顺序双掺杂策略：协同提高共轭聚合物的电导率

刘铎; 彭忠祥; 韩艳春

doi:10.11777/j.issn1000-3304.2026.26126

您当前的位置：

首页 >

文章列表页 >

顺序双掺杂策略：协同提高共轭聚合物的电导率

研究论文 | 更新时间：2026-07-10

- 顺序双掺杂策略：协同提高共轭聚合物的电导率
- Sequential Dual-doping Strategy: Synergistically Boosting the Electrical Conductivity of Conjugated Polymers
- 高分子学报 2026年页码：1-15
- 作者机构：
  
  1.中国科学院长春应用化学研究所高分子科学与技术全国重点实验室长春 130022
  2.中国科学技术大学应用化学与工程学院合肥 230026
- 作者简介：
  
  E-mail: zxpeng@ciac.ac.cn
  E-mail: ychan@ciac.ac.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣52433009);52403254┫;中国科学院战略性先导科技专项(XDB 0520101)
- DOI：10.11777/j.issn1000-3304.2026.26126
  中图分类号：
- CSTR：32057.14.GFZXB.2026.7626
- 收稿：2026-04-18，
  
  录用：2026-05-13，
  
  网络首发：2026-07-10，
- 稿件说明：
移动端阅览
刘铎, 彭忠祥, 韩艳春. 顺序双掺杂策略：协同提高共轭聚合物的电导率. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26126.

Liu, D.; Peng, Z. X.; Han, Y. C. Sequential dual-doping strategy: synergistically boosting the electrical conductivity of conjugated polymers. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26126.
刘铎, 彭忠祥, 韩艳春. 顺序双掺杂策略：协同提高共轭聚合物的电导率. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26126. DOI： CSTR： 32057.14.GFZXB.2026.7626.

Liu, D.; Peng, Z. X.; Han, Y. C. Sequential dual-doping strategy: synergistically boosting the electrical conductivity of conjugated polymers. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26126. DOI： CSTR： 32057.14.GFZXB.2026.7626.

摘要

共轭聚合物因具有质轻、柔性和溶液可加工等优势，在热电转换、柔性电子等领域展现出广阔的应用前景，而掺杂是实现其高导电率的关键策略. 然而，单一分子掺杂往往难以兼顾载流子浓度与结构有序性. 本研究提出一种顺序双掺杂策略，以聚(3-己基噻吩-2

5-二基) (P3HT)为模型体系，预先在聚合物中引入(2

6-四氟-7

8-四氰基对苯二醌二甲烷) (F4TCNQ)，随后通过FeCl

进行氧化还原深度掺杂. 结果表明，通过F4TCNQ预掺杂，扩大了聚合物烷基侧链间距且保持聚合物结构的有序性，为后续FeCl

的扩散与电荷转移构筑了有利通道；通过第二次掺杂FeCl

，更强氧化性的FeCl

部分替代了F4TCNQ，同时顺序双掺杂薄膜在保持高结晶有序性的同时，实现了更紧凑的

堆叠距离和稳定的分子取向. 顺序双掺杂促进了极化子向双极化子的转变趋势，自旋浓度降低，同时载流子浓度和迁移率均高于单一掺杂体系. 最优条件下，顺序双掺杂P3HT薄膜的电导率达到595.9 S/cm，分别是单一FeCl

掺杂和单一F4TCNQ掺杂薄膜的10.6和9.4倍. 本研究提出的“先结构优化，后深度掺杂”策略为共轭聚合物高电导率的实现提供了有效途径.

Abstract

Conjugated polymers exhibit broad application prospects in fields such as thermoelectric conversion and flexible electronics due to their advantages of light weight

flexibility

and solution processability

with doping being a key strategy for achieving high electrical conductivity. However

single molecular doping often struggles to simultaneously balance carrier concentration and structural order. In this work

we proposed a sequential dual-doping strategy using poly(3-hexylthiophene-2

5-diyl) (P3HT) as a model system. F4TCNQ was first introduced into the polymer

followed by deep redox doping with FeCl

. The results showed that F4TCNQ pre-doping expanded the alkyl side-chain spacing while maintaining structural order

thereby constructing favorable channels for subsequent FeCl

diffusion and charge transfer. During the secondary doping step

the stronger oxidizing agent FeCl

partially replaced F4TCNQ

while the sequentially dual-doped film maintained high crystalline order along with a more compact

stacking distance and stable molecular orientation. Sequential dual-doping promotes the transition tendency from polarons to bipolarons

reduces spin concentration

and achieves higher carrier concentration and mobility compared to single-doping systems. Under optimal conditions

the sequentially dual-doped P3HT film achieved an electrical conductivity of 595.9 S/cm

which was 10.6-fold and 9.4-fold higher than those of films doped with FeCl

alone and F4TCNQ alone

respectively. The "structure optimization first

deep doping second" strategy proposed in this study provides an effective route toward high electrical conductivity in conjugated polymers.

关键词

Keywords

references

Kim D. ; Kim H. ; Seo J. M. ; Jeon I. ; Lee H. ; Kang B. Recent trends in conjugated polymer-based thermoelectrics from materials to device . EcoMat , 2025 , 7 ( 10 ), e 70029 . doi: 10.1002/eom2.70029 http://dx.doi.org/10.1002/eom2.70029

Peng Z. X. ; Chen R. ; Liu X. Y. ; Zhang Y. Z. ; Wang J. H. ; Miao J. H. ; Han Y. C. ; Liu J. Nanoconfinement effect enhances stretchability and mechanical stability of organic photodetectors . Adv. Funct. Mater. , 2025 , 35 ( 1 ), 2410390 . doi: 10.1002/adfm.202410390 http://dx.doi.org/10.1002/adfm.202410390

Li J. H. ; Ding Z. C. ; University S. N. ; Wang Z. H. ; Liu Y. T. ; Jin T. Y. ; Yi X. T. ; Chen R. ; Peng Z. X. ; Zhang R. ; University S. ; Han Y. C. The short-range ordered aggregation structures obtained by controlling the chain segment movement for stretchable IDTBT films . Macromolecules , 2026 , 59 ( 4 ), 2249 - 2260 . doi: 10.1021/acs.macromol.5c03533 http://dx.doi.org/10.1021/acs.macromol.5c03533

Rivnay J. ; Inal S. ; Salleo A. ; Owens R. M. ; Berggren M. ; Malliaras G. G. Organic electrochemical transistors . Nat. Rev. Mater. , 2018 , 3 ( 2 ), 17086 . doi: 10.1038/natrevmats.2017.86 http://dx.doi.org/10.1038/natrevmats.2017.86

Wu C. W. ; University P. ; Zhang Z. ; University P. ; Lei T. ; University P. Doped state engineering in conjugated polymers . Chem. Mater. , 2026 , 38 ( 1 ), 3 - 19 . doi: 10.1021/acs.chemmater.5c02592 http://dx.doi.org/10.1021/acs.chemmater.5c02592

Kim J. ; Ju D. ; Kim S. ; Cho K. Disorder-controlled efficient doping of conjugated polymers for high-performance organic thermoelectrics . Adv. Funct. Mater. , 2024 , 34 ( 6 ), 2309156 . doi: 10.1002/adfm.202309156 http://dx.doi.org/10.1002/adfm.202309156

Min J. ; Im J. ; Kim S. H. ; Choi H. H. ; Cho K. Morphology associated positive correlation between carrier mobility and carrier density in highly doped donor-acceptor conjugated polymers . Adv. Funct. Mater. , 2023 , 33 ( 19 ), 2212825 . doi: 10.1002/adfm.202212825 http://dx.doi.org/10.1002/adfm.202212825

