酯基噻唑对三元共聚物结晶成膜行为的调控及光伏性能研究

赵可新; 刘文静; 申帅帅; 刘亚辉; 宋金生

doi:10.11777/j.issn1000-3304.2025.25044

您当前的位置：

首页 >

文章列表页 >

酯基噻唑对三元共聚物结晶成膜行为的调控及光伏性能研究

研究论文 | 更新时间：2025-07-08

- 酯基噻唑对三元共聚物结晶成膜行为的调控及光伏性能研究
- Influence of Ester-functionalized Thiazole on Crystallization, Film Morphology, and Photovoltaic Performance of the Ternary Copolymers
- 高分子学报 2025年56卷第7期页码：1129-1139
- 作者机构：
  
  1.河南大学纳米科学与工程研究院开封 475100
  2.青岛大学纺织服装学院生物多糖纤维成形与生态纺织国家重点实验室青岛 266071
- 作者简介：
  
  E-mail: songjs@henu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣22475062);22075069┫资助项目、河南省高效重点科研专项(23ZX002);河南省研究生质量提升工程(YJS2025AL100)
- DOI：10.11777/j.issn1000-3304.2025.25044
  中图分类号：
- CSTR：32057.14.GFZXB.2025.7382
- 收稿日期：2025-02-20，
  
  录用日期：2025-03-12，
  
  网络出版日期：2025-04-16，
  
  纸质出版日期：2025-07-20
- 稿件说明：
移动端阅览
赵可新, 刘文静, 申帅帅, 刘亚辉, 宋金生. 酯基噻唑对三元共聚物结晶成膜行为的调控及光伏性能研究. 高分子学报, 2025, 56(7), 1129-1139

Zhao, K. X.; Liu, W. J.; Shen, S. S.; Liu, Y. H.; Song, J. S. Influence of ester-functionalized thiazole on crystallization, film morphology, and photovoltaic performance of the ternary copolymers. Acta Polymerica Sinica, 2025, 56(7), 1129-1139
赵可新, 刘文静, 申帅帅, 刘亚辉, 宋金生. 酯基噻唑对三元共聚物结晶成膜行为的调控及光伏性能研究. 高分子学报, 2025, 56(7), 1129-1139 DOI： 10.11777/j.issn1000-3304.2025.25044. CSTR： 32057.14.GFZXB.2025.7382.

Zhao, K. X.; Liu, W. J.; Shen, S. S.; Liu, Y. H.; Song, J. S. Influence of ester-functionalized thiazole on crystallization, film morphology, and photovoltaic performance of the ternary copolymers. Acta Polymerica Sinica, 2025, 56(7), 1129-1139 DOI： 10.11777/j.issn1000-3304.2025.25044. CSTR： 32057.14.GFZXB.2025.7382.

摘要

有机太阳能电池(OSCs)的长足进步，得益于非富勒烯受体的快速发展，这也对聚合物给体提出了更高要求. 无规三元共聚策略作为一种简单有效的方法，能够实现对聚合物能级、吸收、结晶性以及聚集行为的微调. 设计并合成了一系列含不同比例噻唑-4-羧酸乙酯(E-Tz)的聚合物给体LTz-0、LTz-5、LTz-10和LTz-15. 随着E-Tz含量的增加，给体聚合物表现出更显著的温度依赖聚集特性、结晶性减弱、HOMO能级逐渐降低，从而实现了共混膜形貌的调控和高开路电压(

). 最终，基于LTz-10:Y6的共混膜展现出更均匀的纤维网络结构和优异的电荷传输特性，实现了18.02%能量转换效率(PCE)，较参照系LTz-0提高了13%，为目前基于芳香内酯三元共聚物体系中的领先效率之一. 研究表明，E-Tz的引入能够实现给体聚合物聚集行为的有效调控，并显著提升光伏性能.

