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Evolution of defects during the degradation of metal halide perovskite solar cells under reverse bias and illumination

Nature Energy volume 7, pages 65–73 (2022)Cite this article

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Abstract

The efficiency and stability of perovskite solar cells are essentially determined by defects in the perovskite layer, yet their chemical nature and linking with the degradation mechanism of devices remain unclear. Here we uncover where degradation occurs and the underlying mechanisms and defects involved in the performance degradation of p–i–n perovskite solar cells under illumination or reverse bias. Light-induced degradation starts with the generation of iodide interstitials at the interfacial region between the perovskite and both charge transport layers. While we observe trap annihilation of two types of iodide defect at the anode side, we find negatively charged iodide interstitials near the cathode side, which we show to be more detrimental to the solar cell efficiency. The reverse-bias degradation is initialized by the interaction between iodide interstitials and injected holes at the interface between the electron transport layer and the perovskite. Introducing a hole-blocking layer between the layers suppresses this interaction, improving the reverse-bias stability.

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Fig. 1: Degradation of thin single-crystal perovskite solar cell under reverse bias.
Fig. 2: Degradation of polycrystalline thin film perovskite solar cells under reverse bias.
Fig. 3: Identifying the chemical nature of traps in iodide perovskites.
Fig. 4: Improving the stability of perovskite solar cells under reverse bias.
Fig. 5: Degradation mechanism of perovskite solar cells under illumination.

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All data generated or analysed during this study are included in the article, its Supplementary Information and its data source. Source data are provided with this paper.

References

  1. Queisser, H. J. & Haller, E. E. Defects in semiconductors: some fatal, some vital. Science 281, 945–950 (1998).

    Article  Google Scholar 

  2. Jin, H. et al. It’s a trap! On the nature of localised states and charge trapping in lead halide perovskites. Mater. Horizons 7, 397–410 (2020).

    Article  Google Scholar 

  3. Ball, J. M. & Petrozza, A. Defects in perovskite-halides and their effects in solar cells. Nat. Energy 1, 16149 (2016).

    Article  Google Scholar 

  4. Ono, L. K., Liu, S. F. & Qi, Y. Reducing detrimental defects for high‐performance metal halide perovskite solar cells. Angew. Chem. Int. Ed. 59, 2–25 (2020).

    Article  Google Scholar 

  5. Best research-cell efficiency chart. NREL https://www.nrel.gov/pv/cell-efficiency.html (2021).

  6. Chen, B., Rudd, P. N., Yang, S., Yuan, Y. & Huang, J. Imperfections and their passivation in halide perovskite solar cells. Chem. Soc. Rev. 48, 3842–3867 (2019).

    Article  Google Scholar 

  7. Gao, F., Zhao, Y., Zhang, X. & You, J. Recent progresses on defect passivation toward efficient perovskite solar cells. Adv. Energy Mater. 10, 1902650 (2020).

    Article  Google Scholar 

  8. Aydin, E., De Bastiani, M. & De Wolf, S. Defect and contact passivation for perovskite solar cells. Adv. Mater. 31, e1900428 (2019).

    Article  Google Scholar 

  9. Yang, S. et al. Stabilizing halide perovskite surfaces for solar cell operation with wide-bandgap lead oxysalts. Science 365, 473–478 (2019).

    Article  Google Scholar 

  10. Lin, Y.-H. et al. A piperidinium salt stabilizes efficient metal-halide perovskite solar cells. Science 369, 96–102 (2020).

    Article  Google Scholar 

  11. Hui, Y. et al. Stability of perovskite thin films under working condition: bias‐dependent degradation and grain boundary effects. Adv. Funct. Mater. 31, 2103894 (2021).

    Article  Google Scholar 

  12. Hailegnaw, B., Sariciftci, N. S. & Scharber, M. C. Impedance spectroscopy of perovskite solar cells: studying the dynamics of charge carriers before and after continuous operation. Phys. Status Solidi A 217, 2000291 (2020).

    Article  Google Scholar 

  13. Xie, H. et al. Decoupling the effects of defects on efficiency and stability through phosphonates in stable halide perovskite solar cells. Joule 5, 1246–1266 (2021).

    Article  Google Scholar 

  14. Wu, J. et al. Quantifying the interface defect for the stability origin of perovskite solar cells. Adv. Energy Mater. 9, 1901352 (2019).

    Article  Google Scholar 

  15. Yin, W.-J., Shi, T. & Yan, Y. Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber. Appl. Phys. Lett. 104, 063903 (2014).

    Article  Google Scholar 

  16. Meggiolaro, D. et al. Iodine chemistry determines the defect tolerance of lead-halide perovskites. Energy Environ. Sci. 11, 702–713 (2018).

    Article  Google Scholar 

  17. Du, M.-H. Density functional calculations of native defects in CH3NH3PbI3: effects of spin–orbit coupling and self-interaction error. J. Phys. Chem. Lett. 6, 1461–1466 (2015).

    Article  Google Scholar 

  18. Motti, S. G. et al. Controlling competing photochemical reactions stabilizes perovskite solar cells. Nat. Photon. 13, 532–539 (2019).

    Article  Google Scholar 

  19. Zhang, X., Turiansky, M. E., Shen, J.-X. & Van de Walle, C. G. Iodine interstitials as a cause of nonradiative recombination in hybrid perovskites. Phys. Rev. B 101, 140101 (2020).

    Article  Google Scholar 

  20. Reichert, S. et al. Probing the ionic defect landscape in halide perovskite solar cells. Nat. Commun. 11, 6098 (2020).

    Article  Google Scholar 

  21. Tan, S. et al. Shallow iodine defects accelerate the degradation of α-phase formamidinium perovskite. Joule 4, 2426–2442 (2020).

    Article  Google Scholar 

  22. Wang, R. et al. Unraveling the surface state of photovoltaic perovskite thin film. Matter 4, 2417–2428 (2021).

    Article  Google Scholar 

  23. Walter, T., Herberholz, R., Müller, C. & Schock, H. W. Determination of defect distributions from admittance measurements and application to Cu(In,Ga)Se2 based heterojunctions. J. Appl. Phys. 80, 4411–4420 (1996).

    Article  Google Scholar 

  24. Ni, Z. et al. Resolving spatial and energetic distributions of trap states in metal halide perovskite solar cells. Science 367, 1352–1358 (2020).

    Article  Google Scholar 

  25. Heath, J. T., Cohen, J. D. & Shafarman, W. N. Bulk and metastable defects in CuIn1−xGaxSe2 thin films using drive-level capacitance profiling. J. Appl. Phys. 95, 1000–1010 (2004).

    Article  Google Scholar 

  26. Chen, Z. et al. Thin single crystal perovskite solar cells to harvest below-bandgap light absorption. Nat. Commun. 8, 1890 (2017).

    Article  Google Scholar 

  27. Karlsson, M. et al. Mixed halide perovskites for spectrally stable and high-efficiency blue light-emitting diodes. Nat. Commun. 12, 361 (2021).

    Article  Google Scholar 

  28. Awni, R. A. et al. Influence of charge transport layers on capacitance measured in halide perovskite solar cells. Joule 4, 644–657 (2020).

    Article  Google Scholar 

  29. Futscher, M. H. et al. Quantification of ion migration in CH3NH3PbI3 perovskite solar cells by transient capacitance measurements. Mater. Horizons 6, 1497–1503 (2019).

    Article  Google Scholar 

  30. Nguyen, H. T., Nguyen, D. D. & Spanget-Larsen, J. Ionic reaction products of iodine with pyridine, 4-methylpyridine, and 4-tert-butylpyridine in a polyethylene matrix. A FTIR polarization spectroscopic investigation. Chem. Phys. Lett. 716, 119–125 (2019).

    Article  Google Scholar 

  31. Chen, P. et al. In situ growth of 2D perovskite capping layer for stable and efficient perovskite solar cells. Adv. Funct. Mater. 28, 1706923 (2018).

    Article  Google Scholar 

  32. Huang, W., Sadhu, S. & Ptasinska, S. Heat- and gas-induced transformation in CH3NH3PbI3 perovskites and its effect on the efficiency of solar cells. Chem. Mater. 29, 8478–8485 (2017).

    Article  Google Scholar 

  33. Zhang, W., Ensing, B., Rothenberg, G. & Raveendran Shiju, N. Designing effective solid catalysts for biomass conversion: aerobic oxidation of ethyl lactate to ethyl pyruvate. Green Chem. 20, 1866–1873 (2018).

