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:

Degradation mechanisms of perovskite solar cells under vacuum and one atmosphere of nitrogen

Nature Energy volume 6, pages 977–986 (2021)Cite this article

Subjects

An Author Correction to this article was published on 30 March 2022

This article has been updated

Abstract

Extensive studies have focused on improving the operational stability of perovskite solar cells, but few have surveyed the fundamental degradation mechanisms. One aspect overlooked in earlier works is the effect of the atmosphere on device performance during operation. Here we investigate the degradation mechanisms of perovskite solar cells operated under vacuum and under a nitrogen atmosphere using synchrotron radiation-based operando grazing-incidence X-ray scattering methods. Unlike the observations described in previous reports, we find that light-induced phase segregation, lattice shrinkage and morphology deformation occur under vacuum. Under nitrogen, only lattice shrinkage appears during the operation of solar cells, resulting in better device stability. The different behaviour under nitrogen is attributed to a larger energy barrier for lattice distortion and phase segregation. Finally, we find that the migration of excessive PbI2 to the interface between the perovskite and the hole transport layer degrades the performance of devices under vacuum or under nitrogen.

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: Structure and performance of the devices analysed.
Fig. 2: Structure evolution of MAFA PSCs operating in different atmospheres.
Fig. 3: Morphology evolution of MAFA PSCs operating in different atmospheres.
Fig. 4: The thermodynamic driving force of lattice shrinkage and phase segregation.
Fig. 5: Degradation mechanisms of MAFA PSCs under the ISOS-L-1I protocol in different atmospheres.

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 and source data files. The data can also be found at the following public repository: https://doi.org/10.14459/2021mp1620140.

Change history

References

  1. Rong, Y. et al. Challenges for commercializing perovskite solar cells. Science 361, eaat8235 (2018).

    Article  Google Scholar 

  2. Jeon, N. J. et al. Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells. Nat. Mater. 13, 897–903 (2014).

    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. Yang, W. S. et al. Iodide management in formamidinium-lead-halide-based perovskite layers for efficient solar cells. Science 356, 1376–1379 (2017).

    Article  Google Scholar 

  5. National Renewable Energy Laboratory Best Research-Cell Efficiencies https://www.nrel.gov/pv/cell-efficiency.html (2021).

  6. Cardinaletti, I. et al. Organic and perovskite solar cells for space applications. Sol. Energy Mater. Sol. Cells 182, 121–127 (2018).

    Article  Google Scholar 

  7. Tu, Y. et al. Mixed-cation perovskite solar cells in space. Sci. China Phys. Mech. Astron. 62, 974221 (2019).

    Article  Google Scholar 

  8. Reb, L. K. et al. Perovskite and organic solar cells on a rocket flight. Joule 4, 1880–1892 (2020).

    Article  Google Scholar 

  9. Deretzis, I. et al. Stability and degradation in hybrid perovskites: is the glass half-empty or half-full? J. Phys. Chem. Lett. 9, 3000–3007 (2018).

    Article  Google Scholar 

  10. Mahesh, S. et al. Revealing the origin of voltage loss in mixed-halide perovskite solar cells. Energy Environ. Sci. 13, 258–267 (2020).

    Article  Google Scholar 

  11. Li, N. et al. Microscopic degradation in formamidinium-cesium lead iodide perovskite solar cells under operational stressors. Joule 4, 1743–1758 (2020).

    Article  Google Scholar 

  12. Tsai, H. et al. Light-induced lattice expansion leads to high-efficiency perovskite solar cells. Science 360, 67–70 (2018).

    Article  Google Scholar 

  13. Rolston, N. et al. Comment on ‘Light-induced lattice expansion leads to high-efficiency perovskite solar cells’. Science 368, eaay8691 (2020).

    Article  Google Scholar 

  14. 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).

    Article  Google Scholar 

  15. 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).

    Article  Google Scholar 

  16. Zhou, Q. et al. High-performance perovskite solar cells with enhanced environmental stability based on a (p-FC6H4C2H4NH3)2[PbI4] capping layer. Adv. Energy Mater. 9, 1802595 (2019).

    Article  Google Scholar 

  17. Bi, D. et al. Efficient luminescent solar cells based on tailored mixed-cation perovskites. Sci. Adv. 2, e1501170 (2016).

    Article  Google Scholar 

  18. Jesper Jacobsson, T. et al. Exploration of the compositional space for mixed lead halogen perovskites for high efficiency solar cells. Energy Environ. Sci. 9, 1706–1724 (2016).

    Article  Google Scholar 

  19. Zhang, Y. et al. Trash into treasure: δ-FAPbI3 polymorph stabilized MAPbI3 perovskite with power conversion efficiency beyond 21%. Adv. Mater. 30, 1707143 (2018).

