Sequential Dual-doping Strategy: Synergistically Boosting the Electrical Conductivity of Conjugated Polymers

Duo Liu; Zhong-xiang Peng; Yan-chun Han

doi:10.11777/j.issn1000-3304.2026.26126

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Sequential Dual-doping Strategy: Synergistically Boosting the Electrical Conductivity of Conjugated Polymers

更新时间：2026-07-10

- Sequential Dual-doping Strategy: Synergistically Boosting the Electrical Conductivity of Conjugated Polymers
- Acta Polymerica Sinica Pages: 1-15(2026)
- 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：
  
  Zhong-xiang Peng, E-mail: zxpeng@ciac.ac.cn
  Yan-chun Han, E-mail: ychan@ciac.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26126
  CLC：
- CSTR：32057.14.GFZXB.2026.7626
- Received：18 April 2026，
  
  Accepted：13 May 2026，
  
  Online First：10 July 2026，
- 稿件说明：
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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

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