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Co-deposition of hole-selective contact and absorber for improving the processability of perovskite solar cells

Abstract

Simplifying the manufacturing processes of renewable energy technologies is crucial to lowering the barriers to commercialization. In this context, to improve the manufacturability of perovskite solar cells (PSCs), we have developed a one-step solution-coating procedure in which the hole-selective contact and perovskite light absorber spontaneously form, resulting in efficient inverted PSCs. We observed that phosphonic or carboxylic acids, incorporated into perovskite precursor solutions, self-assemble on the indium tin oxide substrate during perovskite film processing. They form a robust self-assembled monolayer as an excellent hole-selective contact while the perovskite crystallizes. Our approach solves wettability issues and simplifies device fabrication, advancing the manufacturability of PSCs. Our PSC devices with positive–intrinsic–negative (p-i-n) geometry show a power conversion efficiency of 24.5% and retain >90% of their initial efficiency after 1,200 h of operating at the maximum power point under continuous illumination. The approach shows good generality as it is compatible with different self-assembled monolayer molecular systems, perovskites, solvents and processing methods.

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Fig. 1: Perovskite thin-film preparation and characterization.
Fig. 2: Characterization of SAM formation, energetic alignment and carrier lifetime.
Fig. 3: Device photovoltaic characteristics and stability.
Fig. 4: Blade coating of PSCs and evaluation of different PAs.
Fig. 5: Evaluation of different SAM molecular systems and solvents.

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All data generated or analysed during this study are included in the published article and its Supplementary Information.

References

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

    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. Zhang, H. et al. A universal co-solvent dilution strategy enables facile and cost-effective fabrication of perovskite photovoltaics. Nat. Commun. 13, 89 (2022).

    Article  Google Scholar 

  4. Min, H. et al. Efficient, stable solar cells by using inherent bandgap of α-phase formamidinium lead iodide. Science 366, 749–753 (2019).

    Article  Google Scholar 

  5. 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 

  6. Kim, M. et al. Conformal quantum dot–SnO2 layers as electron transporters for efficient perovskite solar cells. Science 375, 302–306 (2022).

    Article  Google Scholar 

  7. Peng, J. et al. Centimetre-scale perovskite solar cells with fill factors of more than 86 per cent. Nature 601, 573–578 (2022).

    Article  Google Scholar 

  8. Chen, S. et al. Stabilizing perovskite–substrate interfaces for high-performance perovskite modules. Science 373, 902–907 (2021).

    Article  Google Scholar 

  9. Li, X. et al. Constructing heterojunctions by surface sulfidation for efficient inverted perovskite solar cells. Science 375, 434–437 (2022).

    Article  Google Scholar 

  10. Zhang, F. et al. Metastable Dion–Jacobson 2D structure enables efficient and stable perovskite solar cells. Science 375, 71–76 (2022).

    Article  Google Scholar 

  11. Luo, D. et al. Enhanced photovoltage for inverted planar heterojunction perovskite solar cells. Science 360, 1442–1446 (2018).

    Article  Google Scholar 

  12. Jiang, Q. et al. Surface passivation of perovskite film for efficient solar cells. Nat. Photon. 13, 460–466 (2019).

    Article  Google Scholar 

  13. Zheng, X. et al. Managing grains and interfaces via ligand anchoring enables 22.3%-efficiency inverted perovskite solar cells. Nat. Energy 5, 131–140 (2020).

    Article  Google Scholar 

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

    Article  Google Scholar 

  15. Wang, R. et al. Constructive molecular configurations for surface-defect passivation of perovskite photovoltaics. Science 366, 1509–1513 (2019).

    Article  Google Scholar 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  18. Wu, W.-Q. et al. Molecular doping enabled scalable blading of efficient hole-transport-layer-free perovskite solar cells. Nat. Commun. 9, 1625 (2018).

    Article  Google Scholar 

  19. Zhou, Z. et al. Organic/inorganic hybrid p-type semiconductor doping affords hole transporting layer free thin-film perovskite solar cells with high stability. ACS Appl. Mater. Interfaces 11, 22603–22611 (2019).

    Article  Google Scholar 

  20. Ye, S. et al. A strategy to simplify the preparation process of perovskite solar cells by co-deposition of a hole-conductor and a perovskite layer. Adv. Mater. 28, 9648–9654 (2016).

    Article  Google Scholar 

  21. Zhou, Z. & Pang, S. Highly efficient inverted hole-transport-layer-free perovskite solar cells. J. Mater. Chem. A 8, 503–512 (2020).