    Article  Google Scholar 

  20. Jiang, Q. et al. Planar-structure perovskite solar cells with efficiency beyond 21%. Adv. Mater. 29, 1703852 (2017).

    Article  Google Scholar 

  21. Roose, B., Dey, K., Chiang, Y.-H., Friend, R. H. & Stranks, S. D. Critical assessment of the use of excess lead iodide in lead halide perovskite solar cells. J. Phys. Chem. Lett. 11, 6505–6512 (2020).

    Article  Google Scholar 

  22. Beal, R. E. et al. Structural origins of light-induced phase segregation in organic-inorganic halide perovskite photovoltaic materials. Matter 2, 207–219 (2020).

    Article  Google Scholar 

  23. Hoke, E. T. et al. Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics. Chem. Sci. 6, 613–617 (2015).

    Article  Google Scholar 

  24. Banerjee, S. & Mukhopadhay, P. Pergamon Materials Series: Phase Transformations Vol. 12, 783–800 (Pergamon, 2007).

  25. Gleiter, H. in Physical Metallurgy 4th edn (eds Cahn, R. W. & Haasen, P.) 843–942 (North-Holland, 1996).

  26. Lu, K., Lu, L. & Suresh, S. Strengthening materials by engineering coherent internal boundaries at the nanoscale. Science 324, 349–352 (2009).

    Article  Google Scholar 

  27. Jariwala, S. et al. Local crystal misorientation influences non-radiative recombination in halide perovskites. Joule 3, 3048–3060 (2019).

    Article  Google Scholar 

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

    Article  Google Scholar 

  29. Agnew, S. R. in Advances in Wrought Magnesium Alloys (eds Bettles, C. & Barnett, M.) 63–104 (Woodhead Publishing, 2012).

  30. Eperon, G. E. et al. The role of dimethylammonium in bandgap modulation for stable halide perovskites. ACS Energy Lett. 5, 1856–1864 (2020).

    Article  Google Scholar 

  31. Brunauer, S., Deming, L. S., Deming, W. E. & Teller, E. On a theory of the van der Waals adsorption of gases. J. Am. Chem. Soc. 62, 1723–1732 (1940).

    Article  Google Scholar 

  32. Hutter, E. M. et al. Thermodynamic stabilization of mixed-halide perovskites against phase segregation. Cell Rep. Phys. Sci. 1, 100120 (2020).

    Article  Google Scholar 

  33. Muscarella, L. A. et al. Lattice compression increases the activation barrier for phase segregation in mixed-halide perovskites. ACS Energy Lett. 5, 3152–3158 (2020).

    Article  Google Scholar 

  34. Hu, Z. et al. The impact of atmosphere on energetics of lead halide perovskites. Adv. Energy Mater. 10, 2000908 (2020).

    Article  Google Scholar 

  35. Juarez-Perez, E. J. et al. Photoinduced giant dielectric constant in lead halide perovskite solar cells. J. Phys. Chem. Lett. 5, 2390–2394 (2014).

    Article  Google Scholar 

  36. Ahmadi, M. et al. Environmental gating and galvanic effects in single crystals of organic–inorganic halide perovskites. ACS Appl. Mater. Interfaces 11, 14722–14733 (2019).

    Article  Google Scholar 

  37. Wang, X. et al. Suppressed phase separation of mixed-halide perovskites confined in endotaxial matrices. Nat. Commun. 10, 695 (2019).

    Article  Google Scholar 

  38. Erkey, C. in Supercritical Fluid Science and Technology Vol. 1 (ed. Erkey, C.) 41–77 (Elsevier, 2011).

  39. Alberti, A. et al. Nitrogen soaking promotes lattice recovery in polycrystalline hybrid perovskites. Adv. Energy Mater. 9, 1803450 (2019).

    Article  Google Scholar 

  40. Correa Baena, J. P. et al. Highly efficient planar perovskite solar cells through band alignment engineering. Energy Environ. Sci. 8, 2928–2934 (2015).

    Article  Google Scholar 

  41. Jiang, Y. et al. Mitigation of vacuum and illumination-induced degradation in perovskite solar cells by structure engineering. Joule 4, 1087–1103 (2020).

    Article  Google Scholar 

  42. Burgelman, M., Nollet, P. & Degrave, S. Modelling polycrystalline semiconductor solar cells. Thin Solid Films 361–362, 527–532 (2000).

    Article  Google Scholar 

  43. Jeangros, Q. et al. In situ TEM analysis of organic–inorganic metal-halide perovskite solar cells under electrical bias. Nano Lett. 16, 7013–7018 (2016).

    Article  Google Scholar 

  44. Kaienburg, P. et al. How contact layers control shunting losses from pinholes in thin-film solar cells. J. Phys. Chem. C 122, 27263–27272 (2018).

