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:

Suppression of phase segregation in wide-bandgap perovskites with thiocyanate ions for perovskite/organic tandems with 25.06% efficiency

Abstract

Mixed halide wide-bandgap perovskites are suitable for integration in tandem photovoltaics such as perovskite/organic tandem solar cells. However, halide phase segregation originating from halogen vacancy-assisted ion migration in wide-bandgap perovskites limits the device efficiency and lifetime. Here we incorporate pseudo-halogen thiocyanate (SCN) ions in iodide/bromide mixed halide perovskites and show that they enhance crystallization and reduce grain boundaries. Trace amount of SCN ions in the bulk enter the perovskite lattice, forming an I/Br/SCN alloy, and occupy iodine vacancies, blocking halide ion migration via steric hindrance. Taken together, these effects retard halide phase segregation under operation and reduce energy loss in the wide-bandgap perovskite cells. The resulting perovskite/organic tandem solar cell achieves a power conversion efficiency of 25.82% (certified 25.06%) and an operational stability of 1,000 h.

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

Access options

Buy this article

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

Fig. 1: Regulating the crystallization of perovskites.
Fig. 2: Characteristics of the pseudo-triple-halide alloyed perovskite.
Fig. 3: Ion migration behaviour and halide phase segregation.
Fig. 4: Performance of single-junction cells and TSCs.

Similar content being viewed by others

Data availability

The authors declare that the experimental data that support the findings of this paper are available within this article and its Supplementary Information files. Other findings in this study are available from the corresponding authors on reasonable request. Source data are provided with this paper.

References

  1. Chen, T. et al. Compromising charge generation and recombination of organic photovoltaics with mixed diluents strategy for certified 19.4% efficiency. Adv. Mater. 35, 2300400 (2023).

    Article  Google Scholar 

  2. Lin, H. et al. Silicon heterojunction solar cells with up to 26.81% efficiency achieved by electrically optimized nanocrystalline-silicon hole contact layers. Nat. Energy 8, 789–799 (2023).

    Article  Google Scholar 

  3. Chen, W. et al. A semitransparent inorganic perovskite film for overcoming ultraviolet light instability of organic solar cells and achieving 14.03% efficiency. Adv. Mater. 30, 1800855 (2018).

    Article  Google Scholar 

  4. Brinkmann, K. O. et al. Perovskite/organic tandem solar cells with indium oxide interconnect. Nature 604, 280–286 (2022).

    Article  Google Scholar 

  5. Chen, W. et al. Monolithic perovskite/organic tandem solar cells with 23.6% efficiency enabled by reduced voltage losses and optimized interconnecting layer. Nat. Energy 7, 229–237 (2022).

    Article  Google Scholar 

  6. Yang, H. et al. Regulating charge carrier recombination in the interconnecting layer to boost the efficiency and stability of monolithic perovskite/organic tandem solar cells. Adv. Mater. 35, 2208604 (2023).

    Article  Google Scholar 

  7. Wang, X. et al. Highly efficient perovskite/organic tandem solar cells enabled by mixed-cation surface modulation. Adv. Mater. 35, 2305946 (2023).

    Article  Google Scholar 

  8. An, Y. et al. Optimizing crystallization in wide-bandgap mixed halide perovskites for high-efficiency solar cells. Adv. Mater. https://doi.org/10.1002/adma.202306568 (2023).

  9. Ma, Z. et al. Transparent recombination electrode with dual-functional transport and protective layer for efficient and stable monolithic perovskite/organic tandem solar cells. Adv. Mater. 35, 2307502 (2023).

    Article  Google Scholar 

  10. Abdi-Jalebi, M. et al. Maximizing and stabilizing luminescence from halide perovskites with potassium passivation. Nature 555, 497–501 (2018).

    Article  Google Scholar 

  11. Yang, G. et al. Defect engineering in wide-bandgap perovskites for efficient perovskite-silicon tandem solar cells. Nat. Photon. 16, 588–594 (2022).

    Article  Google Scholar 

  12. Wang, S. et al. Inorganic perovskite surface reconfiguration for stable inverted solar cell with 20.38% efficiency and its application in tandem devices. Adv. Mater. 35, 2300581 (2023).