    Article  Google Scholar 

  22. Al-Ashouri, A. et al. Conformal monolayer contacts with lossless interfaces for perovskite single junction and monolithic tandem solar cells. Energy Environ. Sci. 12, 3356–3369 (2019).

    Article  Google Scholar 

  23. Al-Ashouri, A. et al. Monolithic perovskite/silicon tandem solar cell with >29% efficiency by enhanced hole extraction. Science 370, 1300–1309 (2020).

    Article  Google Scholar 

  24. Levine, I. et al. Charge transfer rates and electron trapping at buried interfaces of perovskite solar cells. Joule 5, 2915–2933 (2021).

    Article  Google Scholar 

  25. Liu, J. et al. 28.2%-efficient, outdoor-stable perovskite/silicon tandem solar cell. Joule 5, 3169–3186 (2021).

    Article  Google Scholar 

  26. Jiang, Q. et al. Surface reaction for efficient and stable inverted perovskite solar cells. Nature 611, 278–283 (2022).

    Article  Google Scholar 

  27. Li, G. et al. Structure and performance evolution of perovskite solar cells under extreme temperatures. Adv. Energy Mater. 12, 2202887 (2022).

    Article  Google Scholar 

  28. Cassella, E. J. et al. Gas-assisted spray coating of perovskite solar cells incorporating sprayed self-assembled monolayers. Adv. Sci. 9, e2104848 (2022).

    Article  Google Scholar 

  29. Shi, W. & Ye, H. Efficient and stable perovskite solar cells with a superhydrophobic two-dimensional capping layer. J. Phys. Chem. Lett. 12, 4052–4058 (2021).

    Article  Google Scholar 

  30. Chen, H. et al. Quantum-size-tuned heterostructures enable efficient and stable inverted perovskite solar cells. Nat. Photon. 16, 352–358 (2022).

    Article  Google Scholar 

  31. Chen, S. et al. Crystallization in one-step solution deposition of perovskite films: upward or downward? Sci. Adv. 7, eabb2412 (2021).

    Article  Google Scholar 

  32. Hotchkiss, P. J. et al. The modification of indium tin oxide with phosphonic acids: mechanism of binding, tuning of surface properties, and potential for use in organic electronic applications. Acc. Chem. Res. 45, 337–346 (2012).

    Article  Google Scholar 

  33. Xiao, C. et al. Junction quality of SnO2-based perovskite solar cells investigated by nanometer-scale electrical potential profiling. ACS Appl. Mater. Interfaces 9, 38373–38380 (2017).

    Article  Google Scholar 

  34. Jiang, C.-S. et al. Carrier separation and transport in perovskite solar cells studied by nanometre-scale profiling of electrical potential. Nat. Commun. 6, 8397 (2015).

    Article  Google Scholar 

  35. Park, S. M., Abtahi, A., Boehm, A. M. & Graham, K. R. Surface ligands for methylammonium lead iodide films: surface coverage, energetics, and photovoltaic performance. ACS Energy Lett. 5, 799–806 (2020).

    Article  Google Scholar 

  36. Stolterfoht, M. et al. Visualization and suppression of interfacial recombination for high-efficiency large-area pin perovskite solar cells. Nat. Energy 3, 847–854 (2018).

    Article  Google Scholar 

  37. Li, L. et al. Flexible all-perovskite tandem solar cells approaching 25% efficiency with molecule-bridged hole-selective contact. Nat. Energy 7, 708–717 (2022).

    Article  Google Scholar 

  38. Zhao, Y. et al. Molecular interaction regulates the performance and longevity of defect passivation for metal halide perovskite solar cells. J. Am. Chem. Soc. 142, 20071–20079 (2020).

    Article  Google Scholar 

  39. Zheng, X., Alsalloum, A. Y., Hou, Y., Sargent, E. H. & Bakr, O. M. All-perovskite tandem solar cells: a roadmap to uniting high efficiency with high stability. Acc. Mater. Res. 1, 63–76 (2020).

    Article  Google Scholar 

  40. Kim, M., Schmitt, S. K., Choi, J. W., Krutty, J. D. & Gopalan, P. From self-assembled monolayers to coatings: advances in the synthesis and nanobio applications of polymer brushes. Polymers 7, 1346–1378 (2015).

    Article  Google Scholar 

  41. Cheng, H. & Hu, Y. Influence of chain ordering on frictional properties of self-assembled monolayers (SAMs) in nano-lubrication. