Design, Synthesis, and Photovoltaic Performance of Polymer Donor Materials Incorporating 4-Cyanothiazole Units

Zhi-yi Chen; Lu Xing; Ming-wei Deng; Hao-yong Shi; Xiao-hei Wu; Yi-ming Shao; Rui Sun; Jie Min

doi:10.11777/j.issn1000-3304.2025.25002

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Design, Synthesis, and Photovoltaic Performance of Polymer Donor Materials Incorporating 4-Cyanothiazole Units

Research Article | 更新时间：2025-07-08

- Design, Synthesis, and Photovoltaic Performance of Polymer Donor Materials Incorporating 4-Cyanothiazole Units
- Acta Polymerica Sinica Vol. 56, Issue 7, Pages: 1099-1107(2025)
- 作者机构：
  
  武汉大学高等研究院武汉 430072
- 作者简介：
  
  Yi-ming Shao, E-mail: 2021106490043@whu.edu.cn
  Rui Sun, E-mail: sun.rui@whu.edu.cn
  Jie Min, E-mail: min.jie@whu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25002
  CLC：
- CSTR：32057.14.GFZXB.2025.7360
- Received：02 January 2025，
  
  Accepted：12 February 2025，
  
  Published Online：07 April 2025，
  
  Published：20 July 2025
- 稿件说明：
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陈至一, 邢陆, 邓明玮, 石浩永, 吴小黑, 邵一鸣, 孙瑞, 闵杰. 基于4-氰基噻唑单元的聚合物给体材料设计合成及其光伏性能研究. 高分子学报, 2025, 56(7), 1099-1107

Chen, Z. Y.; Xing, L.; Deng, M. W.; Shi, H. Y.; Wu, X. H.; Shao, Y. M.; Sun, R.; Min, J. Design, synthesis, and photovoltaic performance of polymer donor materials incorporating 4-cyanothiazole units. Acta Polymerica Sinica, 2025, 56(7), 1099-1107
陈至一, 邢陆, 邓明玮, 石浩永, 吴小黑, 邵一鸣, 孙瑞, 闵杰. 基于4-氰基噻唑单元的聚合物给体材料设计合成及其光伏性能研究. 高分子学报, 2025, 56(7), 1099-1107 DOI： 10.11777/j.issn1000-3304.2025.25002. CSTR： 32057.14.GFZXB.2025.7360.

Chen, Z. Y.; Xing, L.; Deng, M. W.; Shi, H. Y.; Wu, X. H.; Shao, Y. M.; Sun, R.; Min, J. Design, synthesis, and photovoltaic performance of polymer donor materials incorporating 4-cyanothiazole units. Acta Polymerica Sinica, 2025, 56(7), 1099-1107 DOI： 10.11777/j.issn1000-3304.2025.25002. CSTR： 32057.14.GFZXB.2025.7360.

摘要

从结构简单、可商业购买的原料2-溴-4-氰基噻唑出发，本文作者设计合成了以4-氰基噻唑作为受体单元的聚合物给体材料PBTTzCN和PBTTzCN2Cl. 由于氰基和噻唑单元的协同吸电子性质，所开发聚合物给体PBTTzCN和PBTTzCN2Cl都展现出低最高占有轨道(HOMO)，宽能隙. PBTTzCN与非富勒烯小分子受体材料L8-BO共混制备的活性层薄膜具有良好的相分离形貌，可实现优异的电荷传输性能，相应器件的能量转化效率(power conversion efficiency，PCE)达到了14.22%. 然而，基于PBTTzCN2Cl:L8-BO的活性层体系展现出2.02%的PCE，这可能是由于PBTTzCN2Cl的HOMO能级远低于L8-BO的HOMO能级，导致了该体系具有极差的激子分离性能和较低的电子传输性能.

Abstract

Based on the simple and commercially available starting material 2-bromo-4-cyanothiazole

we have for the first time successfully designed and synthesized two novel polymer donor materials

PBTTzCN and PBTTzCN2Cl

incorporating 4-cyanothiazole as the electron-withdrawing acceptor unit. The rational molecular design of these polymer donors takes advantage of the strong electron-withdrawing nature of both the cyano (CN) and thiazole units

which act synergistically to effectively lower the highest occupied molecular orbital (HOMO) energy levels while simultaneously broadening the optical band gaps of the resulting polymers. These characteristics are crucial for optimizing the energy level alignment and absorption properties in organic photovoltaic (OPV) applications. To systematically evaluate the photovoltaic performance of these newly developed materials

we fabricated bulk heterojunction (BHJ) solar cells using PBTTzCN and PBTTzCN2Cl as polymer donors in combination with the well-established non-fullerene small-molecule acceptor L8-BO. The active layer film based on the PBTTzCN:‍L8-BO blend demonstrated a favorable nanoscale phase separation morphology

which promotes efficient charge carrier transport and exciton dissociation

resulting in an outstanding power conversion efficiency (PCE) of 14.22%. In stark contrast

the PBTTzCN2Cl:‍L8-BO-based active layer exhibited a significantly lower PCE of only 2.02%. This drastic reduction in efficiency is primarily attributed to the much deeper HOMO energy level of PBTTzCN2Cl compared to that of L8-BO

which disrupts the energetic driving force necessary for exciton dissociation and leads to inefficient charge generation and inferior electron transport properties. Consequently

the poor photovoltaic performance of PBTTzCN2Cl:‍L8-BO highlights the critical impact of molecular energy level alignment on the overall efficiency of organic solar cells.

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