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:

Improved fatigue behaviour of perovskite solar cells with an interfacial starch–polyiodide buffer layer

Subjects

Abstract

Metal halide perovskite solar cells are expected to lead the revolution in photovoltaics. However, due to their soft and ionic lattice, perovskites are sensitive to external stimuli, and the resulting devices suffer from noticeable fatigue under cyclic stressors in real-world applications. Due to the lack of a fundamental understanding of the metastable dynamics of materials degradation, effective means to alleviate device fatigue under cyclic illumination are lacking. Here we introduce a starch–polyiodide supermolecule as a bifunctional buffer layer at the perovskite interface, which can both suppress ion migration and promote defect self-healing. The modified perovskite solar cells exhibit improved stability by retaining 98% of their original power conversion efficiency after operation for 42 diurnal cycles (12/12 h light/dark cycle). The devices also deliver a power conversion efficiency of 24.3% (certified, 23.9%) and an intense electroluminescence with external quantum efficiencies above 12.0%. Our findings shed light on how supramolecular chemistry modulates the metastable dynamics of degradation in perovskites and other materials with soft lattices.

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: Properties of Starch-I supermolecule and its interaction with the perovskite.
Fig. 2: Characterization of ionic behaviour in perovskites.
Fig. 3: Characterization of PL recovery on perovskite films with and without Starch-I.
Fig. 4: Characterization of the perovskite films and devices with and without Starch-I.
Fig. 5: Photovoltaic performance and operational stability of the devices.

Similar content being viewed by others

Data availability

All the data supporting the findings of this study are available within this Article and its Supplementary Information. Any additional information can be obtained from the corresponding authors on reasonable request.

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).

    Google Scholar 

  2. Kim, H.-S. et al. Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%. Sci. Rep. 2, 591 (2012).

    Google Scholar 

  3. Li, N., Niu, X., Chen, Q. & Zhou, H. Towards commercialization: the operational stability of perovskite solar cells. Chem. Soc. Rev. 49, 8235–8286 (2020).

    Google Scholar 

  4. Tumen‐Ulzii, G. et al. Detrimental effect of unreacted PbI2 on the long‐term stability of perovskite solar cells. Adv. Mater. 32, 1905035 (2020).

    Google Scholar 

  5. Wang, L. et al. A Eu3+-Eu2+ ion redox shuttle imparts operational durability to Pb-I perovskite solar cells. Science 363, 265–270 (2019).

    ADS  Google Scholar 

  6. Zhang, Y. & Zhou, H. Intrinsic stability of organic-inorganic hybrid perovskite. Acta Phys. Sin. 68, 158804 (2019).

    Google Scholar 

  7. Wang, Y. et al. Stabilizing heterostructures of soft perovskite semiconductors. Science 365, 687–691 (2019).

    ADS  Google Scholar 

  8. Domanski, K. et al. Migration of cations induces reversible performance losses over day/night cycling in perovskite solar cells. Energy Environ. Sci. 10, 604–613 (2017).

    Google Scholar 

  9. Schwenzer, J. A. et al. Temperature variation-induced performance decline of perovskite solar cells. ACS Appl. Mater. Interfaces 10, 16390–16399 (2018).

    Google Scholar 

  10. Zai, H., Ma, Y., Chen, Q. & Zhou, H. Ion migration in halide perovskite solar cells: mechanism, characterization, impact and suppression. J. Energy Chem. 63, 528–549 (2021).

    Google Scholar 

  11. Zhao, C. et al. Revealing underlying processes involved in light soaking effects and hysteresis phenomena in perovskite solar cells. Adv. Energy Mater. 5, 1500279 (2015).

    Google Scholar 

  12. Nie, W. et al. Light-activated photocurrent degradation and self-healing in perovskite solar cells. Nat. Commun. 7, 11574 (2016).

    ADS  Google Scholar 

  13. Zhou, S. et al. Thin film electrochemical capacitors based on organolead triiodide perovskite. Adv. Electron. Mater. 2, 1600114 (2016).

    Google Scholar 

  14. Finkenauer, B. P., Akriti, Ma, K. & Dou, L. Degradation and self-healing in perovskite solar cells. ACS Appl. Mater. Interfaces 14, 24073–24088 (2022).

    Google Scholar 

  15. Yu, Y., Zhang, F. & Yu, H. Self-healing perovskite solar cells. Sol. Energy 209, 408–414 (2020).

    ADS  Google Scholar 

  16. Huang, F. et al. Fatigue behavior of planar CH3NH3PbI3 perovskite solar cells revealed by light on/off diurnal cycling. Nano Energy 27, 509–514 (2016).