    Article  Google Scholar 

  13. Tao, L. et al. Stabilizing wide-bandgap halide perovskites through hydrogen bonding. Sci. China Chem. 65, 1650–1660 (2022).

    Article  Google Scholar 

  14. Zhao, Y. et al. A bilayer conducting polymer structure for planar perovskite solar cells with over 1,400 hours operational stability at elevated temperatures. Nat. Energy 7, 144–152 (2022).

    Article  Google Scholar 

  15. Wang, J. et al. Halide homogenization for low energy loss in 2-eV-bandgap perovskites and increased efficiency in all-perovskite triple-junction solar cells. Nat. Energy 9, 70–80 (2024).

    Article  Google Scholar 

  16. Kim, T. et al. Mapping the pathways of photo-induced ion migration in organic–inorganic hybrid halide perovskites. Nat. Commun. 14, 1846 (2023).

    Article  Google Scholar 

  17. Zhan, Y. et al. Elastic lattice and excess charge carrier manipulation in 1D–3D perovskite solar cells for exceptionally long-term operational stability. Adv. Mater. 33, 2105170 (2021).

    Article  Google Scholar 

  18. Yuan, Y. & Huang, J. Ion migration in organometal trihalide perovskite and its impact on photovoltaic efficiency and stability. Acc. Chem. Res. 49, 286–293 (2016).

    Article  Google Scholar 

  19. Kerner, R. A. & Rand, B. P. Linking chemistry at the TiO2/CH3NH3PbI3 interface to current–voltage hysteresis. J. Phys. Chem. Lett. 8, 2298–2303 (2017).

    Article  Google Scholar 

  20. Zhu, W. et al. Ion migration in organic–inorganic hybrid perovskite solar cells: current understanding and perspectives. Small 18, 2105783 (2022).

    Article  Google Scholar 

  21. Draguta, S. et al. Rationalizing the light-induced phase separation of mixed halide organic-inorganic perovskites. Nat. Commun. 8, 200 (2017).

    Article  Google Scholar 

  22. Chen, Z., Brocks, G., Tao, S. & Bobbert, P. A. Unified theory for light-induced halide segregation in mixed halide perovskites. Nat. Commun. 12, 2687 (2021).

    Article  Google Scholar 

  23. Xu, J. et al. Triple-halide wide-bandgap perovskites with suppressed phase segregation for efficient tandems. Science 367, 1097–1104 (2020).

    Article  Google Scholar 

  24. Stoddard, R. J. et al. Enhancing defect tolerance and phase stability of high-bandgap perovskites via guanidinium alloying. ACS Energy Lett. 3, 1261–1268 (2018).

    Article  Google Scholar 

  25. Wang, C. et al. Suppressing phase segregation in wide-bandgap perovskites for monolithic perovskite/organic tandem solar cells with reduced voltage loss. Small 18, 2204081 (2022).

  26. Grater, L. et al. Sterically suppressed phase segregation in 3D hollow mixed halide wide-bandgap perovskites. J. Phys. Chem. Lett. 14, 6157–6162 (2023).

    Article  Google Scholar 

  27. Ruth, A. et al. Vacancy-mediated anion photosegregation kinetics in mixed halide hybrid perovskites: coupled kinetic Monte Carlo and optical measurements. ACS Energy Lett. 3, 2321–2328 (2018).

    Article  Google Scholar 

  28. Liu, H. et al. Suppressing the photoinduced halide segregation in wide-bandgap perovskite solar cells by strain relaxation. Adv. Funct. Mater. 33, 2303673 (2023).

    Article  Google Scholar 

  29. Luo, X. et al. Progress of all-perovskite tandem solar cells: the role of narrow-bandgap absorbers. Sci. China Chem. 64, 218–227 (2021).

    Article  Google Scholar 

  30. Chen, W. et al. Surface reconstruction for stable monolithic all-inorganic perovskite/organic tandem solar cells with over 21% efficiency. Adv. Funct. Mater. 32, 2109321 (2022).

    Article  Google Scholar 

  31. Lin, P.-Y. et al. Revealing the role of thiocyanate for improving the performance of perovskite solar cells. ACS Appl. Energy Mater. 6, 79–88 (2023).

