journal article·2025-07

Decoding the Role of Molecular Orientation in Conjugated Self‐Assembled Monolayers for High‐Performance Binary Organic Photovoltaics Approaching 20% Efficiency

Yibo Kong, Wanhai Wang, Xiangwei Guo, Yuhui Yang, Tianyi Chen, Xiangjun Zheng, Wenxuan Yu, Yiming Wang, Mengting Wang, Yibo Hu, Chenran Xu, Yongjun Wu, Dawei Wang, Zijian Hong, Weihua Tang, Hongzheng Chen, Lijian Zuo

Advanced Materials· Volume 37· Issue 26
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Abstract

Abstract Molecular orientation stands as the quintessential hallmark of conjugated self‐assembled monolayers (SAMs), which have recently catalyzed noteworthy advancements in organic photovoltaics (OPVs). Nevertheless, an unambiguous understanding of these directional arrangements and their impact on optoelectronic properties remains elusive. To address this issue, herein three SAMs with representative orientations, i.e., edge‐on (BCZ‐1), tilt‐on (4PACz) and face‐on (BCZ‐2) are meticulously designed. These orientations have been rigorously validated by sum frequency generation vibrational spectroscopy and first‐principles calculations. Remarkably, an unequivocal correlation between the molecular orientation and the device performance is discerned. Particularly, the edge‐on oriented BCZ‐1 exhibits the largest dipole moment normal to the electrode, accompanied by a dense and uniform coverage. These features collectively contribute to its strongest work function increment for ultra‐fast hole extraction and minimum interfacial carrier recombination. As a result, a champion power conversion efficiency of 19.93% is achieved in devices based on BCZ‐1 with D18:L8‐BO as the active layer, representing one of the highest values reported for binary bulk heterojunction OPVs. Besides, BCZ‐1 shows great potential for practical applications due to its superior up‐scalability and enhanced device shelf‐stability. Overall, this work offers in‐depth insights into the orientation behaviors of SAMs, opening new avenues to unlock the efficiency potential of OPVs.
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Research context

OpenAlex topics: Perovskite Materials and Applications · Organic Electronics and Photovoltaics · Molecular Junctions and Nanostructures

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

State Key Laboratory of Silicon and Advanced Semiconductor Materials Department of Polymer Science and Engineering Zhejiang University Hangzhou 310027 P. R. China

College of Materials College of Chemistry and Chemical Engineering Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM) Xiamen University Xiamen 361005 P. R. China

State Key Laboratory of Silicon and Advanced Semiconductor Materials School of Materials Science and Engineering Zhejiang University Hangzhou Zhejiang 310027 P. R. China

Institute of Fundamental and Transdisciplinary Research Zhejiang University Hangzhou 311121 P. R. China

Zhejiang Key Laboratory of Advanced Solid State Energy Storage Technology and Applications Taizhou Institute of Zhejiang University Taizhou Zhejiang 318000 P. R. China

School of Chemistry and Chemical Engineering Key Laboratory of Surface & Interface Science of Polymer Materials of Zhejiang Province Zhejiang Sci‐Tech University Hangzhou 310018 P. R. China

Zhejiang Key Laboratory of Micro‐Nano Quantum Chips and Quantum Control School of Physics and State Key Laboratory for Extreme Photonics and Instrumentation Zhejiang University Hangzhou 310027 P. R. China

Zhejiang University‐Hangzhou Global Scientific and Technological Innovation Center Hangzhou 310014 P. R. China

Funding

National Natural Science Foundation of China · National Key Research and Development Program of China · Shenzhen Science and Technology Innovation Program · China Postdoctoral Science Foundation · Fundamental Research Funds for the Central Universities

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