    Article  Google Scholar 

  45. 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 

  46. Saliba, M. et al. How to make over 20% efficient perovskite solar cells in regular (n–i–p) and inverted (p–i–n) architectures. Chem. Mater. 30, 4193–4201 (2018).

    Article  Google Scholar 

  47. Buffet, A. et al. P03, the microfocus and nanofocus X-ray scattering (MiNaXS) beamline of the PETRA III storage ring: the microfocus endstation. J. Synchrotron Radiat. 19, 647–653 (2012).

    Article  Google Scholar 

  48. Chen, W. et al. Operando structure degradation study of PbS quantum dot solar cells. Energy Environ. Sci. 14, 3420–3429 (2021).

    Article  Google Scholar 

  49. Gunthard, B., Wolfgang, W., Chenghao, L., Stephan, V. R. & Peter, F. A customizable software for fast reduction and analysis of large X-ray scattering data sets: applications of the new DPDAK package to small-angle X-ray scattering and grazing-incidence small-angle X-ray scattering. J. Appl. Crystallogr. 47, 1797–1803 (2014).

    Article  Google Scholar 

  50. Jiang, Z. GIXSGUI: a MATLAB toolbox for grazing-incidence X-ray scattering data visualization and reduction, and indexing of buried three-dimensional periodic nanostructured films. J. Apppl. Crystallogr. 48, 917–926 (2015).

    Article  Google Scholar 

  51. Xie, L.-Q. et al. Understanding the cubic phase stabilization and crystallization kinetics in mixed cations and halides perovskite single crystals. J. Am. Chem. Soc. 139, 3320–3323 (2017).

    Article  Google Scholar 

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

    Article  Google Scholar 

  53. Clerc, D. G. & Cleary, D. A. Spinodal decomposition as an interesting example of the application of several thermodynamic principles. J. Chem. Educ. 72, 112 (1995).

    Article  Google Scholar 

  54. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  Google Scholar 

  55. Perdew, J. P. et al. Restoring the density-gradient expansion for exchange in solids and surfaces. Phys. Rev. Lett. 100, 136406 (2008).

    Article  Google Scholar 

  56. Umari, P., Mosconi, E. & De Angelis, F. Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications. Sci. Rep. 4, 4467 (2014).

    Article  Google Scholar 

  57. Brivio, F., Butler, K. T., Walsh, A. & van Schilfgaarde, M. Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers. Phys. Rev. B 89, 155204 (2014).

    Article  Google Scholar 

  58. Thind, A. S., Huang, X., Sun, J. & Mishra, R. First-principles prediction of a stable hexagonal phase of CH3NH3PbI3. Chem. Mater. 29, 6003–6011 (2017).

    Article  Google Scholar 

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

    Article  Google Scholar 

  60. Calado, P. et al. Evidence for ion migration in hybrid perovskite solar cells with minimal hysteresis. Nat. Commun. 7, 13831 (2016).

    Article  Google Scholar 

  61. Miyata, A. et al. Direct measurement of the exciton binding energy and effective masses for charge carriers in organic–inorganic tri-halide perovskites. Nat. Phys. 11, 582–587 (2015).

    Article  Google Scholar 

Download references

Acknowledgements

Financial support from Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) via Germany´s Excellence Strategy – EXC 2089/1 – 390776260 (e-conversion) and via International Research Training Group 2022 Alberta/Technical University of Munich International Graduate School for Environmentally Responsible Functional Materials (ATUMS), as well as from TUM.solar in the context of the Bavarian Collaborative Research Project Solar Technologies Go Hybrid (SolTech) is acknowledged. L.D. thanks the Cambridge Trust and R.G., W.C., L.D., N.L., T.X. and S. Liang acknowledge financial support from the Chinese Scholarship Council (CSC). S.P. acknowledges support from the TUM International Graduate School of Science and Engineering (IGSSE) via the GreenTech Initiative Interface Science for Photovoltaics (ISPV) of the EuroTech Universities, the excellence cluster Nanosystems Initiative Munich (NIM) and the Centre for NanoScience (CeNS). K.J. and S.D.S. acknowledge the Royal Society (UF150033) for funding. We acknowledge the Engineering and Physical Sciences Research Council (EPSRC) for funding (EP/R023980/1). This work was supported by the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (HYPERION, grant agreement number 756962).

