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Sn4+ precursor enables 12.4% efficient kesterite solar cell from DMSO solution with open circuit voltage deficit below 0.30 V

全面积效率12.4%、 开路电压损失低于0.30 V的CZTSSe太阳能电池: Sn4+前驱体在DMSO溶液中的使用

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Abstract

The limiting factor preventing further performance improvement of the kesterite (sulfide Cu2ZnSnS4 (CZTS), selenide Cu2ZnSnSe4 (CZTSe), and their alloying Cu2ZnSn(S,Se)4 (CZTSSe)) thin film solar cells is the large open-circuit voltage deficit (Voc,def) issue, which is 0.345 V for the current world record device with an efficiency of 12.6%. In this study, SnCl4 and SnCl2·2H2O were respectively used as tin precursor to investigate the Voc,def issue of dimethyl sulfoxide (DMSO) solution processed CZTSSe solar cells. Different complexations of tin compounds with thiourea (Tu) and DMSO resulted in different reaction pathways from the solution to the absorber material and thus dramatic differences in photovoltaic performance. The coordination of Sn2+ with Tu led to the formation of SnS, ZnS and Cu2S in the precursor film, which converted to selenides first and then fused to CZTSSe, resulting in poor film quality and device performance. The highest efficiency obtained from this film was 8.84% with a Voc,def of 0.391 V. The coordination of Sn4+ with DMSO facilitated direct formation of CZTS phase in the precursor film which directly converted to CZTSSe during selenization, resulting in compositional uniform absorber and high device performance. A device with an active area efficiency of 12.2% and a Voc,def of 0.344 V was achieved from the Sn4+ solution processed absorber. Furthermore, CZTSSe/CdS heterojunction heat treatment (JHT) significantly improved the performance of the Sn4+ device but had slightly negative effect on the Sn2+ device. A champion CZTSSe solar cell with a total area efficiency of 12.4% (active area efficiency of 13.6%) and a low Voc,def of 0.297 V was achieved from the Sn4+ solution. Our results demonstrate the preformed uniform CZTSSe phase enabled by Sn4+ precursor is the key for the highly efficient CZTSSe absorber. The lowest Voc,def and high efficiency achieved here shines new light on the future of CZTSSe solar cell.

摘要

开路电压损失(Voc,def)大是制约锌黄锡矿结构CZTSSe太阳能电池效率的关键因素, 目前世界纪录效率(12.6%) CZTSSe电池的 Voc,def为0.345 V. 本文分别以SnCl4和SnCl2·2H2O为锡前驱体研究二甲基亚砜(DMSO)溶液法制备的CZTSSe太阳能电池的开路电压损失问题. 研究发现不同价态的锡前驱体化合物与有机配体硫脲(Tu)和溶剂DMSO发生不同的配位反应, 使得从溶液到CZTSSe吸光层薄膜的反应路径截然不同. Sn2+与Tu配位导致前驱体薄膜中SnS、 ZnS和Cu2S的生成, 这些硫化物在硒化过程中首先转化成硒化物而后逐步熔合生成CZTSSe, 其反应路径中多物相的转化和熔合导致薄膜光电性能差, 由该薄膜获得的最优器件有效面积效率仅为 8.84%, Voc,def 为0.391 V. 而Sn4+与DMSO配位, 该前驱体溶液经退火直接得到组成均匀的CZTS前驱体薄膜, 在硒化过程中CZTS直接发生取代反应生成CZTSSe, 得到的CZTSSe薄膜组成均匀, 光电性能优异, 由该薄膜制备的器件有效面积效率达到12.2%, Voc,def降低至0.344 V. 此外, CZTSSe薄膜性质的不同导致CZTSSe/CdS异质结热处理(JHT)结果的不同. JHT显著提高了Sn4+器件的性能, 却略微降低了Sn2+器件的性能. 最终, 由Sn4+溶液获得了全面积效率为 12.4%, 有效面积效率高达13.6%, Voc,def低至0.297 V的CZTSSe太阳能电池器件. 研究结果表明通过控制溶液中化学组成获得组成均匀的CZTS预制膜是获得高效CZTSSe电池薄膜材料和降低器件 Voc,def的关键. 本报道不仅为进一步提高CZTSSe电池效率提供了新的思路, 而且实现了Voc,def首次低于0.30 V, 预示了CZTSSe未来的应用前景.