Kim S. H. ; Yook H. ; Sung W. ; Choi J. ; Lim H. ; Chung S. ; Han J. W. ; Cho K. Extremely suppressed energetic disorder in a chemically doped conjugated polymer . Adv. Mater. , 2023 , 35 ( 1 ), 2207320 . doi: 10.1002/adma.202207320 http://dx.doi.org/10.1002/adma.202207320

Zhong Y. H. ; Untilova V. ; Muller D. ; Guchait S. ; Kiefer C. ; Herrmann L. ; Zimmermann N. ; Brosset M. ; Heiser T. ; Brinkmann M. Preferential location of dopants in the amorphous phase of oriented regioregular poly (3 -hexylthiophene-2 , 5 -diyl) films helps reach charge conductivities of 3000 S cm-1. Adv. Funct. Mater., 2022 , 32 ( 30 ), 2202075 .

Zuo G. Z. ; Abdalla H. ; Kemerink M. Impact of doping on the density of states and the mobility in organic semiconductors . Phys. Rev. B , 2016 , 93 ( 23 ), 235203 . doi: 10.1103/physrevb.93.235203 http://dx.doi.org/10.1103/physrevb.93.235203

Chai H. Y. ; Xu Z. ; Li H. ; Zhong F. ; Bai S. Q. ; Chen L. D. Sequential-twice-doping approach toward synergistic optimization of carrier concentration and mobility in thiophene-based polymers . ACS Appl. Electron. Mater. , 2022 , 4 ( 10 ), 4947 - 4954 . doi: 10.1021/acsaelm.2c00940 http://dx.doi.org/10.1021/acsaelm.2c00940

Murrey T. L. ; Berteau-Rainville M. ; Gonel G. ; Saska J. ; Shevchenko N. E. ; Fergerson A. S. ; Talbot R. M. ; Yacoub N. L. ; Zhang F. Y. ; Kahn A. ; Mascal M. ; Salzmann I. ; Moulé A. J. Quantifying polaron densities in sequentially doped conjugated polymers: exploring the upper limits of molecular doping and conductivity . J. Mater. Chem. C , 2023 , 11 ( 42 ), 14884 - 14895 . doi: 10.1039/d3tc01569f http://dx.doi.org/10.1039/d3tc01569f

Yamashita Y. ; Tsurumi J. ; Ohno M. ; Fujimoto R. ; Kumagai S. ; Kurosawa T. ; Okamoto T. ; Takeya J. ; Watanabe S. Efficient molecular doping of polymeric semiconductors driven by anion exchange . Nature , 2019 , 572 ( 7771 ), 634 - 638 . doi: 10.1038/s41586-019-1504-9 http://dx.doi.org/10.1038/s41586-019-1504-9

Yuan D. F. ; Plunkett E. ; Nguyen P. H. ; Rawlings D. ; Le M. L. ; Kroon R. ; Müller C. ; Segalman R. A. ; Chabinyc M. L. Double doping of semiconducting polymers using ion-exchange with a dianion . Adv. Funct. Mater. , 2023 , 33 ( 29 ), 2300934 . doi: 10.1002/adfm.202300934 http://dx.doi.org/10.1002/adfm.202300934

Chen C. ; Jacobs I. E. ; Kang K. ; Lin Y. ; Jellett C. ; Kang B. ; Lee S. B. ; Huang Y. X. ; BaloochQarai M. ; Ghosh R. ; Statz M. ; Wood W. ; Ren X. L. ; Tjhe D. ; Sun Y. H. ; She X. J. ; Hu Y. Y. ; Jiang L. ; Spano F. C. ; McCulloch I. ; Sirringhaus H. Observation of weak counterion size dependence of thermoelectric transport in ion exchange doped conducting polymers across a wide range of conductivities . Adv. Energy Mater. , 2023 , 13 ( 9 ), 2202797 . doi: 10.1002/aenm.202202797 http://dx.doi.org/10.1002/aenm.202202797

Hyun Suh E. ; Beom Kim S. ; Jung J. ; Jang J. Extremely electron-withdrawing lewis-paired CN groups for organic p-dopants . Angew. Chim. Int. Ed. , 2023 , 62 ( 37 ), e 202304245 . doi: 10.1002/anie.202304245 http://dx.doi.org/10.1002/anie.202304245

Mansour A. E. ; Warren R. ; Lungwitz D. ; Forster M. ; Scherf U. ; Opitz A. ; Malischewski M. ; Koch N. Coordination of Tetracyanoquinodimethane-derivatives with Tris(pentafluorophenyl)borane provides stronger p-Dopants with enhanced stability . ACS Appl. Mater. Interfaces , 2023 , 15 ( 39 ), 46148 - 46156 . doi: 10.1021/acsami.3c10373 http://dx.doi.org/10.1021/acsami.3c10373

Gilhooly-Finn P. A. ; Jacobs I. E. ; Bardagot O. ; Zaffar Y. ; Lemaire A. ; Guchait S. ; Zhang L. ; Freeley M. ; Neal W. ; Richard F. ; Palma M. ; Banerji N. ; Sirringhaus H. ; Brinkmann M. ; Nielsen C. B. Interplay between side chain density and polymer alignment: two competing strategies for enhancing the thermoelectric performance of P3HT analogues . Chem. Mater. , 2023 , 35 ( 21 ), 9029 - 9039 . doi: 10.1021/acs.chemmater.3c01680 http://dx.doi.org/10.1021/acs.chemmater.3c01680

Yoon S. E. ; Kang Y. ; Im J. ; Lee J. ; Lee S. Y. ; Park J. ; Gao Y. J. ; Jeon D. ; Son J. Y. ; Kim J. ; Kousseff C. J. ; Kim T. ; Seo H. ; Kang K. ; McCulloch I. ; Kwak S. K. ; Choi H. H. ; Kim B. G. ; Kim J. H. Enhancing dopant diffusion for ultrahigh electrical conductivity and efficient thermoelectric conversion in conjugated polymers . Joule , 2023 , 7 ( 10 ), 2291 - 2317 . doi: 10.1016/j.joule.2023.09.002 http://dx.doi.org/10.1016/j.joule.2023.09.002

Liu, D.;, Peng, Z. X.;, Han, Y. C. ;. Conductivity boost by the loading-soaking doping (LSD) procedure: a crystalline structure-preserving strategy. ACS Appl. Mater. Interfaces , 2025 , 17 ( 49 ), 66988 - 66997 . doi: 10.1021/acsami.5c21830 http://dx.doi.org/10.1021/acsami.5c21830

Peng Z. X. ; Zhang Y. W. ; Sun X. K. ; Zhao W. C. ; Bian F. G. ; Geng Y. H. ; Ye L. ; Yang C. M. Real-time probing and unraveling the morphology formation of blade-coated ternary nonfullerene organic photovoltaics with in situ X-ray scattering . Adv. Funct. Mater. , 2023 , 33 ( 14 ), 2213248 . doi: 10.1002/adfm.202213248 http://dx.doi.org/10.1002/adfm.202213248

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 . Chin. J. Polym. Sci. , 2023 , 41 ( 5 ), 811 - 823 . doi: 10.1007/s10118-023-2939-x http://dx.doi.org/10.1007/s10118-023-2939-x

Zhang R. ; Yang H. ; Zhou K. ; Zhang J. D. ; Yu X. H. ; Liu J. G. ; Han Y. C. Molecular orientation and phase separation by controlling chain segment and molecule movement in P3HT/N2200 blends . Macromolecules , 2016 , 49 ( 18 ), 6987 - 6996 . doi: 10.1021/acs.macromol.6b01526 http://dx.doi.org/10.1021/acs.macromol.6b01526

