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Nature Energy (2025)
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Atomic disorder is a widespread issue in multi-element crystalline materials and poses a critical challenge to the performance of Cu2ZnSn(S, Se)4 (CZTSSe) photovoltaic devices. In particular, Cu–Zn disorder is prevalent in CZTSSe due to its low formation energy, leading to the formation of high-concentration deep defects and severe charge loss. The regulation of this disorder remains challenging because of the trade-off between the thermodynamics of the disorder–order phase transition and the kinetics of atom interchange. Here we introduce additional vacancy defects at the CZTSSe surface via magnesium doping to reduce the energy barrier for atom interchange. This vacancy-assisted approach enhances the kinetics of Cu–Zn ordering, thereby reducing charge loss in the device. As a result, we achieve a power conversion efficiency of 14.9% certified by the Chinese National PV Industry Measurement and Testing Center in CZTSSe solar cells, marking an advancement in the development of emerging inorganic thin-film photovoltaics.
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We acknowledge the Excellent Science and Technology Innovation Group of Jiangsu Province in Nanjing University of Science and Technology for their help in the theoretical calculations and appreciate the valuable help from X. Cheng and Z. Li at Hebei University in the deep level transient spectroscopy measurements. This work was supported by the National Key R&D Program of China (2024YFB4205000 (to J.S.)), National Natural Science Foundation of China (52222212 (to J.S.), 52227803 (to Q.M.), 52172261 (to Y. Luo), 52502322 (to J.W.)), and China National Postdoctoral Program for Innovative Talents (BX20250177 (to J.W.)). J.S. also gratefully acknowledges the support from the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2022006).
These authors contributed equally: Jinlin Wang, Fanqi Meng, Licheng Lou, Kang Yin.
Beijing National Laboratory for Condensed Matter Physics, Renewable Energy Laboratory, Institute of Physics, Chinese Academy of Sciences (CAS), Beijing, People’s Republic of China
Jinlin Wang, Licheng Lou, Kang Yin, Xiao Xu, Menghan Jiao, Bowen Zhang, Yiming Li, Jiangjian Shi, Huijue Wu, Yanhong Luo, Dongmei Li & Qingbo Meng
School of Physical Sciences, University of Chinese Academy of Sciences, Beijing, People’s Republic of China
Jinlin Wang, Licheng Lou, Kang Yin, Menghan Jiao, Bowen Zhang, Yanhong Luo, Dongmei Li & Qingbo Meng
School of Materials Science and Engineering, Peking University, Beijing, People’s Republic of China
Fanqi Meng
Songshan Lake Materials Laboratory, Dongguan, People’s Republic of China
Yanhong Luo, Dongmei Li & Qingbo Meng
Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, People’s Republic of China
Qingbo Meng
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J.W., J.S., D.L. and Q.M. conceived the idea and designed the experiments. J.W. and J.S. proposed the theoretical mechanism, and did the experiments and the data analysis. F.M. performed structural measurement and analysis. L.L. and K.Y. participated in improving cell performance and conducting characterization. X.X., M.J. and B.Z. supported CZTSSe solar cell fabrication. Y. Li participated in microstructure and photoelectric characterization. H.W. and Y. Luo supported the discussion. J.W., J.S., D.L. and Q.M. participated in writing the paper.
Correspondence to Jiangjian Shi, Dongmei Li or Qingbo Meng.
The authors declare no competing interests.
Nature Energy thanks Simona Olga Binetti and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Notes 1 and 2, Figs. 1–31, Tables 1–3, and references.
Supplementary data for Supplementary Figs. 1–6, 10 and 27.
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Wang, J., Meng, F., Lou, L. et al. Vacancy-enhanced cation ordering via magnesium doping to enable kesterite solar cells with 14.9% certified efficiency. Nat Energy (2025). https://doi.org/10.1038/s41560-025-01902-w
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