Abstract

The remarkable progress of organic solar cells (OSCs) has been driven by the rapid advancement of non-fullerene acceptors

which has in turn raised high demands for polymer donors. As a simple and effective approach

the random ternary copolymerization strategy optimizes existing polymers to enhance their energy levels

absorption

crystallinity

and aggregation behavior. A series of polymer donors LTz-0

LTz-5

LTz-10

and LTz-15 containing different ratios of ester-functionalized thiazole (E-Tz) were designed and synthesized. As the E-Tz content increases

the polymer donor exhibits ideal temperature-dependent aggregation characteristics

crystallinity decreases

and its HOMO energy level gradually deepens

effectively regulating the phase separation of the blend film and increasing the open circuit voltage (

). Finally

the device based on LTz-10:Y6 exhibits compact interpenetrated networks and excellent charge transport properties. Its power conversion efficiency (PCE) reaches 18.02%

which is 13% higher than that of LTz-0

marking it one of the highest efficiencies among the reported lactone based copolymers. The results shows that the addition of E-Tz can optimize the film morphology and significantly improve the final photovoltaic performance.

关键词

Keywords

references

Inganäs O. Organic photovoltaics over three decades . Adv. Mater. , 2018 , 30 ( 35 ), 1800388 . doi: 10.1002/adma.201800388 http://dx.doi.org/10.1002/adma.201800388

王思怡 , 钟文楷 , 黄飞 . 可拉伸高分子光电器件的研究进展 . 高分子学报 , 2024 , 55 ( 9 ), 1091 - 1110 . doi: 10.11777/j.issn1000-3304.2024.24131 http://dx.doi.org/10.11777/j.issn1000-3304.2024.24131

Li Y. K. ; He C. L. ; Zuo L. J. ; Zhao F. ; Zhan L. L. ; Li X. ; Xia R. X. ; Yip H. L. ; Li C. Z. ; Liu X. ; Chen H. Z. High-performance semi-transparent organic photovoltaic devices via improving absorbing selectivity . Adv. Energy Mater. , 2021 , 11 ( 11 ), 2003408 . doi: 10.1002/aenm.202003408 http://dx.doi.org/10.1002/aenm.202003408

Li Y. W. ; Xu G. Y. ; Cui C. H. ; Li Y. F. Flexible and semitransparent organic solar cells . Adv. Energy Mater. , 2018 , 8 ( 7 ), 1701791 . doi: 10.1002/aenm.201701791 http://dx.doi.org/10.1002/aenm.201701791

Li C. ; Song J. L. ; Lai H. J. ; Zhang H. T. ; Zhou R. K. ; Xu J. Q. ; Huang H. D. ; Liu L. M. ; Gao J. X. ; Li Y. X. ; Jee M. H. ; Zheng Z. L. ; Liu S. ; Yan J. ; Chen X. K. ; Tang Z. ; Zhang C. ; Woo H. Y. ; He F. ; Gao F. ; Yan H. ; Sun Y. M. Non-fullerene acceptors with high crystallinity and photoluminescence quantum yield enable >20% efficiency organic solar cells . Nat. Mater. , 2025 , 24 ( 3 ), 433 - 443 . doi: 10.1038/s41563-024-02087-5 http://dx.doi.org/10.1038/s41563-024-02087-5

Single-junction organic solar cells with a power conversion efficiency of more than 20%. Nat. Energy, 2024 , 9 ( 8 ), 930 - 931 . doi: 10.1038/s41560-024-01558-y http://dx.doi.org/10.1038/s41560-024-01558-y

Jiang P. C. ; Liu Y. H. ; Song J. S. ; Bo Z. S. Emergence of low-cost and high-performance nonfused ring electron acceptors . Acc. Chem. Res. , 2024 , 57 ( 23 ), 3419 - 3432 . doi: 10.1021/acs.accounts.4c00592 http://dx.doi.org/10.1021/acs.accounts.4c00592

Shen S. S. ; Mi Y. ; Ouyang Y. N. ; Lin Y. ; Deng J. J. ; Zhang W. J. ; Zhang J. Q. ; Ma Z. F. ; Zhang C. F. ; Song J. S. ; Bo Z. S. Macrocyclic encapsulation in a non-fused tetrathiophene acceptor for efficient organic solar cells with high short-circuit current density . Angew. Chem. Int. Ed. , 2023 , 62 ( 52 ), e 202316495 . doi: 10.1002/anie.202316495 http://dx.doi.org/10.1002/anie.202316495

Song J. S. ; Bo Z. S. Asymmetric molecular engineering in recent nonfullerene acceptors for efficient organic solar cells . Chin. Chem. Lett. , 2023 , 34 ( 10 ), 108163 . doi: 10.1016/j.cclet.2023.108163 http://dx.doi.org/10.1016/j.cclet.2023.108163

Lu H. ; Liu W. L. ; Ran G. L. ; Liang Z. Z. ; Li H. X. ; Wei N. ; Wu H. B. ; Ma Z. F. ; Liu Y. H. ; Zhang W. K. ; Xu X. J. ; Bo Z. S. High-pressure fabrication of binary organic solar cells with high molecular weight D18 yields record 19.65% efficiency . Angew. Chem. Int. Ed. , 2023 , 62 ( 50 ), e 202314420 . doi: 10.1002/anie.202314420 http://dx.doi.org/10.1002/anie.202314420

Wei N. ; Chen J. N. ; Cheng Y. T. ; Bian Z. Q. ; Liu W. L. ; Song H. M. ; Guo Y. W. ; Zhang W. K. ; Liu Y. H. ; Lu H. ; Zhou J. J. ; Bo Z. S. Constructing multiscale fibrous morphology to achieve 20% efficiency organic solar cells by mixing high and low molecular weight D18 . Adv. Mater. , 2024 , 36 ( 41 ), 2408934 . doi: 10.1002/adma.202408934 http://dx.doi.org/10.1002/adma.202408934

Lee B. ; Kim S. ; Nho H. W. ; Oh J. ; Park G. ; Jeong M. ; Cho Y. ; Lee S. M. ; Kwon O. H. ; Yang C. Viable mixing protocol based on formulated equations for achieving desired molecular weight and maximal charge separation of photovoltaic polymer . Adv. Energy Mater. , 2021 , 11 ( 46 ), 2102594 . doi: 10.1002/aenm.202102594 http://dx.doi.org/10.1002/aenm.202102594

Cheng F. L. ; Cui Y. J. ; Ding F. ; Chen Z. ; Xie Q. ; Xia X. X. ; Zhu P. P. ; Lu X. H. ; Zhu H. M. ; Liao X. F. ; Chen Y. W. Terpolymerization and regioisomerization strategy to construct efficient terpolymer donors enabling high-performance organic solar cells . Adv. Mater. , 2023 , 35 ( 30 ), 2300820 . doi: 10.1002/adma.202300820 http://dx.doi.org/10.1002/adma.202300820

Pang B. ; Liao C. T. ; Xu X. P. ; Yu L. Y. ; Li R. P. ; Peng Q. Benzo [d ] thiazole based wide bandgap donor polymers enable 19.54% efficiency organic solar cells along with desirable batch-to-batch reproducibility and general applicability. Adv. Mater. , 2023 , 35 ( 21 ), 2300631 . doi: 10.1002/adma.202300631 http://dx.doi.org/10.1002/adma.202300631

殷亮 , 樊本虎 , 王一丹 , 彭文博 , 赵志国 , 邬俊波 . 含有呋喃衍生物的窄带隙共轭聚合物的合成及光伏性能研究 . 高分子学报 , 2014 , ( 12 ), 1687 - 1692 . doi: 10.11777/j.issn1000-3304.2014.14145 http://dx.doi.org/10.11777/j.issn1000-3304.2014.14145

李大伟 , 马雪晴 , 崔新悦 , 陈亚男 , 魏楠 , 言行 , 李翠红 , 刘玉强 , 刘亚辉 , 薄志山 . 含炔键的聚合物给体材料设计合成及在有机太阳能电池中的性能研究 . 高分子学报 . 2024 , 55 ( 1 ), 48 - 57 .