Wenzel F. A. ; Welz H. ; van der Zwan K. P. ; Stäter S. ; Kreger K. ; Hildner R. ; Senker J. ; Schmidt H. W. Highly efficient supramolecular nucleating agents for poly(3-hexylthiophene) . Macromolecules , 2022 , 55 ( 7 ), 2861 - 2871 . doi: 10.1021/acs.macromol.1c02283 http://dx.doi.org/10.1021/acs.macromol.1c02283

Futamata K. ; Onodera T. ; Yamamoto S. ; Mitsuishi M. ; Oikawa H. Semicrystalline structural correlations of conductivity in conjugated polymer thin films surface-doped by the vapor phase method . ACS Appl. Electron. Mater. , 2022 , 4 ( 2 ), 755 - 760 . doi: 10.1021/acsaelm.1c01150 http://dx.doi.org/10.1021/acsaelm.1c01150

Li J. H. ; Zhang C. J. ; Zhang Q. ; Wang S. C. ; Zhang R. ; Ding Z. C. ; Han Y. C. 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 ( 6 ), 3208 - 3220 . doi: 10.1021/acs.macromol.5c00316 http://dx.doi.org/10.1021/acs.macromol.5c00316

Ma J. ; Wang J. H. ; Peng Z. X. ; Hu J. L. ; Liu J. ; Liu Y. C. Highly transparent organic photodetectors with transfer-printed PEDOT: PSS top electrodes . Sci. China Mater. , 2025 , 68 ( 11 ), 4051 - 4058 . doi: 10.1007/s40843-025-3518-2 http://dx.doi.org/10.1007/s40843-025-3518-2

Zhao K. F. ; Zhang Q. ; Chen L. ; Zhang T. ; Han Y. C. Nucleation and growth of P(NDI2OD-T2) nanowires via side chain ordering and backbone planarization . Macromolecules , 2021 , 54 ( 5 ), 2143 - 2154 . doi: 10.1021/acs.macromol.0c02436 http://dx.doi.org/10.1021/acs.macromol.0c02436

Zhao K. ; Xue L. J. ; Liu J. G. ; Gao X. ; Wu S. P. ; Han Y. C. ; Geng Y. H. A new method to improve poly(3-hexyl thiophene) (P3HT) crystalline behavior: decreasing chains entanglement to promote order-disorder transformation in solution . Langmuir , 2010 , 26 ( 1 ), 471 - 477 . doi: 10.1021/la903381f http://dx.doi.org/10.1021/la903381f

Chen L. ; Wang H. Y. ; Liu J. G. ; Xing R. B. ; Yu X. H. ; Han Y. C. Tuning the π - π stacking distance and J-aggregation of DPP-based conjugated polymer via introducing insulating polymer . J. Polym. Sci. Part B Polym. Phys. , 2016 , 54 ( 8 ), 838 - 847 . doi: 10.1002/polb.23984 http://dx.doi.org/10.1002/polb.23984

Liu Y. T. ; Chen R. ; Jiang Y. ; Zhang X. ; Shen Y. ; Huang S. C. ; Li H. X. ; University S. ; Peng Z. X. ; Zhang Q. ; Ding Z. C. ; University S. N. ; Duan X. Z. ;, Han, Y. C. Spatial distribution regulated chemical doping toward high-performance stretchable conjugated polymer films. Macromolecules , 2025 , 58 ( 15 ), 7802 - 7814 . doi: 10.1021/acs.macromol.5c00724 http://dx.doi.org/10.1021/acs.macromol.5c00724

Mansour A. E. ; Valencia A. M. ; Lungwitz D. ; Wegner B. ; Tanaka N. ; Shoji Y. ; Fukushima T. ; Opitz A. ; Cocchi C. ; Koch N. Understanding the evolution of the Raman spectra of molecularly p-doped poly(3-hexylthiophene-2,5-diyl): signatures of polarons and bipolarons . Phys. Chem. Chem. Phys. , 2022 , 24 ( 5 ), 3109 - 3118 . doi: 10.1039/d1cp04985b http://dx.doi.org/10.1039/d1cp04985b