    Article  Google Scholar 

  32. Zhao, Y. et al. Suppressing ion migration in metal halide perovskite via interstitial doping with a trace amount of multivalent cations. Nat. Mater. 21, 1396–1402 (2022).

    Article  Google Scholar 

  33. Chen, H. et al. Regulating surface potential maximizes voltage in all-perovskite tandems. Nature 613, 676–681 (2023).

    Article  Google Scholar 

  34. Wei, L. et al. Phase segregation enhanced ion movement in efficient inorganic CsPbIBr2 solar cells. Adv. Energy Mater. 7, 1700946 (2017).

    Article  Google Scholar 

  35. Wen, J. et al. Steric engineering enables efficient and photostable wide-bandgap perovskites for all-perovskite tandem solar cells. Adv. Mater. 34, 2110356 (2022).

    Article  Google Scholar 

  36. Rau, U. Reciprocity relation between photovoltaic quantum efficiency and electroluminescent emission of solar cells. Phys. Rev. B 76, 085303 (2007).

    Article  Google Scholar 

  37. Lin, R. et al. All-perovskite tandem solar cells with 3D/3D bilayer perovskite heterojunction. Nature 620, 994–1000 (2023).

    Article  Google Scholar 

  38. Kirchartz, T., Rau, U., Kurth, M., Mattheis, J. & Werner, J.H. Comparative study of electroluminescence from Cu(InGa)Se2 and Si solar cells. Thin Solid Films 515, 6238–6242 (2007).

  39. Zeng, Q. et al. A two-terminal all-inorganic perovskite/organic tandem solar cell. Sci. Bull. 64, 885–887 (2019).

    Article  Google Scholar 

  40. Chen, X. et al. Efficient and reproducible monolithic perovskite/organic tandem solar cells with low-loss interconnecting layers. Joule 4, 1594–1606 (2020).

    Article  Google Scholar 

  41. Wang, P. et al. Tuning of the interconnecting layer for monolithic perovskite/organic tandem solar cells with record efficiency exceeding 21%. Nano Lett. 21, 7845–7854 (2021).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant nos. 52325307, 22075194, 52203233, 52273188 and 52102287), the National Key Research and Development Program of China (grant no. 2022YFB4200302 and 2020YFB1506400), Department of Science and Technology of Jiangsu Province (grant no. BE2022023), the National Postdoctoral Program for Innovative Talents (grant no. BX2021205), project funded by China Postdoctoral Science Foundation (grant no. 2022M710102), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), Collaborative Innovation Center of Suzhou Nano Science and Technology, and the Key Laboratory of Polymeric Materials Design and Synthesis for Biomedical Function, Soochow University.

Author information

Authors and Affiliations

Authors

Contributions

W.C., C.J.B. and Yaowen Li conceived the project. Z.Z. and J.C. made the devices and contributed to the performance improvement. X.J. conducted the DFT calculation. Y.S. conducted the GIWAXS measurement and performed the results analysis. Z.Z. and Heyi Yang analysed the MPP stability and impedance spectra. Q.C. measured the absorption spectra and performed the results analysis. Z.Z. and X.C. measured the in situ absorption spectra and PL spectra. S.K. measured the XRD spectra. X.T. encapsulated the devices for certification. H.C., F.Y., Haidi Yang and X.-m.O. participated in the characterizations of devices. Z.Z., W.C., C.J.B., Yaowen Li and Yongfang Li contributed to the results analysis. W.C. and Yaowen Li wrote the paper. W.C., C.J.B., Yaowen Li and Yongfang Li supervised the project. All authors discussed the results and commented on the final paper.

Corresponding authors

Correspondence to Weijie Chen, Christoph J. Brabec or Yaowen Li.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Energy thanks Peter Chen, Byungha Shin and Zonglong Zhu 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 Notes 1–12, Figs. 1–45 and Tables 1–10.

Reporting Summary

Source data

Source Data Fig. 1

Statistical source data.

Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

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

Zhang, Z., Chen, W., Jiang, X. et al. Suppression of phase segregation in wide-bandgap perovskites with thiocyanate ions for perovskite/organic tandems with 25.06% efficiency. Nat Energy 9, 592–601 (2024). https://doi.org/10.1038/s41560-024-01491-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-024-01491-0

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