Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Surface in situ reconstruction of inorganic perovskite films enabling long carrier lifetimes and solar cells with 21% efficiency

Nature Energy volume 8, pages 372–380 (2023)Cite this article

Subjects

An Author Correction to this article was published on 25 July 2023

This article has been updated

Abstract

All-inorganic perovskites are emerging as excellent photovoltaic candidates for single-junction or tandem solar cells. However, large energy loss due to non-radiative recombination is the main constraint for performance enhancement. Accordingly, we developed a surface in situ reconstruction (SISR) strategy for inorganic perovskite by CsF treatment, which can suppress non-radiative recombination and promote hole extraction simultaneously. Surface defects can be effectively passivated by the introduced fluorine, and carrier lifetime was prolonged from 11.5 ns to 737.2 ns. In addition, a wider-bandgap perovskite layer can be generated as a graded heterojunction to facilitate hole extraction. The SISR reaction mechanism was also verified from both kinetic calculations and experiments. As a result, CsPbIxBr3−x solar cell with SISR achieved an efficiency of 21.02% with a high open-circuit voltage of 1.27 V and fill factor of 85.3%. This work provides an effective approach to modulate inorganic perovskite surfaces for the design of efficient solar cells.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: The passivation of fluoride for inorganic perovskite materials.
Fig. 2: Chemical states, microstructure and morphologies of inorganic perovskite films before and after SISR.
Fig. 3: SISR mechanisms and the formation of graded heterojunctions.
Fig. 4: Photovoltaic performance for the PSCs.
Fig. 5: Photoelectronic characterization of the solar cell devices.

Similar content being viewed by others

Data availability

All data generated or analysed during this study are included in the published article and its Supplementary Information. Additional data are available from the corresponding author upon reasonable request.

Change history

References

  1. Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131, 6050–6051 (2009).

    Article  Google Scholar 

  2. Lee, M. M., Teuscher, J., Miyasaka, T., Murakami, T. N. & Snaith, H. J. Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science 338, 643–647 (2012).

    Article  Google Scholar 

  3. Jeon, N. J. et al. Compositional engineering of perovskite materials for high-performance solar cells. Nature 517, 476–480 (2015).

    Article  Google Scholar 

  4. Kim, J. Y., Lee, J.-W., Jung, H. S., Shin, H. & Park, N.-G. High-efficiency perovskite solar cells. Chem. Mater. 120, 7867–7918 (2020).

    Google Scholar 

  5. Grätzel, M. The light and shade of perovskite solar cells. Nat. Mater. 13, 838–842 (2014).

    Article  Google Scholar 

  6. Jeong, J. et al. Pseudo-halide anion engineering for α-FAPbI3 perovskite solar cells. Nature 592, 381–385 (2021).

    Article  Google Scholar 

  7. Kim, G. et al. Impact of strain relaxation on performance of α-formamidinium lead iodide perovskite solar cells. Science 370, 108–112 (2020).

    Article  Google Scholar 

  8. Beal, R. E. et al. Cesium lead halide perovskites with improved stability for tandem solar cells. J. Phys. Chem. Lett. 7, 746–751 (2016).

    Article  Google Scholar 

  9. Wang, P. et al. Solvent-controlled growth of inorganic perovskite films in dry environment for efficient and stable solar cells. Nat. Commun. 9, 2225 (2018).

  10. Wang, Y. et al. Thermodynamically stabilized β-CsPbI3–based perovskite solar cells with efficiencies >18%. Science 365, 591–595 (2019).

    Article  Google Scholar 

  11. Wang, Q. et al. Stabilizing the α-phase of CsPbI3 perovskite by sulfobetaine zwitterions in one-step spin-coating films. Joule 1, 371–382 (2017).

    Article  Google Scholar 

  12. Wang, J. et al. Highly efficient all-inorganic perovskite solar cells with suppressed non-radiative recombination by a Lewis base. Nat. Commun. 11, 177 (2020).

  13. Steele, J. et al. Thermal unequilibrium of strained black CsPbI3 thin films. Science 365, 679–684 (2019).

    Article  Google Scholar 

  14. Yoon, S. M. et al. Surface engineering of ambient-air-processed cesium lead triiodide layers for efficient solar cells. Joule 5, 183–196 (2021).

    Article  Google Scholar 

  15. Yu, B. et al. Efficient (>20%) and stable all‐inorganic cesium lead triiodide solar cell enabled by thiocyanate molten salts. Angew. Chem. Int. Ed. 60, 13436 (2021).