    Google Scholar 

  17. Khenkin, M. V. et al. Consensus statement for stability assessment and reporting for perovskite photovoltaics based on ISOS procedures. Nat. Energy 5, 35–49 (2020).

    ADS  Google Scholar 

  18. Azpiroz, J. M., Mosconi, E., Bisquert, J. & De Angelis, F. Defect migration in methylammonium lead iodide and its role in perovskite solar cell operation. Energy Environ. Sci. 8, 2118–2127 (2015).

    Google Scholar 

  19. Jiang, L. et al. Fatigue stability of CH3NH3PbI3 based perovskite solar cells in day/night cycling. Nano Energy 58, 687–694 (2019).

    Google Scholar 

  20. Khenkin, M. V. et al. Dynamics of photoinduced degradation of perovskite photovoltaics: from reversible to irreversible processes. ACS Appl. Energy Mater. 1, 799–806 (2018).

    Google Scholar 

  21. Domanski, K., Alharbi, E. A., Hagfeldt, A., Grätzel, M. & Tress, W. Systematic investigation of the impact of operation conditions on the degradation behaviour of perovskite solar cells. Nat. Energy 3, 61–67 (2018).

    ADS  Google Scholar 

  22. Li, N. et al. Cation and anion immobilization through chemical bonding enhancement with fluorides for stable halide perovskite solar cells. Nat. Energy 4, 408–415 (2019).

    ADS  Google Scholar 

  23. Son, D.-Y. et al. Universal approach toward hysteresis-free perovskite solar cell via defect engineering. J. Am. Chem. Soc. 140, 1358–1364 (2018).

    Google Scholar 

  24. Bai, S. et al. Planar perovskite solar cells with long-term stability using ionic liquid additives. Nature 571, 245–250 (2019).

    ADS  Google Scholar 

  25. Liu, Y. et al. Ultrahydrophobic 3D/2D fluoroarene bilayer-based water-resistant perovskite solar cells with efficiencies exceeding 22%. Sci. Adv. 5, eaaw2543 (2019).

    ADS  Google Scholar 

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

    ADS  Google Scholar 

  27. Copeland, L., Blazek, J., Salman, H. & Tang, M. C. Form and functionality of starch. Food Hydrocoll. 23, 1527–1534 (2009).

    Google Scholar 

  28. Madhu, S. et al. Infinite polyiodide chains in the pyrroloperylene–iodine complex: insights into the starch–iodine and perylene–iodine complexes. Angew. Chem. Int. Ed. 55, 8032–8035 (2016).

    Google Scholar 

  29. Teitelbaum, R. C., Ruby, S. L. & Marks, T. J. On the structure of starch-iodine. J. Am. Chem. Soc. 100, 3215–3217 (1978).

    Google Scholar 

  30. Shlenskaya, N. N., Goodilin, E. A. & Tarasov, A. B. Isolation of methylammonium room temperature reactive polyiodide melt into a new starch complex. Mendeleev Commun. 28, 242–244 (2018).

    Google Scholar 

  31. Zhou, H., Yamada, T. & Kimizuka, N. Supramolecular thermocells based on thermo-responsiveness of host–guest chemistry. Bull. Chem. Soc. Jpn 94, 1525–1546 (2021).

    Google Scholar 

  32. Nozaki, K. Iodometric method of analysis for organic peroxides. Ind. Eng. Chem. Res. 18, 583 (1946).

    Google Scholar 

  33. Yang, X. et al. Buried interfaces in halide perovskite photovoltaics. Adv. Mater. 33, 2006435 (2021).

    Google Scholar 

  34. Li, L. et al. Carrier-activated polarization in organometal halide perovskites. J. Phys. Chem. C 120, 2536–2541 (2016).

    ADS  Google Scholar 

  35. Richardson, G. et al. Can slow-moving ions explain hysteresis in the current–voltage curves of perovskite solar cells? Energy Environ. Sci. 9, 1476–1485 (2016).

    Google Scholar 

  36. Hooper, K. et al. Probing the degradation and homogeneity of embedded perovskite semiconducting layers in photovoltaic devices by Raman spectroscopy. Phys. Chem. Chem. Phys. 19, 5246–5253 (2017).

    Google Scholar 

  37. Ledinsky, M. et al. Raman spectroscopy of organic–inorganic halide perovskites. J. Phys. Chem. Lett. 6, 401–406 (2015).