Nightingale J. ; Wade J. ; Moia D. ; Nelson J. ; Kim J. S. Impact of molecular order on polaron formation in conjugated polymers . J. Phys. Chem. C , 2018 , 122 ( 51 ), 29129 - 29140 . doi: 10.1021/acs.jpcc.8b09706 http://dx.doi.org/10.1021/acs.jpcc.8b09706

Stewart K. ; Pagano K. ; Tan E. ; Daboczi M. ; Rimmele M. ; Luke J. ; Eslava S. ; Kim J. S. Understanding effects of alkyl side-chain density on polaron formation via electrochemical doping in thiophene polymers . Adv. Mater. , 2024 , 36 ( 20 ), 2211184 . doi: 10.1002/adma.202211184 http://dx.doi.org/10.1002/adma.202211184

Furukawa Y. ; Shimokawa D. Polarons, bipolarons, and electrical properties of crystalline conducting polymers . Bull. Chem. Soc. Jpn. , 2023 , 96 ( 11 ), 1243 - 1251 . doi: 10.1246/bcsj.20230175 http://dx.doi.org/10.1246/bcsj.20230175

Li H. ; Xu Z. ; Song J. ; Chai H. Y. ; Wu L. L. ; Chen L. D. Single-solution doping enabling dominant integer charge transfer for synergistically improved carrier concentration and mobility in donor-acceptor polymers . Adv. Funct. Mater. , 2022 , 32 ( 14 ), 2110047 . doi: 10.1002/adfm.202110047 http://dx.doi.org/10.1002/adfm.202110047

Chen C. ; Ma H. B. ; Lu K. Q. ; Zhang X. X. ; Yue B. Q. ; Song C. ; Huang P. C. ; Cheng H. F. ; Lin Y. Boosting thermoelectric performance of semicrystalline conducting polymers by simply adding nucleating agent . Adv. Mater. , 2025 , 37 ( 9 ), 2417594 . doi: 10.1002/adma.202417594 http://dx.doi.org/10.1002/adma.202417594

Woo G. W. ; Lee C. M. ; Lee W. W. ; Jung M. J. ; Lee S. M. ; Lee H. W. ; Yoo H. ; Kim Y. H. ; Lee E. K. Detachable and reusable: reinforced π -ion film for modular synaptic reservoir computing . Adv. Mater. , 2025 , 37 ( 41 ), 2506729 . doi: 10.1002/adma.70826 http://dx.doi.org/10.1002/adma.70826

Jacobs I. E. ; Aasen E. W. ; Oliveira J. L. ; Fonseca T. N. ; Roehling J. D. ; Li J. ; Zhang G. ; Augustine M. P. ; Mascal M. ; Moulé A. J. Comparison of solution-mixed and sequentially processed P 3HT: F 4 TCNQ films: Effect of doping-induced aggregation on film morphology. J. Mater. Chem. C , 2016 , 4 ( 16 ), 3454 - 3466 . doi: 10.1039/c5tc04207k http://dx.doi.org/10.1039/c5tc04207k

Yoon S. E. ; Kang Y. ; Jeon G. G. ; Jeon D. ; Lee S. Y. ; Ko S. J. ; Kim T. ; Seo H. ; Kim B. G. ; Kim J. H. Exploring wholly doped conjugated polymer films based on hybrid doping: strategic approach for optimizing electrical conductivity and related thermoelectric properties . Adv. Funct. Mater. , 2020 , 30 ( 42 ), 2004598 . doi: 10.1002/adfm.202070276 http://dx.doi.org/10.1002/adfm.202070276

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

高透光率咔唑类聚合物空穴传输材料用于反式钙钛矿太阳能电池

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

可拉伸高分子光电器件的研究进展

氢键侧链修饰共轭聚合物骨架的自愈合发光弹性体的设计合成与性能研究

多尺度增强体改性对聚醚醚酮复合材料摩擦磨损性能的影响