Song J. S. ; Bo Z. S. Planar copolymers for high-efficiency polymer solar cells . Sci. China Chem. , 2019 , 62 ( 1 ), 9 - 13 . doi: 10.1007/s11426-018-9363-8 http://dx.doi.org/10.1007/s11426-018-9363-8

蔡厚继 , 谭若兮 , 董方亮 , 张杰 , 胡正伟 , 赵海洋 , 刘春晨 , 王明 , 黄飞 , 曹镛 . 基于苯并二吲哚二酮的低聚物共轭长度调节及应用: 共轭聚合物构建及载流子传输性能调控 . 高分子学报 , 2025 , 56 ( 2 ), 286 - 298 .

Lee J. W. ; Lee H. G. ; Oh E. S. ; Lee S. W. ; Phan T. N. ; Li S. ; Kim T. S. ; Kim B. J. Rigid- and soft-block-copolymerized conjugated polymers enable high-performance intrinsically stretchable organic solar cells . Joule , 2024 , 8 ( 1 ), 204 - 223 . doi: 10.1016/j.joule.2023.11.005 http://dx.doi.org/10.1016/j.joule.2023.11.005

Yu J. E. ; Jeon S. J. ; Choi J. Y. ; Han Y. W. ; Ko E. J. ; Moon D. K. A 3-fluoro-4-hexylthiophene-based wide bandgap donor polymer for 10.9% efficiency eco-friendly nonfullerene organic solar cells . Small , 2019 , 15 ( 9 ), 1805321 . doi: 10.1002/smll.201902241 http://dx.doi.org/10.1002/smll.201902241

Huang X. X. ; Zhang L. F. ; Cheng Y. J. ; Oh J. ; Li C. Q. ; Huang B. ; Zhao L. ; Deng J. W. ; Zhang Y. H. ; Liu Z. J. ; Wu F. Y. ; Hu X. T. ; Yang C. ; Chen L. ; Chen Y. W. Novel narrow bandgap terpolymer donors enables record performance for semitransparent organic solar cells based on all-narrow bandgap semiconductors . Adv. Funct. Mater. , 2022 , 32 ( 5 ), 2108634 . doi: 10.1002/adfm.202108634 http://dx.doi.org/10.1002/adfm.202108634

Keshtov M. L. ; Konstantinov I. O. ; Godovsky D. Y. ; Ostapov I. E. ; Alekseev V. G. ; Agrawal A. ; Dahiya H. ; Sharma G. D. Wide-bandgap donor-acceptor copolymer based on BDTTz donor and TPD acceptor for polymer solar cells using fullerene and nonfullerene acceptors . Energy Technol. , 2022 , 10 ( 8 ), 2200215 . doi: 10.1002/ente.202200215 http://dx.doi.org/10.1002/ente.202200215

Shanahan J. ; Yan L. ; Olanrewaju Y. ; Kashani S. ; Ade H. ; So F. ; You W. Acid-triggered side chain cleavage leads to doped conjugated polymers of high conductivity . J. Am. Chem. Soc. , 2024 , 146 ( 47 ), 32243 - 32248 . doi: 10.1021/jacs.4c09843 http://dx.doi.org/10.1021/jacs.4c09843

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. ; Liang J. E. ; Feng K. ; Lu X. H. ; Guo X. G. ; Gao F. ; Yan H. 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 ( 11 ), 3328 - 3337 . doi: 10.1039/c9ee01890e http://dx.doi.org/10.1039/c9ee01890e

