<i>π</i>-共轭扩展二萘并咔唑膦酸作为反式钙钛矿太阳能电池的空穴选择层

引用本文: 张善涛, 侯天骜, 王艳东, 方志敏, 吴宇, 王灝霖, 陈涛, 陈爽, 张文华, 刘生忠, 杨上峰. π-共轭扩展二萘并咔唑膦酸作为反式钙钛矿太阳能电池的空穴选择层[J]. 物理化学学报, 2026, 42(3): 100194. doi: 10.1016/j.actphy.2025.100194 shu

Citation: Shantao Zhang, TianAo Hou, Yandong Wang, Zhimin Fang, Yu Wu, Haolin Wang, Tao Chen, Shuang Chen, Wenhua Zhang, Shengzhong (Frank) Liu, Shangfeng Yang. π-Conjugation-extended dinaphthocarbazole phosphonic acid as a hole-selective layer for inverted perovskite solar cells[J]. Acta Physico-Chimica Sinica, 2026, 42(3): 100194. doi: 10.1016/j.actphy.2025.100194 shu

π-共轭扩展二萘并咔唑膦酸作为反式钙钛矿太阳能电池的空穴选择层

张善涛 ^1, ,
侯天骜 ^1, ,
王艳东 ^4, ,
方志敏 ^{2,
,} ,
吴宇 ^5, ,
王灝霖 ^1, ,
陈涛 ^1, ,
陈爽 ^5, ,
张文华 ^4, ,
刘生忠 ^{3,
,} ,
杨上峰 ^{1,
,}

1.
中国科学技术大学, 精准智能化学全国重点实验室, 能源材料化学协同创新中心, 材料科学与工程系, 安徽合肥 230026;
2.
扬州大学, 碳中和技术研究院, 江苏扬州 225127;
3.
中国科学院大连化学物理研究所, 太阳能光电转化与利用重点实验室, 辽宁大连 116023;
4.
云南大学, 材料与能源学院, 云南省碳中和绿色低碳技术重点实验室, 云南昆明 650000;
5.
南京大学, 匡亚明学院, 江苏南京 210023

通讯作者: 方志敏,Email:fangzm@yzu.edu.cn; 刘生忠,Email:szliu@dicp.ac.cn; 杨上峰,Email:sfyang@ustc.edu.cn

基金项目:
国家自然科学基金(51925206, 52461160328, 52350710208, 62174103)；中国科学院战略性先导科技专项(XDB0450301, XDB1140000)；中央高校基本科研业务费专项资金(20720220009, WK2490000002, GK202103106)；知识创新工程项目(Y261261606)；111计划(B21005, B1404)，陕西省重点研发计划(2022LL-JB-08)资助项目

摘要: 自组装单层(SAMs)是当前高效率反式钙钛矿太阳能电池(PSCs)中关键的空穴选择层材料(HSLs)。SAMs不仅决定了界面空穴的提取效率，还显著影响顶部钙钛矿层的薄膜质量，从而精细调控钙钛矿太阳能电池的效率和稳定性。本研究开发了一种新型SAM材料——(4-(8H-二萘并[2,3-c:2'，3'-g]咔唑-8-基)丁基)膦酸(4PADNC)，它含有二萘并咔唑(DNC)结构单元，可作为反式PSCs的高性能HSL。与常用的咔唑类SAM (如4PACZ)相比，4PADNC中的DNC单元展现出扩展的π共轭特征，能够产生更大的分子偶极矩，从而调节氧化铟锡(ITO)电极的功函数，实现与钙钛矿能级的精准匹配，并显著降低界面能量损失。此外，该分子的非平面结构有效地抑制了π-π堆积，促进在ITO基底上形成致密且均匀的选择层，进而诱导高质量钙钛矿薄膜的沉积。得益于上述优势，采用4PADNC作为HSL的PSCs器件实现了24.32%的功率转换效率，显著优于基于4PACZ的参比器件(22.89%)。此外，基于4PADNC的器件还表现出卓越的热稳定性和运行稳定性。

关键词:

English

π-Conjugation-extended dinaphthocarbazole phosphonic acid as a hole-selective layer for inverted perovskite solar cells

