双缆共轭聚合物中的间隔基异构化工程用于优化分子堆积和增强光伏性能

引用本文: 张文浩, 方海盛, 刘丽娟, 汤怀皓, 肖承义, 李韦伟. 双缆共轭聚合物中的间隔基异构化工程用于优化分子堆积和增强光伏性能[J]. 物理化学学报, 2026, 42(10): 100229. doi: 10.1016/j.actphy.2025.100229 shu

Citation: Wenhao Zhang, Haisheng Fang, Lijuan Liu, Huaihao Tang, Chengyi Xiao, Weiwei Li. Spacer isomerization engineering in double-cable conjugated polymers for optimized molecular packing and enhanced photovoltaic performance[J]. Acta Physico-Chimica Sinica, 2026, 42(10): 100229. doi: 10.1016/j.actphy.2025.100229 shu

双缆共轭聚合物中的间隔基异构化工程用于优化分子堆积和增强光伏性能

北京化工大学, 北京软物质科学与工程高精尖创新中心, 有机无机复合材料国家重点实验室, 北京 100029

通讯作者: 方海盛,E-mail:2021410015@mail.buct.edu.cn; 李韦伟,E-mail:liweiwei@iccas.ac.cn

基金项目:
国家自然科学基金(52473165, 22475013)，中央高校基本科研业务费专项资金(buctrc201828, XK1802-2)，武汉光电国家研究中心开放基金(2023WNLOKF012)。

摘要: 双缆共轭聚合物由给体主链与受体侧链构成，二者通过较长的柔性间隔基连接，而连接位置对聚合物的物理化学性质具有显著影响。本研究通过间隔基异构化工程设计并合成了两种间隔基分别连接在茚酮苯环的对位和邻位上的化合物，分别称为ZP-1和ZP-2。研究发现，将取代位置从邻位(ZP-2)调整至对位(ZP-1)，可实现更优的分子堆积并提高薄膜结晶度。这种结构优化促进了激子解离与电荷传输过程，使得基于ZP-1的器件在短路电流密度和填充因子上均显著提升。最终，ZP-1器件实现了10.43%的功率转换效率(PCE)，性能优于ZP-2。此外，两种聚合物均展现出优异的热稳定性：经过外推时间8000 h连续热老化后，仍能保持初始PCE的80%以上。值得注意的是，当ZP-1作为第三组分掺入D18:BTP-eC9二元共混体系时，可有效优化给体-受体界面，使器件实现了19.81%的高PCE。本研究为高效稳定的单组分有机太阳能电池及新型三元体系的合理设计提供了宝贵见解。

关键词:

English

Spacer isomerization engineering in double-cable conjugated polymers for optimized molecular packing and enhanced photovoltaic performance

Beijing Advanced Innovation Center for Soft Matter Science and Engineering, State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China

Corresponding author: Haisheng Fang, ; Weiwei Li,

Received Date: 19 October 2025
Accepted Date: 10 December 2025
Revised Date: 27 November 2025

Abstract: Double-cable conjugated polymers consist of a donor backbone and acceptor side chains linked by a long, flexible spacer. While this molecular design offers a promising solution to address the thermal instability and phase separation issues inherent in conventional binary blend systems, the development of high-performance double-cable polymers faces multiple significant challenges. The synthetic complexity is considerably high, requiring multi-step functionalization to attach the spacer to the acceptor unit, which often results in low yields and difficulties in purification. Moreover, the selection of suitable acceptor materials is severely limited, as only a narrow range of acceptors possess appropriate sites for spacer attachment while maintaining their intrinsic electronic properties. This limitation greatly restricts the exploration of material combinations and the potential for performance breakthroughs. Another critical yet underexplored challenge lies in the precise engineering of the spacer itself. Although studies have investigated the effect of spacer length, the role of spacer attachment position—a subtle but crucial structural parameter—remains poorly understood. This study designed and synthesized two such polymers, ZP-1 (with the spacer attached at the para-positions of the indenone benzene ring) and ZP-2 (at the ortho-positions), through spacer isomerization engineering. Investigations reveal that shifting the substitution from the ortho-(ZP-2) to the para-position (ZP-1) optimizes favorable molecular packing and enhances film crystallinity. This structural optimization facilitates exciton dissociation and charge transport, resulting in a significant improvement in the short-circuit current density and fill factor for ZP-1-based devices. Consequently, a power conversion efficiency (PCE) of 10.43% has been achieved, outperforming ZP-2 (9.44%). Furthermore, both polymers exhibit excellent thermal stability, retaining over 80% of their initial PCE after 8,000 h of continuous thermal aging. Notably, when incorporated as a third component into the D18:BTP-eC9 binary blend, ZP-1 effectively optimizes the donor-acceptor interface, leading to a simultaneous enhancement in short-circuit current density (J_SC) and fill factor (FF) and a high PCE of 19.81%. This improvement is attributed to its templating effect during film formation and the promotion of charge generation at the optimized interface. The ternary device also demonstrates significantly enhanced thermal stability compared to the binary counterpart. This work provides valuable insights for the rational design of efficient and stable single-component organic solar cells, as well as novel ternary systems, by highlighting spacer isomerization engineering—specifically, the precise control of linkage position—as a powerful strategy to tailor molecular packing, crystallinity, and ultimate device performance.

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沈阳化工大学材料科学与工程学院沈阳 110142

双缆共轭聚合物中的间隔基异构化工程用于优化分子堆积和增强光伏性能

通讯作者: 方海盛,E-mail:2021410015@mail.buct.edu.cn; 李韦伟,E-mail:liweiwei@iccas.ac.cn

English

Spacer isomerization engineering in double-cable conjugated polymers for optimized molecular packing and enhanced photovoltaic performance

Corresponding author: Haisheng Fang, ; Weiwei Li,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

双缆共轭聚合物中的间隔基异构化工程用于优化分子堆积和增强光伏性能

通讯作者: 方海盛,E-mail:2021410015@mail.buct.edu.cn; 李韦伟,E-mail:liweiwei@iccas.ac.cn

English

Spacer isomerization engineering in double-cable conjugated polymers for optimized molecular packing and enhanced photovoltaic performance

Corresponding author: Haisheng Fang, ; Weiwei Li,

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs