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Multinary alloying for facilitated cation exchange and suppressed defect formation in kesterite solar cells with above 14% certified efficiency

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Abstract

Kesterite Cu2ZnSn(S, Se)4 (CZTSSe) solar cells are highly promising low-cost thin-film photovoltaics. However, the efficiency of these solar cells is challenged by severe charge losses and complex defects. Here we reveal through a data-driven correlation analysis that the dominant deep defect in CZTSSe exhibits a donor character. We further propose that incomplete cation exchange in the multi-step crystallization reactions of CZTSSe is the kinetic mechanism responsible for the defect formation. To facilitate the cation exchange, we introduce a multi-elemental alloying approach aimed at weakening the metal–chalcogen bond strength and the stability of intermediate phases. This strategy leads to a significant reduction in charge losses within the CZTSSe absorber and to a total-area cell efficiency of 14.6% (certified at 14.2%). Overall, these results not only present a significant advancement for kesterite solar cells but could also help identify and regulate defects in photovoltaic materials.

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Fig. 1: Defect-type analysis of CZTSSe.
Fig. 2: Kinetic mechanism and regulation of SnZn defect formation.
Fig. 3: Influence of elemental alloying on the solid-phase reaction in CZTSSe films.
Fig. 4: Solar cell characterization.

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Data availability

The data supporting the findings of this study are available within the main text, Supplementary Information and source data files. The structures used in the theoretical modelling are provided as Supplementary Datasets. Source data are provided with this paper.

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Acknowledgements

We acknowledge the Excellent Science and Technology Innovation Group of Jiangsu Province in Nan**g University of Science and Technology for their help in the theoretical calculations and appreciate the valuable help from B. Yang and Z. Li at Hebei University in the deep level transient spectroscopy measurements. This work is supported by the National Natural Science Foundation of China (numbers 52222212 (J.S.), U2002216 (Q.M.), 52227803 (Q.M.), 51972332 (H.W.), 52172261 (Y.L.), 52103284 (F.M.)). J.S. sincerely appreciates the support from the Youth Innovation Promotion Association of the Chinese Academy of Sciences (2022006).

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Author notes

  1. These authors contributed equally: Jiangjian Shi, **lin Wang, Fanqi Meng, Jiazheng Zhou.

Authors and Affiliations

  1. Bei**g National Laboratory for Condensed Matter Physics, Renewable Energy Laboratory, Institute of Physics, Chinese Academy of Sciences, Bei**g, People’s Republic of China

    Jiangjian Shi, **lin Wang, Jiazheng Zhou, **ao Xu, Kang Yin, Licheng Lou, Menghan Jiao, Bowen Zhang, Huijue Wu, Yanhong Luo, Dongmei Li & Qingbo Meng

  2. School of Physics Science, University of Chinese Academy of Sciences, Bei**g, People’s Republic of China

    **lin Wang, Jiazheng Zhou, **ao Xu, Kang Yin, Licheng Lou, Menghan Jiao, Bowen Zhang, Yanhong Luo, Dongmei Li & Qingbo Meng

  3. School of Materials Science and Engineering, Peking University, Bei**g, People’s Republic of China

    Fanqi Meng

  4. Songshan Lake Materials Laboratory, Dongguan, People’s Republic of China

    Yanhong Luo, Dongmei Li & Qingbo Meng

  5. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Bei**g, People’s Republic of China

    Qingbo Meng

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  1. Jiangjian Shi
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Contributions

J.S., J.W. and Q.M. conceived the idea. J.S. did the device simulation, data analysis, device characterization and theoretical calculations and proposed the kinetic mechanism. J.W. and J.Z. fabricated solar cells and did the material/device characterization. F.M. did the STEM characterization and data analysis. X.X., K.Y. and L.L. participated in the device fabrication, optimization and data collection. M.J. and B.Z. participated in the device fabrication. H.W., Y.L. and D.L. participated in the experiment design and discussions. J.S. and Q.M. participated in paper writing and revising. All authors were involved in the discussions and approved the paper.

Corresponding author

Correspondence to Qingbo Meng.

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Nature Energy thanks Jonathan Staaf Scragg 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 Note 1, Figs. 1–33 and Tables 1 and 2.

Reporting Summary

Supplementary Dataset 1

Cif files for the DFT calculations.

Source data

Source Data Fig. 1

Source data for device performance and temperature-dependent PL intensity.

Source Data Fig. 4

Unprocessed current–voltage and EQE data of the champion cell.

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Shi, J., Wang, J., Meng, F. et al. Multinary alloying for facilitated cation exchange and suppressed defect formation in kesterite solar cells with above 14% certified efficiency. Nat Energy (2024). https://doi.org/10.1038/s41560-024-01551-5

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