Rasool S. ; Vu D. V. ; Song C. E. ; Lee H. K. ; Lee S. K. ; Lee J. C. ; Moon S. J. ; Shin W. S. Room temperature processed highly efficient large-area polymer solar cells achieved with molecular engineering of copolymers . Adv. Energy Mater. , 2019 , 9 ( 21 ), 1900168 . doi: 10.1002/aenm.201900168 http://dx.doi.org/10.1002/aenm.201900168

Huang T. H. ; Zhang Y. ; Wang J. J. ; Cao Z. L. ; Geng S. ; Guan H. ; Wang D. J. ; Zhang Z. L. ; Liao Q. G. ; Zhang J. Dual-donor organic solar cells with 19.13% efficiency through optimized active layer crystallization behavior . Nano Energy , 2024 , 121 , 109226 . doi: 10.1016/j.nanoen.2023.109226 http://dx.doi.org/10.1016/j.nanoen.2023.109226

Lee S. W. ; Hussain M. W. ; Lee J. ; Whang D. R. ; Jeong W. H. ; Choi H. ; Chang D. W. Effect of chlorine substituents on the photovoltaic properties of monocyanated quinoxaline-based D-A-type polymers . ACS Appl. Mater. Interfaces , 2023 , 15 ( 4 ), 5547 - 5555 . doi: 10.1021/acsami.2c19702 http://dx.doi.org/10.1021/acsami.2c19702

Song J. S. ; Guo Y. J. ; Liu L. J. ; Wang H. Efficient synthesis of dibenzopyran building block and its application in organic photovoltaics . Dyes Pigm. , 2015 , 122 , 184 - 191 . doi: 10.1016/j.dyepig.2015.06.032 http://dx.doi.org/10.1016/j.dyepig.2015.06.032

Zhou Y. Y. ; Li M. ; Guo Y. J. ; Lu H. ; Song J. S. ; Bo Z. S. ; Wang H. Dibenzopyran-based wide band gap conjugated copolymers: structural design and application for polymer solar cells . ACS Appl. Mater. Interfaces , 2016 , 8 ( 45 ), 31348 - 31358 . doi: 10.1021/acsami.6b11348 http://dx.doi.org/10.1021/acsami.6b11348

Yang L. S. ; Li M. ; Song J. S. ; Zhou Y. Y. ; Bo Z. S. ; Wang H. Molecular consideration for small molecular acceptors based on ladder-type dipyran: Influences of O-fun ctionalization and π -bridges . Adv. Funct. Mater. , 2018 , 28 ( 8 ), 1705927 . doi: 10.1002/adfm.201705927 http://dx.doi.org/10.1002/adfm.201705927

Liu J. F. ; Liu L. ; Zuo C. T. ; Xiao Z. ; Zou Y. P. ; Jin Z. W. ; Ding L. M. 5 H-dithieno [3,2 -b : 2 ',3'-d ] pyran-5-one unit yields efficient wide-bandgap polymer donors. Sci. Bull., 2019, 64 ( 22 ), 1655 - 1657 . doi: 10.1016/j.scib.2019.09.001 http://dx.doi.org/10.1016/j.scib.2019.09.001

张有地 , 石来涛 , 陈义旺 . 无规共聚策略设计聚合物太阳能电池的展望与思考 . 高分子学报 , 2019 , 50 ( 1 ), 13 - 26 .

章中强 , 刘志玺 , 严康荣 , 李焕斌 , 刘文清 , 路新慧 , 李寒莹 , 陈红征 , 李昌治 . 基于吡咯并吡咯二酮的二元和三元共轭聚合物的光电性能研究 . 高分子学报 , 2018 , ( 2 ), 295 - 303 .

Cheng F. L. ; Lai S. T. ; Zhang Y. H. ; Xue L. ; Xia X. X. ; Zhu P. P. ; Lu X. H. ; Liao X. F. ; Chen Y. W. Random terpolymer based on simple siloxane-functionalized thiophene unit enabling high-performance non-fullerene organic solar cells . Chinese J. Polym. Sci. , 2024 , 42 ( 3 ), 311 - 321 . doi: 10.1007/s10118-023-3051-y http://dx.doi.org/10.1007/s10118-023-3051-y

Liao Z. H. ; Yang K. ; Hou L. C. ; Li J. ; Lv J. ; Singh R. ; Kumar M. ; Chen Q. Q. ; Dong X. Y. ; Xu T. L. ; Hu C. ; Duan T. N. ; Kan Z. P. ; Lu S. R. ; Xiao Z. Y. Thiazole-functionalized terpolymer donors obtained via random ternary copolymerization for high-performance polymer solar cells . Macromolecules , 2020 , 53 ( 20 ), 9034 - 9042 . doi: 10.1021/acs.macromol.0c01462 http://dx.doi.org/10.1021/acs.macromol.0c01462

Liao Z. H. ; Hu D. Q. ; Tang H. ; Huang P. H. ; Singh R. ; Chung S. ; Cho K. ; Kumar M. ; Hou L. C. ; Chen Q. Q. ; Yu W. Y. ; Chen H. Y. ; Yang K. ; Kan Z. P. ; Liu F. ; Xiao Z. Y. ; Li G. ; Lu S. R. 18.42% efficiency polymer solar cells enabled by terpolymer donors with optimal miscibility and energy levels . J. Mater. Chem. A , 2022 , 10 ( 14 ), 7878 - 7887 . doi: 10.1039/d1ta10644a http://dx.doi.org/10.1039/d1ta10644a

Wang B. N. ; Kong Y. B. ; Ye X. K. ; Ye S. N. ; Chen T. Y. ; Wang S. L. ; Li S. X. ; Shi M. M. ; Xu J. T. ; Chen H. Z. Thiophene copolymer donors containing ester-substituted thiazole for organic solar cells . ACS Appl. Mater. Interfaces , 2025 , 17 ( 5 ), 7707 - 7715 . doi: 10.1021/acsami.4c18536 http://dx.doi.org/10.1021/acsami.4c18536

Wang P. C. ; Jiang H. X. ; Bi F. Z. ; Wang J. X. ; Yang C. M. ; Li Y. H. ; Chu J. H. ; Bao X. C. Heterojunction interactions modulated film-forming kinetics for 19.65% efficiency binary organic solar cells . CCS Chem. , 2025 , 1 - 14 . doi: 10.31635/ccschem.024.202405021 http://dx.doi.org/10.31635/ccschem.024.202405021

Deng J. W. ; Liu J. B. ; Jin C. K. ; Huang S. R. ; Zhang S. J. ; Qin Z. ; Xie J. P. ; Liu L. ; Chen L. ; Chen Y. W. " Double-gene" small molecule as guest component promotes the efficiency of organic solar cells beyond 19.5 % . Angew. Chem. Int. Ed. , 2025 , 64 ( 8 ), e 202420385 . doi: 10.1002/anie.202420385 http://dx.doi.org/10.1002/anie.202420385

Yang F. ; Fang H. S. ; Guo E. Q. ; Xiao C. Y. ; Lu Z. H. ; Wang Y. W. ; Fan H. Y. ; Zhang A. D. ; Lai W. B. ; Li W. W. Oligomerized electron acceptors with alkynyl linkages to suppress electron-photon coupling for low-energy-loss organic solar cells . Angew. Chem. Int. Ed. , 2025 , e 202501302 . doi: 10.1002/anie.202501302 http://dx.doi.org/10.1002/anie.202501302

浏览量

114

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

基于多氟聚合物的高性能三元有机太阳能电池

分子掺杂半透明有机太阳能电池研究进展

引入柔性链的聚合物给体设计策略获得可非卤溶剂加工的高效柔性大面积有机太阳能电池