物理化学学报 >> 2026, Vol. 42 >> Issue (3): 100194.doi: 10.1016/j.actphy.2025.100194

所属专题： 太阳能转化与储存

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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. 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
  • 收稿日期:2025-07-17 修回日期:2025-09-13 录用日期:2025-09-23 发布日期:2026-01-05
  • 通讯作者: Email: sfyang@ustc.edu.cn (杨上峰)fangzm@yzu.edu.cn (方志敏)szliu@dicp.ac.cn (刘生忠)
  • 作者简介:

    †这些作者对本文做出同等贡献。

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

Shantao Zhang1, TianAo Hou1, Yandong Wang4, Zhimin Fang2,*(), Yu Wu5, Haolin Wang1, Tao Chen1, Shuang Chen5, Wenhua Zhang4, Shengzhong (Frank) Liu3,*(), Shangfeng Yang1,*()   

  1. 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
  • Received:2025-07-17 Revised:2025-09-13 Accepted:2025-09-23 Published:2026-01-05
  • Contact: Email: sfyang@ustc.edu.cn (Shangfeng Yang)fangzm@yzu.edu.cn (Zhimin Fang)szliu@dicp.ac.cn (Shengzhong (Frank) Liu)

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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: 钙钛矿太阳能电池, 空穴选择层, 自组装单层, 二萘并咔唑, π共轭

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.

Key words: Perovskite solar cells, Hole-selective layer, Self-assembled monolayer, Dinaphtho carbazole, π-conjugation