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Acknowledgements

This work was supported primarily by the National Natural Science Foundation of China (21571106 and U1902218). Jiang J and Yu S acknowledge the support from the Postgraduate Research and Practice Innovation Program of Jiangsu Province. Jedlicka E and Giridharagopal R acknowledge the support from the Molecular Analysis Facility, a National Nanotechnology Coordinated Infrastructure site at the University of Washington which is supported in part by the National Science Foundation (NNCI-1542101), the University of Washington, the Molecular Engineering & Sciences Institute, the Clean Energy Institute, and the National Institutes of Health.

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Authors and Affiliations

  1. Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials (IAM), Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, Nanjing, 210023, China

    Yuancai Gong  (龚元才), Yifan Zhang  (张一凡), Weibo Yan  (闫伟博), Chuanyou Niu  (牛传友), Ruichan Qiu  (邱瑞婵), Jingjing Jiang  (江晶晶), Shaotang Yu  (余绍棠), Sanping Wu  (吴三平), Wei Huang  (黄维) & Hao Xin  (辛颢)

  2. Department of Chemistry, University of Washington, Seattle, WA, 98195, USA

    Erin Jedlicka, Rajiv Giridharagopal & David S. Ginger

  3. Department of Chemical Engineering, University of Washington, Seattle, WA, 98195, USA

    James A. Clark & Hugh W. Hillhouse

Authors
  1. Yuancai Gong  (龚元才)
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  2. Yifan Zhang  (张一凡)
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  3. Erin Jedlicka
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  4. Rajiv Giridharagopal
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  5. James A. Clark
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  6. Weibo Yan  (闫伟博)
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  7. Chuanyou Niu  (牛传友)
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  8. Ruichan Qiu  (邱瑞婵)
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  9. Jingjing Jiang  (江晶晶)
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  11. Sanping Wu  (吴三平)
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  14. Wei Huang  (黄维)
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  15. Hao Xin  (辛颢)
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Contributions

Author contributions Gong Y and Xin H conceived the idea and co-wrote the manuscript. Xin H and Huang W supervised this study. Gong Y and Zhang Y fabricated the devices and conducted most of the measurements. Jedlicka E and Giridharagopal R conducted the GDOES measurements and initial data process. Clark J conducted the PL measurements. Niu C, Qiu R, Jiang J, Yu S and Wu S provided assistance in the device fabrication and measurements. Yan W, Huang W, Hillhouse H and Ginger D discussed the results and provided valuable suggestions to the manuscript.

Corresponding author

Correspondence to Hao Xin  (辛颢).

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Conflict of interest The authors declare no conflict of interest.

Additional information

Yuancai Gong is a PhD candidate in the Institute of Advanced Materials, School of Materials Science and Engineering, Nanjing University of Posts & Telecommunications, under the supervision of Prof. Hao Xin. His research focuses on earth-abundant kesterite thin film solar cells.

Hao Xin is a professor of materials science and engineering at Nanjing University of Posts and Telecommunications. She received her PhD from Peking University in 2003. She was a JST CREST researcher at NIMS and a JSPS fellow at JAIST from 2003 to 2006. Then she worked in the Department of Chemical Engineering at the University of Washington until 2012. Her current research interests are solution processed thin film solar cells including CZTS, CIGS and perovskite.

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Sn4+ Precursor Enables 12.4% Efficient Kesterite Solar Cell from DMSO Solution with Open Circuit Voltage Deficit Below 0.30 V

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Gong, Y., Zhang, Y., Jedlicka, E. et al. Sn4+ precursor enables 12.4% efficient kesterite solar cell from DMSO solution with open circuit voltage deficit below 0.30 V. Sci. China Mater. 64, 52–60 (2021). https://doi.org/10.1007/s40843-020-1408-x

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