Author information

Author notes

  1. These authors contributed equally: Renjun Guo, Dan Han, Wei Chen.

Authors and Affiliations

  1. Lehrstuhl für Funktionelle Materialien, Physik-Department, Technische Universität München, Garching, Germany

    Renjun Guo, Wei Chen, Lennart K. Reb, Manuel A. Scheel, Shambhavi Pratap, Nian Li, Shanshan Yin, Tianxiao Xiao, Suzhe Liang, Anna Lena Oechsle, Christian L. Weindl & Peter Müller-Buschbaum

  2. Department Chemie, Ludwig-Maximilians-Universität München, Munich, Germany

    Dan Han & Hubert Ebert

  3. Department of Electrical and Electronic Engineering, Southern University of Science and Technology, Shenzhen, China

    Wei Chen & Kai Wang

  4. Cavendish Laboratory, University of Cambridge, Cambridge, UK

    Linjie Dai, Kangyu Ji, Neil C. Greenham, Samuel D. Stranks & Richard H. Friend

  5. Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, China

    Qiu Xiong & Peng Gao

  6. Department of Chemistry, Nankai University, Tianjin, China

    Saisai Li & Mingjian Yuan

  7. Deutsches Elektronen-Synchrotron (DESY), Hamburg, Germany

    Matthias Schwartzkopf & Stephan V. Roth

  8. Chemical Engineering and Biotechnology, University of Cambridge, Cambridge, UK

    Samuel D. Stranks

  9. Department of Fiber and Polymer Technology, KTH Royal Institute of Technology, Stockholm, Sweden

    Stephan V. Roth

  10. Heinz Maier-Leibnitz-Zentrum, Technische Universität München, Garching, Germany

    Peter Müller-Buschbaum

Authors
  1. Renjun Guo
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Dan Han
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Wei Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Linjie Dai
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Kangyu Ji
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Qiu Xiong
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Saisai Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Lennart K. Reb
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Manuel A. Scheel
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Shambhavi Pratap
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Nian Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  12. Shanshan Yin
    View author publications

    You can also search for this author in PubMed Google Scholar

  13. Tianxiao Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  14. Suzhe Liang
    View author publications

    You can also search for this author in PubMed Google Scholar

  15. Anna Lena Oechsle
    View author publications

    You can also search for this author in PubMed Google Scholar

  16. Christian L. Weindl
    View author publications

    You can also search for this author in PubMed Google Scholar

  17. Matthias Schwartzkopf
    View author publications

    You can also search for this author in PubMed Google Scholar

  18. Hubert Ebert
    View author publications

    You can also search for this author in PubMed Google Scholar

  19. Peng Gao
    View author publications

    You can also search for this author in PubMed Google Scholar

  20. Kai Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  21. Mingjian Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  22. Neil C. Greenham
    View author publications

    You can also search for this author in PubMed Google Scholar

  23. Samuel D. Stranks
    View author publications

    You can also search for this author in PubMed Google Scholar

  24. Stephan V. Roth
    View author publications

    You can also search for this author in PubMed Google Scholar

  25. Richard H. Friend
    View author publications

    You can also search for this author in PubMed Google Scholar

  26. Peter Müller-Buschbaum
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

R.G. provided conceptualization, methodology, formal analysis, investigation, resources, data curation, writing (original draft), project administration and visualization. D.H. and H.E. performed investigation and formal analysis for density function calculation and writing (original draft). W.C. provided resource and investigation for beamtime and supervision. L.D. performed investigation and formal analysis for transient absorption spectra and writing (original draft). K.W. carried out validation and provided resources for the project. K.J. and S.D.S. provided resources and investigation for transient absorption spectra. Q.X. and P.G. contributed resources and investigations for X-ray photoelectron spectroscopy. S. Li and M.Y. provided resources and investigation for Brunauer–Emmett–Teller measurements. L.K.R. contributed software and resources. M.A.S., S.P., S.Y., N.L., T.X. and A.L.O. provided resources and investigation for the beamtime. S. Liang and C.L.W. provided visualizations. N.C.G. and R.F. carried out investigation and formal analysis for transient absorption spectra. M.S. and S.V.R. provided resources, investigation, methodology and curation for the beamtime. P.M.-B. provided conceptualization, funding acquisition, project administration and validation. All authors contributed to writing, review and editing.

Corresponding author

Correspondence to Peter Müller-Buschbaum.

Ethics declarations

Competing interests

S.D.S. is a co-founder of Swift Solar. All other authors declare no competing interests.

Additional information

Peer review information Nature Energy thanks Antonino La Magna, Michael McGehee and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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

Supplementary information

Supplementary Information

Supplementary Notes 1–7, Figs. 1–14 and Tables 1–13.

Reporting Summary

Supplementary Data 1

Raw data for GIXS evolution.

Supplementary Data 2

Crystallographic data for perovskite.

Source data

Source Data Fig. 1

Numerical source data.

Source Data Fig. 2

Numerical source data.

Source Data Fig. 3

Numerical source data.

Source Data Fig. 4

Numerical source data.

Source Data Fig. 5

Numerical source data.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Guo, R., Han, D., Chen, W. et al. Degradation mechanisms of perovskite solar cells under vacuum and one atmosphere of nitrogen. Nat Energy 6, 977–986 (2021). https://doi.org/10.1038/s41560-021-00912-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41560-021-00912-8

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