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Ion migration suppression mechanism via 4-sulfobenzoic acid monopotassium salt for 22.7% stable perovskite solar cells

通过4-磺基苯甲酸单钾盐抑制离子迁移以实现效率为22.7%的稳定钙钛矿太阳能电池

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Abstract

The deep-level traps at grain boundaries (GBs) and halide ion migration are quite challenging for further enhancement of the stability and efficiency of perovskite solar cells (PSCs) as well as for the elimination of notorious hysteresis. Herein, we report a large-sized strongly coordinated organic anion GB anchoring strategy for suppressing ion migration and passivating defects in planar PSCs. The practical implementation of this strategy involves the incorporation of potassium salts containing a large-sized organic counter anion (4-sulfobenzoic acid monopotassium salt, SAMS) into the perovskite precursor. It has been found that anions within SAMS can be firmly anchored at GBs due to the strong coordination interaction between C=O and/or S=O at both ends of bulky anion and undercoordinated Pb2+ and/or halide vacancies, along with the hydrogen bond between −OH and formamidinium. SAMS can not only passivate shallow-level defects but also cause more effective passivation of the deep-level defects. The GB manipulation strategy results in a reduced defect density, an increased carrier lifetime as well as suppressed ion migration, which in turn contributed to enhanced efficiency and stability of PSCs together with a thorough elimination of hysteresis. As a result, the SAMS-modified device with an outstanding fill factor of 0.84 delivers a significant improvement in efficiency (22.7%) in comparison with the control device (20.3%). The unencapsulated modified device demonstrates only little degradation after 1320 h at 60°C.

摘要

晶界处的深能级缺陷和严重的卤素离子迁移对进一步提高钙钛矿太阳能电池的稳定性和效率以及消除迟滞现象提出了严峻的挑战. 本文报道了一种大尺寸强配位的有机阴离子晶界锚定策略来抑制离子迁移并钝化薄膜缺陷. 本策略通过将含有大尺寸有机阴离子的钾盐(4-磺基苯甲酸单钾盐, SAMS)加入到钙钛矿前驱液中来实现. 研究表明, 阴离子两端的C=O和/或S=O能够与未配位的Pb2+离子和/或卤化物空位之间发生强配位作用, 阴离子中的–OH能够与甲脒阳离子形成氢键, 以上化学作用使阴离子紧紧锚定在晶界处. SAMS不仅能够钝化浅能级缺陷, 而且能够更有效地钝化深能级缺陷. 该晶界锚定策略能降低钙钛矿薄膜的缺陷密度、 延长载流子寿命和抑制离子迁移, 提高电池的效率和稳定性以及消除迟滞效应. 结果表明, 基于SAMS改性的电池实现了22.7%的效率, 而对照器件显示了20.3%的效率. 未封装改性的器件在60°C加热老化1320小时后几乎没有发生衰减.

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Acknowledgements

This work was financially supported by the Support Plan for Overseas Students to Return to China for Entrepreneurship and Innovation (cx2020003), the Fundamental Research Funds for the Central Universities (2020CDJQY-A028 and 2020CDJ-LHZZ-074), and the Natural Science Foundation of Chongqing (cstc2020jcyj-msxmX0629). We would like to thank the Analytical and Testing Center of Chongqing University for performing various characterization and measurements.

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Authors and Affiliations

  1. Key Laboratory of Optoelectronic Technology & Systems (Ministry of Education), College of Optoelectronic Engineering, Chongqing University, Chongqing, 400044, China

    Le Bai  (白乐), Baibai Liu  (刘白白), Dongmei He  (何冬梅), Qian Zhou  (周倩), Wenqi Wang  (王文奇), Zhigang Zang  (臧志刚) & Jiangzhao Chen  (陈江照)

  2. Key Lab of Artificial Micro- and Nano-Structures of Ministry of Education of China, School of Physics and Technology, Wuhan University, Wuhan, 430072, China

    Fang Yao  (姚方) & Qianqian Lin  (林乾乾)

  3. Department of Electronic Engineering, East China Normal University, Shanghai, 200241, China

    Rui Wang  (王锐), Xiaobo Hu  (胡小波) & Shaoqiang Chen  (陈少强)