1.
State Key Laboratory of Precision and Intelligent Chemistry, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, Anhui Province, China;
2.
Institute of Technology for Carbon Neutralization, Yangzhou University, Yangzhou 225127, Jiangsu Province, China;
3.
Key Laboratory of Photoelectric Conversion and Utilization of Solar Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China;
4.
Yunnan Key Laboratory of Carbon Neutrality and Green, Low-carbon Technologies, School of Materials and Energy, Yunnan University, Kunming 650000, Yunnan Province, China;
5.
Kuang Yaming Honors School, Nanjing University, Nanjing 210023, Jiangsu Province, China

Corresponding author: Zhimin Fang, ; Shengzhong (Frank) Liu, ; Shangfeng Yang,

Received Date: 17 July 2025
Accepted Date: 23 September 2025
Revised Date: 13 September 2025

Abstract: In the rapidly evolving field of photovoltaic technology, self-assembled monolayers (SAMs) have become essential hole-selective layers (HSLs) for inverted perovskite solar cells (PSCs). SAMs not only determine interfacial hole extraction but also significantly influence the film quality of the atop perovskite layers, consequently affecting the efficiency and stability of perovskite solar cells. Among various SAMs, carbazole-based SAMs, exemplified by 4PACZ, have emerged as prominent due to their electron-rich characteristics, making them some of the most prevalent HSLs in modern inverted PSCs. Nevertheless, 4PACZ exhibits significant limitations: one major issue is its limited molecular dipole, which leads to insufficient energy level alignment between the treated substrate and the perovskite, causing substantial interfacial energy loss. Another critical challenge is the flat structure of the carbazole unit, which often promotes molecular stacking, resulting in incomplete substrate coverage and non-uniform film formation, thereby compromising both device performance and stability. In this study, we designed a novel SAM based on a polycyclic aromatic hydrocarbon derivative, (4-(8H-dinaphtho[2,3-c:2',3'-g]carbazol-8-yl)butyl)phosphonic acid (4PADNC), with the aim of optimizing hole transport in inverted PSCs. This SAM incorporates the structurally extended dinaphtho[2,3-c:2',3'-g]carbazole (DNC) as the functional terminal group, replacing the single carbazole unit in the traditional material 4PACZ. The key structural difference is that the DNC group provides a significantly expanded π-conjugated skeleton and enhanced electron-rich characteristics. These features not only greatly enhance hole extraction and transport at the interface but also induce a significant increase in the molecular dipole moment, which is crucial for effectively adjusting the work function of ITO, ensuring proper alignment with the perovskite layer. Additionally, there is an intramolecular dihedral angle of approximately 34.62° in the DNC unit at the core of 4PADNC. This non-planar configuration contrasts sharply with the planar carbazole structure. The larger dihedral angle effectively suppresses excessive π-π stacking between molecules, which not only aids in forming a denser and more ordered molecular layer on the ITO surface but also provides a more favorable and defect-free substrate for the growth of the upper perovskite. With these upgrades, the inverted PSCs based on 4PADNC achieved a PCE as high as 24.32%, compared to 22.89% for the control devices based on 4PACZ. Furthermore, the 4PADNC-based devices also exhibited superior thermal stability and operational stability.

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沈阳化工大学材料科学与工程学院沈阳 110142

π-共轭扩展二萘并咔唑膦酸作为反式钙钛矿太阳能电池的空穴选择层

通讯作者: 方志敏,Email:fangzm@yzu.edu.cn; 刘生忠,Email:szliu@dicp.ac.cn; 杨上峰,Email:sfyang@ustc.edu.cn

English

π-Conjugation-extended dinaphthocarbazole phosphonic acid as a hole-selective layer for inverted perovskite solar cells

Corresponding author: Zhimin Fang, ; Shengzhong (Frank) Liu, ; Shangfeng Yang,

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

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中国化学会秘书处

π-共轭扩展二萘并咔唑膦酸作为反式钙钛矿太阳能电池的空穴选择层

通讯作者: 方志敏,Email:fangzm@yzu.edu.cn; 刘生忠,Email:szliu@dicp.ac.cn; 杨上峰,Email:sfyang@ustc.edu.cn

English

π-Conjugation-extended dinaphthocarbazole phosphonic acid as a hole-selective layer for inverted perovskite solar cells

Corresponding author: Zhimin Fang, ; Shengzhong (Frank) Liu, ; Shangfeng Yang,

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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