    Google Scholar 

  38. Zhao, Y. et al. A polymer scaffold for self-healing perovskite solar cells. Nat. Commun. 7, 10228 (2016).

    ADS  Google Scholar 

  39. Peng, H. et al. Structurally reinforced all‐inorganic CsPbI2Br perovskite by nonionic polymer via coordination and hydrogen bonds. Sol. RRL 4, 2000216 (2020).

    Google Scholar 

  40. Jo, B. et al. Cross-linked perovskite/polymer using sodium borate composites for efficient and stable perovskite solar cells. J. Mater. Chem. A 10, 14884–14893 (2022).

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

    ADS  Google Scholar 

  42. Cheng, Y. et al. Revealing the degradation and self‐healing mechanisms in perovskite solar cells by sub‐bandgap external quantum efficiency spectroscopy. Adv. Mater. 33, 2006170 (2021).

    Google Scholar 

  43. Shlenskaya, N. N., Belich, N. A., Grätzel, M., Goodilin, E. A. & Tarasov, A. B. Light-induced reactivity of gold and hybrid perovskite as a new possible degradation mechanism in perovskite solar cells. J. Mater. Chem. A 6, 1780–1786 (2018).

    Google Scholar 

  44. 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).

    ADS  Google Scholar 

  45. Game, O. S., Buchsbaum, G. J., Zhou, Y., Padture, N. P. & Kingon, A. I. Ions matter: description of the anomalous electronic behavior in methylammonium lead halide perovskite devices. Adv. Funct. Mater. 27, 1606584 (2017).

    Google Scholar 

  46. 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).

    Google Scholar 

  47. Khenkin, M. V. et al. Reconsidering figures of merit for performance and stability of perovskite photovoltaics. Energy Environ. Sci. 11, 739–743 (2018).

    Google Scholar 

  48. Duong, T. et al. Rubidium multication perovskite with optimized bandgap for perovskite‐silicon tandem with over 26% efficiency. Adv. Energy Mater. 7, 1700228 (2017).

    ADS  Google Scholar 

  49. Rundle, R. & French, D. The configuration of starch in the starch-iodine complex. III. X-ray diffraction studies of the starch-iodine complex. J. Am. Chem. Soc. 65, 1707–1710 (1943).

    Google Scholar 

Download references

Acknowledgements

We thank J. Zhou (Peking University) for her support in the discussions and characterizations. We acknowledge the data analysis of X-ray sources from Y. Ma and Y. Wang of Jiangnan University. We thank X. Wang (Peking University) for his help with the use of confocal fluorescence microscopy; J. Shi and Q. Meng (Institute of Physics, CAS) for the modulated transient photocurrent measurements; J. Wang (Nanjing Tech University) for the PLQY measurement; and H. Yan (The Hong Kong University of Science and Technology) for the secondary ion mass spectrometry measurements. We thank Y. Jiang (Peking University) for help with the operation of the stylus profilometer. H. Zhou acknowledges the National Key Research and Development Program of China (grant no. 2020YFB1506400), the National Natural Science Foundation of China (grant nos. 52125206 and 51972004) and the New Cornerstone Science Foundation through the XPLORER PRIZE. G.L. acknowledges the National Natural Science Foundation of China (grant no. 52202241).

Author information

Authors and Affiliations

Authors

Contributions

Y.Z. and H. Zhou conceived the project. Y.Z. prepared the samples, fabricated and characterized the devices, performed the stability test, analysed the data and wrote the first draft of the manuscript. H. Zhou supervised the project. Q.S. designed and performed the density functional theory calculations. Y.C., N.L., Z.Q., W.Z. and Z.G. contributed to the PL and scanning electron microscopy measurements. Z.G. helped with the EL measurements. X.N. helped with the EQE, PL mapping and XPS measurements. G.L. helped build the light/dark cycle stability test equipment. W.H. conducted the grazing-incidence wide-angle X-ray scattering measurements. Y.B., Y.C., N.L., Z.H., C.Z., S.M. and H. Zai contributed to the fabrication of high-performance PSCs. Y.Z., Q.C. and H. Zhou revised the manuscript. All authors contributed to the discussion and commented on the manuscript.

Corresponding author

Correspondence to Huanping Zhou.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Photonics thanks Davide Raffaele Ceratti 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. 1–39, Notes 1–14 and Tables 1–7.

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, Y., Song, Q., Liu, G. et al. Improved fatigue behaviour of perovskite solar cells with an interfacial starch–polyiodide buffer layer. Nat. Photon. 17, 1066–1073 (2023). https://doi.org/10.1038/s41566-023-01287-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41566-023-01287-w

This article is cited by

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