    Article  Google Scholar 

  16. Zhang, S. et al. Spontaneous construction of multidimensional heterostructure enables enhanced hole extraction for inorganic perovskite solar cells to exceed 20% efficiency. Adv. Energy Mater. 12, 2103007 (2021).

    Article  Google Scholar 

  17. Fu, S. et al. Tailoring in situ healing and stabilizing post-treatment agent for high-performance inverted CsPbI3 perovskite solar cells with efficiency of 16.67%. ACS Energy Lett. 5, 3314–3321 (2020).

    Article  Google Scholar 

  18. Swarnkar, A. et al. Quantum dot-induced phase stabilization of α-CsPbI3 perovskite for high-efficiency photovoltaics. Science 354, 92–95 (2016).

    Article  Google Scholar 

  19. Huang, Y., Yin, W.-J. & He, Y. Intrinsic point defects in inorganic cesium lead iodide perovskite CsPbI3. J. Phys. Chem. C. 122, 1345–1350 (2018).

    Article  Google Scholar 

  20. Li, Y. et al. Intrinsic point defects in inorganic perovskite CsPbI3 from first-principles prediction. Appl. Phys. Lett. 111, 162106 (2017).

    Article  Google Scholar 

  21. Gu, X., Xiang, W., Tian, Q. & Liu, S. Rational surface-defect control via designed passivation for high-efficiency inorganic perovskite solar cells. Angew. Chem. Int. Ed. 133, 23348–23354 (2021).

    Article  Google Scholar 

  22. Liang, J. et al. Defect-engineering-enabled high-efficiency all-inorganic perovskite solar cells. Adv. Mater. 31, 1903448 (2019).

    Article  Google Scholar 

  23. Ho-Baillie, A. et al. Untapped potentials of inorganic metal halide perovskite solar cells. Joule 3, 938–955 (2019).

    Article  Google Scholar 

  24. Yuan, Y., Yan, G., Hong, R., Liang, Z. & Kirchartz, T. Quantifying efficiency limitations in all-inorganic halide perovskite solar cells. Adv. Mater. 34, 2108132 (2022).

    Article  Google Scholar 

  25. Xiang, W. et al. Europium-doped CsPbI2Br for stable and highly efficient inorganic perovskite solar cells. Joule 3, 205–214 (2019).

    Article  Google Scholar 

  26. Ye, Q. et al. Stabilizing γ-CsPbI3 perovskite via phenylethylammonium for efficient solar cells with open-circuit voltage over 1.3 V. Small 16, 2005246 (2020).

    Article  Google Scholar 

  27. Yu, B. et al. Efficient (>20%) and stable all-inorganic cesium lead triiodide solar cell enabled by thiocyanate molten salts. Angew. Chem. Int. Ed. 60, 13436–13443 (2021).

    Article  Google Scholar 

  28. Li, B. et al. Surface passivation engineering strategy to fully-inorganic cubic CsPbI3 perovskites for high-performance solar cells. Nat. Commun. 9, 1076 (2018).

    Article  Google Scholar 

  29. Wang, K. et al. In-situ hot oxygen cleansing and passivation for all-inorganic perovskite solar cells deposited in ambient to breakthrough 19% efficiency. Adv. Func. Mater. 31, 2101568 (2021).

    Article  Google Scholar 

  30. Wang, X., Wang, Y., Chen, Y., Liu, X. & Zhao, Y. Efficient and stable CsPbI3 inorganic perovskite photovoltaics enabled by crystal secondary growth. Adv. Mater. 33, 2103688 (2021).

    Article  Google Scholar 

  31. Guo, Z. et al. VOC over 1.4 V for amorphous tin-oxide-based dopant-free CsPbI2Br perovskite solar cells. J. Am. Chem. Soc. 142, 9725–9734 (2020).

    Article  Google Scholar 

  32. Tan, S. et al. Temperature-reliable low-dimensional perovskites passivated black-phase CsPbI3 toward stable and efficient photovoltaics. Angew. Chem. Int. Ed. 61, e202201300 (2022).

    Article  Google Scholar 

  33. Ye, Q. et al. Cesium lead inorganic solar cell with efficiency beyond 18% via reduced charge recombination. Adv. Mater. 31, 1905143 (2019).

    Article  Google Scholar 

  34. Huang, L., Huang, J., Peng, R. & Ge, Z. Efficient electron transport layer-free perovskite solar cells enabled by discontinuous polar molecular films: a story of new materials and old ideas? ACS Sus. Chem. 9, 936–943 (2021).

