Perylenocarbazole‐Based Polycyclic Aromatic Self‐Assembled Monolayers with Tailored Electrostatic Potentials for High‐Performance Organic and Perovskite Solar Cells

X Xing Chen (Institute of Molecular Plus, Department of Chemistry, Tianjin University and Haihe Laboratory of Sustainable Chemical Transformations, 92 Weijin Road, Tianjin 300072, China) S Shuzhen Liao (Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education/National Engineering Research Center for Carbohydrate Synthesis College of Chemistry and Materials Jiangxi Normal University Nanchang China) Y Yonglong Yang (College of Chemistry and Materials/Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education/National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University Nanchang P. R. China) Y Yuang Fu (Department of Physics, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China) M Mingtao Liu (Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education/National Engineering Research Center for Carbohydrate Synthesis College of Chemistry and Materials Jiangxi Normal University Nanchang China) P Peipei Zhu W Weilin Zhou M Manjiang Yu (College of Biological and Chemical Engineering Jiaxing University Jiaxing China) J Jin Li D Dan Liu Y Yaoyao Zhu L Lin Hu (The High Magnetic Field Laboratory, Hefei Institutes of Physical Science) Y Yong Huo (Frontier Science Center for Rare Isotopes, School of Nuclear Science and Technology) X Xiaopeng Xu A Aihui Liang (College of Chemistry and Materials/Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, Jiangxi Normal University, 99 Ziyang Avenue, Nanchang 330022, China) X Xinhui Lu (Department of Physics) X Xunfan Liao (Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education/National Engineering Research Center for Carbohydrate Synthesis College of Chemistry and Materials Jiangxi Normal University Nanchang China) Y Yiwang Chen (College of Chemistry and Chemical Engineering/Film Energy Chemistry for Jiangxi Provincial Key Laboratory (FEC), Nanchang University, Nanchang, China.)

Abstract

ABSTRACT The development of universal hole‐transporting layers for organic and perovskite solar cells (OSCs/PSCs) remains challenging due to the lack of molecular strategies that precisely control interfacial energetics, molecular packing, and active layer morphology. Here, we report an electrostatic potential (ESP)‐guided approach to construct nitrogen‐containing polycyclic aromatic self‐assembled monolayers (SAMs) that address this challenge. By integrating a rigid, planar perylenocarbazole (PCz) core with extended π‐conjugation, alkyl chain optimization, and bromination, we designed two novel SAMs, 4PCzBr and 6PCzBr, with precisely tailored ESP distributions. Compared to conventional carbazole‐based SAMs, these designs substantially elevate the average ESP, strengthen intermolecular π–π interactions, and promote dense, ordered monolayer formation on ITO, thereby enhancing work function alignment and hole extraction. Interestingly, the elevated ESP of 6PCzBr strengthens electrostatic interactions with the donor PM6, driving preferential donor crystallization at the buried interface and establishing an ideal vertical phase separation for efficient charge transport. Leveraging this synergy, 6PCzBr‐based OSCs deliver an outstanding efficiency of 20.16%, while inverted PSCs achieve a remarkable efficiency of 26.20% with decent operation stability. This work establishes ESP‐engineered polycyclic aromatic SAMs as a versatile interfacial platform bridging organic and perovskite photovoltaics, offering a broadly applicable molecular design paradigm for high‐efficiency and stable solar cells.

Article Details

Volume / Issue Vol. 1, Issue 1
Published July 07, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (18)

X

Xing Chen

Institute of Molecular Plus, Department of Chemistry, Tianjin University and Haihe Laboratory of Sustainable Chemical Transformations, 92 Weijin Road, Tianjin 300072, China

S

Shuzhen Liao

Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education/National Engineering Research Center for Carbohydrate Synthesis College of Chemistry and Materials Jiangxi Normal University Nanchang China

Y

Yonglong Yang

College of Chemistry and Materials/Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education/National Engineering Research Center for Carbohydrate Synthesis, Jiangxi Normal University Nanchang P. R. China

Y

Yuang Fu

Department of Physics, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China

M

Mingtao Liu

Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education/National Engineering Research Center for Carbohydrate Synthesis College of Chemistry and Materials Jiangxi Normal University Nanchang China

P

Peipei Zhu

W

Weilin Zhou

M

Manjiang Yu

College of Biological and Chemical Engineering Jiaxing University Jiaxing China

J

Jin Li

D

Dan Liu

Y

Yaoyao Zhu

L

Lin Hu

The High Magnetic Field Laboratory, Hefei Institutes of Physical Science

Y

Yong Huo

Frontier Science Center for Rare Isotopes, School of Nuclear Science and Technology

X

Xiaopeng Xu

A

Aihui Liang

College of Chemistry and Materials/Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education, Jiangxi Normal University, 99 Ziyang Avenue, Nanchang 330022, China

X

Xinhui Lu

Department of Physics

X

Xunfan Liao

Key Laboratory of Fluorine and Silicon for Energy Materials and Chemistry of Ministry of Education/National Engineering Research Center for Carbohydrate Synthesis College of Chemistry and Materials Jiangxi Normal University Nanchang China

Y

Yiwang Chen

College of Chemistry and Chemical Engineering/Film Energy Chemistry for Jiangxi Provincial Key Laboratory (FEC), Nanchang University, Nanchang, China.