Abstract
Despite improvements in the power conversion efficiency (PCE) of perovskite solar cells (PSCs), stability issues due to ion migration and phase separation remain critical concerns. Given the ionic crystal nature of perovskites, the use of multivalent cations is supposed to effectively suppress ionic migration. However, multivalent metal cations produce deep-level trap states, thus impairing device efficiency. Therefore, a multivalent cation replacement strategy that minimizes interstitial defects is desirable. Here we develop a divalent cation replacement strategy that mitigates ionic migration while limiting phase segregation. We demonstrate that the replacement of the A-site cations in the perovskite lattice with methylenediammonium cations (MDA2+) substantially suppresses the above issues in wide-bandgap perovskites. This is mainly due to the bivalent state of MDA2+ generating a strong interaction with the inorganic framework and reducing the mobility of halide ions and the formation of defects. As a result, the stability and efficiency of the fabricated PSCs are substantially improved. We demonstrate a champion PCE of 23.20% (certified 22.71%) for a single-junction PSC with a bandgap between 1.67 eV and 1.68 eV. Furthermore, a PCE of 30.13% is obtained for mechanically stacked perovskite/Cu(In,Ga)Se2 tandem devices, and a PCE of 21.88% for translucent perovskite devices. Finally, we obtain a steady-state PCE of 23.28% (certified 22.79%) for flexible monolithic perovskite/Cu(In,Ga)Se2 tandem cells.
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Acknowledgements
R.W. acknowleges the grant from the National Natural Science Foundation of China (grant number 62474143). R.W. and J. Xue acknowledge the grants (grant numbers LDG25E020001, LD22E020002 and LD24E020001) from the Natural Science Foundation of Zhejiang Province of China. J. Xue acknowledges the grants from the Natural Science Foundation of Zhejiang Province of China (grant number LR24F040001) and the National Natural Science Foundation of China (grant number 62274146) as well as the financial support from Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering (2021SZ-FR006). R.W. acknowleges the support of Key R&D Program of Zhejiang (2024SSYS0061). E.B. acknowledges the grant from the Major Industrial Innovation Project of Anhui Province (grant number AHZDCYCX-LSDT2023-10). Computing resources used in this work were provided by the National Center for High Performance Computing of Turkey (UHeM) under the grant number 1015902023. We are grateful to Y. Chen from Instrumentation and Service Center for Physical Sciences, Westlake University, for help with the measurement and analysis of ToF-SIMS data.
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R.W. and J. Xue directed and supervised the project. L.T., R.W. and E.B. conceived the idea and designed the experiment. L.T. fabricated and characterized perovskite films and devices. I.Y. and C.D. conducted the DFT calculations and data analysis. Y.T. and Q.L. performed UPS measurements. Y.T. conducted the tDOS test. S.Z. and J.S. carried out FTIR measurements. Z.C. assisted in the PL imaging test. L.X. contributed to FLIM characterization. Z.Y. assisted in temperature-dependent conductivity measurements. J.Z., L.Y., K.Z., J. Xu, P.S., X.Z., S.W. and S.C. helped with the characterizations and device fabrication. E.B. and M.H. provided CIGS cells. L.T. wrote the paper. R.W., J. Xue, L.T. and E.B. reviewed and edited the paper. All authors discussed the results and commented on the paper.
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R.W., L.T., J. Xue, E.B. and M.H. are inventors on a patent application related to this work filed by Westlake University and Advanced Photovoltaic Technology Research Institute of Xuancheng. The other authors declare no competing interests.
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Nature Photonics thanks Sang Il Seok and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
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Tian, L., Bi, E., Yavuz, I. et al. Divalent cation replacement strategy stabilizes wide-bandgap perovskite for Cu(In,Ga)Se2 tandem solar cells. Nat. Photon. 19, 479–485 (2025). https://doi.org/10.1038/s41566-025-01618-z
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DOI: https://doi.org/10.1038/s41566-025-01618-z
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