    Article  Google Scholar 

  34. Shao, Y., Xiao, Z., Bi, C., Yuan, Y. & Huang, J. Origin and elimination of photocurrent hysteresis by fullerene passivation in CH3NH3PbI3 planar heterojunction solar cells. Nat. Commun. 5, 5784 (2014).

    Article  Google Scholar 

  35. Wang, Q. et al. Qualifying composition dependent p and n self-doping in CH3NH3PbI3. Appl. Phys. Lett. 105, 163508 (2014).

    Article  Google Scholar 

  36. Chen, S., Xiao, X., Gu, H. & Huang, J. Iodine reduction for reproducible and high-performance perovskite solar cells and modules. Sci. Adv. 7, eabe8130 (2021).

    Article  Google Scholar 

  37. Deng, Y. et al. Defect compensation in formamidinium–caesium perovskites for highly efficient solar mini-modules with improved photostability. Nat. Energy 6, 633–641 (2021).

    Article  Google Scholar 

  38. Bowring, A. R., Bertoluzzi, L., O’Regan, B. C. & McGehee, M. D. Reverse bias behavior of halide perovskite solar cells. Adv. Energy Mater. 8, 1702365 (2018).

    Article  Google Scholar 

  39. Razera, R. A. Z. et al. Instability of p–i–n perovskite solar cells under reverse bias. J. Mater. Chem. A 8, 242–250 (2020).

    Article  Google Scholar 

  40. Chen, Y. & Zhou, H. Defects chemistry in high-efficiency and stable perovskite solar cells. J. Appl. Phys. 128, 060903 (2020).

    Article  Google Scholar 

  41. Xiao, Z. et al. Giant switchable photovoltaic effect in organometal trihalide perovskite devices. Nat. Mater. 14, 193–198 (2015).

    Article  Google Scholar 

  42. Samu, G. F. et al. Electrochemical hole injection selectively expels iodide from mixed halide perovskite films. J. Am. Chem. Soc. 141, 10812–10820 (2019).

    Article  Google Scholar 

  43. Jiang, Q. et al. Enhanced electron extraction using SnO2 for high-efficiency planar-structure HC(NH2)2PbI3-based perovskite solar cells. Nat. Energy 2, 16177 (2016).

    Article  Google Scholar 

  44. Christians, J. A. et al. Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability. Nat. Energy 3, 68–74 (2018).

    Article  Google Scholar 

  45. Xie, L. et al. Revealing the compositional effect on the intrinsic long-term stability of perovskite solar cells. J. Mater. Chem. A 8, 7653–7658 (2020).

    Article  Google Scholar 

  46. Lin, Y. et al. Excess charge-carrier induced instability of hybrid perovskites. Nat. Commun. 9, 4981 (2018).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Center for Hybrid Organic Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, Office of Science, within the US Department of Energy. We thank V. Blum in the Department of Mechanical Engineering and Material Science of Duke University for insightful discussions.

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Authors and Affiliations

  1. Department of Applied Physical Sciences, University of North Carolina, Chapel Hill, NC, USA

    Zhenyi Ni, Haoyang Jiao, Chengbin Fei, Hangyu Gu, Shuang Xu, Zhenhua Yu, Guang Yang, Yehao Deng, Qi Jiang, Ye Liu & Jinsong Huang

  2. Department of Physics and Astronomy and Wright Center for Photovoltaics Innovation and Commercialization, University of Toledo, Toledo, OH, USA

    Yanfa Yan

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Contributions

J.H. and Z.N. conceived the idea and designed the experiments. Z.N., H.J., C.F., H.G., S.X., G.Y. and Q.J. fabricated the perovskite polycrystalline thin film solar cells. Z.N. and Y.L. synthesized the perovskite thin single crystals. Z.N. and S.X. carried out the measurements for the devices. Z.Y. performed the ALD for the devices. Y.Y. participated in data analyses and project discussion. Y.D. did the TPC measurement. Z.N. and J.H. wrote the Article, and all authors reviewed it.

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Correspondence to Jinsong Huang.

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Supplementary Information

Supplementary Figs. 1–26, Notes 1–4, Table 1 and Refs. 1–4.

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Source data point for Fig. 1c.

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Ni, Z., Jiao, H., Fei, C. et al. Evolution of defects during the degradation of metal halide perovskite solar cells under reverse bias and illumination. Nat Energy 7, 65–73 (2022). https://doi.org/10.1038/s41560-021-00949-9

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