Zhang, R.; Zhao, K.; Liu, S. Carrier generation engineering toward 18% efficiency organic solar cells by controlling film microstructure. Adv. Energy Mater. 2022 , 12 , 2103940..

Schrickx, H. M.; Sen, P.; Balar, N.; O’Connor, B. T. Strain alignment of conjugated polymers: Method, microstructure, and applications. Cell Rep. Phys. Sci. 2024 , 5 , 102076..

Heintges, G. H. L.; Leenaers, P. J.; Janssen, R. A. J. The effect of side-chain substitution and hot processing on diketopyrrolopyrrole-based polymers for organic solar cells. J. Mater. Chem. A 2017 , 5 , 13748−13756..

Cao, Z.; Li, Z.; Mooney, M.; Do, C.; Hong, K.; Rondeau-Gagné, S.; Xia, W.; Gu, X. Uncovering backbone conformation for rigid DPP-based donor–acceptor conjugated polymer using deuterium labeling and neutron scattering. Macromolecules 2024 , 57 , 10379−10388..

Kim, N.-K.; Shin, E.-S.; Noh, Y. Y.; Kim, D. Y. A selection rule of solvent for highly aligned diketopyrrolopyrrole-based conjugated polymer film for high performance organic field-effect transistors. Org. Electron. 2018 , 55 , 6−14..

Kim, N. K.; Jang, S. Y.; Pace, G.; Caironi, M.; Park, W. T.; Khim, D.; Kim, J.; Kim, D. Y.; Noh, Y. Y. High-performance organic field-effect transistors with directionally aligned conjugated polymer film deposited from pre-aggregated solution. Chem. Mater. 2015 , 27 , 8345−8353..

Un, H. I.; Cheng, P.; Lei, T.; Yang, C. Y.; Wang, J. Y.; Pei, J. Charge-trapping-induced non-ideal behaviors in organic field-effect transistors. Adv. Mater. 2018 , 30 , 1800017..

Zheng, Y.; Wang, G. J. N.; Kang, J.; Nikolka, M.; Wu, H. C.; Tran, H.; Zhang, S.; Yan, H. P.; Chen, H.; Yuen, P. Y.; Mun, J.; Dauskardt, R. H.; McCulloch, I.; Tok, J. B. H.; Gu, X. D.; Bao, Z. N. An intrinsically stretchable high-performance polymer semiconductor with low crystallinity. Adv. Funct. Mater. 2019 , 29 , 1905340..

Gargi, D.; Kline, R. J.; DeLongchamp, D. M.; Fischer, D. A.; Toney, M. F.; O'Connor, B. T. Charge transport in highly face-on poly(3-hexylthiophene) films. J. Phys. Chem. C 2013 , 117 , 17421−17428..

Ogle, J.; Powell, D.; Amerling, E.; Smilgies, D.-M.; Whittaker- Brooks, L. Quantifying multiple crystallite orientations and crystal heterogeneities in complex thin film materials. CrystEngComm 2019 , 21 , 5707−5720..

Li, H.; Yang, H.; Zhang, L.; Wang, S.; Chen, Y.; Zhang, Q.; Zhang, J.; Tian, H.; Han, Y. Optimizing the crystallization behavior and film morphology of donor–acceptor conjugated semiconducting polymers by side-chain–solvent interaction in nonpolar solvents. Macromolecules 2021 , 54 , 10557−10573..

Gao, W.; Ma, R.; Dela Peña, T. A.; Yan, C.; Li, H.; Li, M.; Wu, J.; Cheng, P.; Zhong, C.; Wei, Z.; Jen, A. K. Y.; Li, G. Efficient all-small-molecule organic solar cells processed with non-halogen solvent. Nat. Commun. 2024 , 15 , 1946..

Zhou, Q.; Wang, Z.; Yan, Y.; Yang, L.; Chi, K.; Wu, Y.; Li, W.; Yi, Z.; Liu, Y.; Zhao, Y. Strain-enhanced electrical performance in stretchable semiconducting polymers. npj Flex. Electron. 2023 , 7 , 35..

Wang, Z.; Wu, Y.; Zhou, Q.; Yang, L.; Yi, Z.; Yan, Y.; Liu, Y.; Zhao, Y. Aggregation structure and glass transition of intrinsically stretchable semiconducting polymers. Matter 2023 , 6 , 3434−3448..

Ding, Z.; Zhao, K.; Han, Y. Strain-induced morphology evolution and charge transport in conjugated polymer films. Interdiscip. Mater. 2025 , 4 , 138−161..

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