    Article  Google Scholar 

  35. Li, B., Zhang, Y., Zhang, L. & Yin, L. Graded heterojunction engineering for hole-conductor-free perovskite solar cells with high hole extraction efficiency and conductivity. Adv. Mater. 29, 1701221 (2017).

    Article  Google Scholar 

  36. Wu, Y. et al. Perovskite solar cells with 18.21% efficiency and area over 1 cm2 fabricated by heterojunction engineering. Nat. Energy 1, 16148 (2016).

    Article  Google Scholar 

  37. Kim, H., Lim, K.-G. & Lee, T.-W. Planar heterojunction organometal halide perovskite solar cells: roles of interfacial layers. Energy Environ. Sci. 9, 12–30 (2016).

    Article  Google Scholar 

  38. Luo, D., Su, R., Zhang, W., Gong, Q. & Zhu, R. Minimizing non-radiative recombination losses in perovskite solar cells. Nat. Rev. Mater. 5, 44–60 (2020).

    Article  Google Scholar 

  39. Jung, E. H. et al. Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene). Nature 567, 511–515 (2019).

    Article  Google Scholar 

  40. Juška, G., Arlauskas, K., Viliūnas, M. & Kočka, J. Extraction current transients: new method of study of charge transport in microcrystalline silicon. Phys. Rev. Lett. 84, 4946 (2000).

    Article  Google Scholar 

  41. Son, D.-Y. et al. Self-formed grain boundary healing layer for highly efficient CH3NH3PbI3 perovskite solar cells. Nat. Energy 1, 16081 (2016).

  42. Petrović, M., Ye, T., Vijila, C. & Ramakrishna, S. Influence of charge transport and defects on the performance of planar and mesostructured perovskite solar cells. Adv. Energy Mater. 7, 1602610 (2017).

    Article  Google Scholar 

  43. Yan, Y. et al. Implementing an intermittent spin-coating strategy to enable bottom-up crystallization in layered halide perovskites. Nat. Commun. 12, 6603 (2021).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant numbers 61925405, 62204104, 61922077 and 11874347) and the National Key Research and Development Program of China (grant number 2020YFB1506400). H.-X.D. was also supported by the Youth Innovation Promotion Association of Chinese Academy of Sciences (grant number Y2021042). We thank Z. Wei for helping with KPFM measurements, Y. Li from Soochow University for helping with TAS measurements, L. Meng from the Institute of Chemistry, Chinese Academy of Sciences for helping with CELIV measurement and we also thank C. Yi from Tsinghua University for helping with TPC characterization.

Author information

Authors and Affiliations

  1. Key Laboratory of Semiconductor Materials Science, Institute of Semiconductors, Chinese Academy of Sciences, Beijing, P. R. China

    Xinbo Chu, Qiufeng Ye, Zhenhan Wang, Fei Ma, Zihan Qu, Yang Zhao, Zhigang Yin, Xingwang Zhang & Jingbi You

  2. School of Integrated Circuits, Ludong University, Yantai, P. R. China

    Xinbo Chu

  3. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, P. R. China

    Qiufeng Ye, Zhenhan Wang, Chen Zhang, Fei Ma, Zihan Qu, Yang Zhao, Zhigang Yin, Hui-Xiong Deng, Xingwang Zhang & Jingbi You

  4. State Key Lab Superlattices & Microstructures, Institute of Semiconductors, Chinese Academy of Sciences, Beijing, P. R. China

    Chen Zhang & Hui-Xiong Deng

Authors
  1. Xinbo Chu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Qiufeng Ye
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Zhenhan Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Chen Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Fei Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Zihan Qu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yang Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Zhigang Yin
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Hui-Xiong Deng
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Xingwang Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Jingbi You
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.Y. directed and supervised the project. X.C. and J.Y. conceived the idea and designed the experiment. X.C. performed and was involved in all the experimental parts. Q.Y. and Z.W. contributed to part of the device fabrication and characterization. F.M., Z.Q., Y.Z., Z.Y. and X.Z. were involved in data analysis. C.Z. and H.-X.D. conducted theoretical calculations. X.C. and J.Y. co-wrote the manuscript. All authors contributed to discussions and finalization of the manuscript.

Corresponding authors

Correspondence to Hui-Xiong Deng or Jingbi You.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Energy thanks Byungha Shin, Yixin Zhao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–34 and Tables 1–8.

Reporting Summary.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chu, X., Ye, Q., Wang, Z. et al. Surface in situ reconstruction of inorganic perovskite films enabling long carrier lifetimes and solar cells with 21% efficiency. Nat Energy 8, 372–380 (2023). https://doi.org/10.1038/s41560-023-01220-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-023-01220-z

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing