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Engineering bonding sites enables uniform and robust self-assembled monolayer for stable perovskite solar cells

Nature Materials volume 24, pages 1265–1272 (2025)Cite this article

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Abstract

The efficiency of perovskite solar cells has recently been dramatically improved by a self-assembled monolayer (SAM), but forming uniform, dense and especially stable SAM remains a challenge. The hydroxyl groups on indium tin oxide (ITO) serve as the bonding sites for the SAM molecule, directly determining the distribution and anchoring stability of SAM. We developed a solution-based strategy to fully hydroxylate the ITO in as fast as 15 s. Moreover, further hydroxylation etching could also create abundant uncoordinated indium ions on the new exposed ITO surface for the anchoring of SAM by forming coordination bonds. In addition, the rapid hydroxylation etching allows commercial ITO to be directly used to omit the conventional multistep ITO pretreatment. Moreover, hydroxylation etching can also spontaneously form nano-antireflective structures on ITO to improve photon transmission. The versatile bonding site engineering resulted in better SAM anchoring, which delivered efficient perovskite solar cells (power conversion efficiency, 26.6%) that only lose 4% of the initial efficiency after 2,800 h of operation at 65 °C (ISOS-L-2 protocol).

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Fig. 1: Bonding site engineering.
Fig. 2: More uniform and denser SAM anchoring.
Fig. 3: More stable SAM anchoring.
Fig. 4: Photovoltaic performance and versatility.

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Data availability

All data generated or analysed during this study are included in the Article and its Supplementary Information. Further data are available from the corresponding author (Q.Z.) on reasonable request.

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Acknowledgements

We thank G. H. J. Zheng and X. Y. Gao from the Shanghai Synchrotron Radiation Facility for grazing-incidence wide‐angle X‐ray scattering measurements. We thank the BL14B1 beamline in the Shanghai Synchrotron Radiation Facility for providing the beam time. We thank Y. L. Wang from the Institute of Chemistry, Chinese Academy of Sciences, for water contact angle tests. We thank X. K. Zeng from Southwest Jiaotong University for the laser etching experiment. We thank Z. Wang and G. H. Wei for assistance with the preparation of the hydroxylation etching solution. This work was supported by the National Natural Science Foundation of China (NSFC 52272178 and 52473301), the National Key Research and Development Program of China (numbers 2023YFE0117700 and 2021YFB3800104), Beijing Nova Program (number 20230484415), the Young Elite Scientists Sponsorship Program by CAST, the Natural Science Foundation of Hubei Province (2022CFA093), the Natural Science Foundation of Jiangsu Province (BK20220244), Suzhou Basic Research Project (SJC2023003), the Natural Science Foundation of the Jiangsu Higher Education Institutions (22KJB480009), the China Postdoctoral Science Foundation (2024M751002 and GZC20240528) and Peking University-BHP Carbon and Climate Wei-Ming PhD Scholars (WM202201).

Author information

Author notes

  1. These authors contributed equally: Chao Luo, Qisen Zhou, Keli Wang.

Authors and Affiliations

  1. State Key Lab for Mesoscopic Physics and Frontiers Science Center for Nano-optoelectronics, School of Physics, Peking University, Beijing, China

    Chao Luo, Keli Wang, Jiandong He, Peng Gao, Changling Zhan, Zhuye Bi & Qing Zhao

  2. Solar Energy Research Institute of Singapore (SERIS), National University of Singapore, Singapore, Singapore

    Chao Luo & Yi Hou

  3. Wuhan National Laboratory for Optoelectronics and School of Optical and Electronic Information, Huazhong University of Science and Technology, Wuhan, China

    Qisen Zhou, Wenpei Li, Wei Chen & Zonghao Liu

  4. Optics Valley Laboratory, Wuhan, China

    Qisen Zhou, Wenpei Li, Wei Chen & Zonghao Liu

  5. Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, China

    Keli Wang

  6. School of Physics and Electrical Engineering, Liupanshui Normal University, Liupanshui, China

    Xianjin Wang

  7. School of Chemical Science, University of Chinese Academy of Sciences, Beijing, China

    Jiandong He

  8. School of Optical and Electronic Information and Jiangsu/Suzhou Key Laboratory of Biophotonics and International Joint Metacenter for Advanced Photonics and Electronics, Suzhou City University, Suzhou, China

    Zhuye Bi & Yingzhuang Ma

  9. Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore

    Yi Hou

  10. Peking University Yangtze Delta Institute of Optoelectronics, Nantong, China

    Qing Zhao

  11. Collaborative Innovation Center of Quantum Matter, Beijing, China

    Qing Zhao

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Contributions

C.L. and Q.Z. conceived the idea. Q.Z., Z.L. and Y.H. directed and supervised the project. C.L., Q.S.Z., K.W. and J.H. prepared the devices. C.L. and X.W. discussed the preparation of hydroxylation etching solutions. K.W. conducted the DFT calculations. C.Z., P.G. and Z.B. helped characterize the perovskite films and devices. Q.Z., Y.H. and C.L. co-wrote the paper. All authors analysed their data and reviewed and commented on the paper.

Corresponding authors

Correspondence to Yi Hou, Zonghao Liu or Qing Zhao.

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Competing interests

C.L. and Q.Z. have filed a provisional patent for this work with the China National Intellectual Property Administration. The other authors declare no competing interests.

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Nature Materials thanks Nam-Gyu Park and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Notes 1–4, Figs. 1–44 and Table 1.

Reporting Summary

Supplementary Video 1

Comparison of water contact angles between the control and target ITO.

Supplementary Video 2

One-shot recording of changing ITO from hydrophobic to superhydrophilic.

Supplementary Video 3

Fast hydroxylation of ITO in 15 s.

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Luo, C., Zhou, Q., Wang, K. et al. Engineering bonding sites enables uniform and robust self-assembled monolayer for stable perovskite solar cells. Nat. Mater. 24, 1265–1272 (2025). https://doi.org/10.1038/s41563-025-02275-x

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