  4. Institute for Clean Energy and Advanced Materials, School of Materials and Energy, Southwest University, Chongqing, 400715, China

    Cunyun Xu  (徐寸云) & Qunliang Song  (宋群梁)

  5. School of Physical Science and Technology, Southwest University, Chongqing, 400715, China

    Tingwei Zhou  (周廷伟)

  6. Department of Materials Science and Engineering, Pohang University of Science and Technology (POSTECH), Pohang, 37673, Korea

    Donghwa Lee

  7. Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, 830011, Xinjiang, China

    Pengjun Zhao  (赵鹏君)

  8. School of Material Science and Engineering, State Key Laboratory of Reliability and Intelligence of Electrical Equipment, Hebei University of Technology, Tianjin, 300130, China

    Cong Chen  (陈聪)

  9. Spallation Neutron Source Science Center, Institute of High Energy Physics, University of Chinese Academy of Sciences (CAS), Dongguan, 523803, China

    Hua Yang  (杨华)

Authors
  1. Le Bai  (白乐)
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  2. Fang Yao  (姚方)
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  3. Rui Wang  (王锐)
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  4. Baibai Liu  (刘白白)
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  5. Dongmei He  (何冬梅)
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  6. Qian Zhou  (周倩)
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  7. Wenqi Wang  (王文奇)
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  8. Cunyun Xu  (徐寸云)
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  9. Xiaobo Hu  (胡小波)
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  10. Shaoqiang Chen  (陈少强)
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  11. Qunliang Song  (宋群梁)
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  12. Tingwei Zhou  (周廷伟)
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  13. Donghwa Lee
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  14. Pengjun Zhao  (赵鹏君)
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  15. Cong Chen  (陈聪)
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  16. Hua Yang  (杨华)
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  17. Qianqian Lin  (林乾乾)
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  18. Zhigang Zang  (臧志刚)
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  19. Jiangzhao Chen  (陈江照)
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Contributions

Author contributions Chen J supervised the project. Chen J and Bai L conceived the idea and designed the experiments. Bai L fabricated perovskite solar cells and performed the most characterizations. Zhou T and Lee D performed the simulation calculation and analysis. Xu C and Song Q performed the measurements of incident photon-to-electron conversion efficiency, transient photocurrent and photovoltage. Yang H and Lin Q performed the time-resolved microwave conductivity measurement. Wang R, Hu X and Chen S carried out the thermal admittance spectroscopy measurement. All authors contributed to reviewing and writing the paper.

Corresponding authors

Correspondence to Tingwei Zhou  (周廷伟), Cong Chen  (陈聪), Zhigang Zang  (臧志刚) or Jiangzhao Chen  (陈江照).

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Conflict of interest The authors declare that they have no conflict of interest.

Le Bai is currently a postgraduate at the College of Optoelectronic Engineering, Chongqing University. She received her BE degree from Chang’an University in 2020 and her current research interests focus on perovskite solar cells.

Tingwei Zhou is a lecturer at the School of Physical Science and Technology, Southwest University. He received his PhD degree from the College of Optoeletronic Engineering, Chongqing University. His current research interests focus on the physical and chemical properties of perovskites.

Cong Chen is currently an associate professor at Hebei University of Technology. He received his PhD degree from Jilin University in June 2019. His main topic of interest is the design of solar cells having high efficiency and long-term stability.

Zhigang Zang received his PhD degree from Kyushu University in 2011. He joined the School of Optoelectronic Engineering, Chongqing University as a professor in 2014. His research interests mainly focus on the synthesis of II–VI, III–V, perovskites semiconductor materials and their applications in solar cells and light-emitting diodes.

Jiangzhao Chen is a professor at the College of Optoelectronic Engineering, Chongqing University. He received his PhD degree from Huazhong University of Science and Technology and worked as a postdoctoral researcher at Sungkyunkwan University and the University of Hong Kong. His current research interests focus on perovskite solar cells.

Supplementary information Supporting data are available in the online version of the paper.

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Bai, L., Yao, F., Wang, R. et al. Ion migration suppression mechanism via 4-sulfobenzoic acid monopotassium salt for 22.7% stable perovskite solar cells. Sci. China Mater. 65, 3368–3381 (2022). https://doi.org/10.1007/s40843-022-2060-9

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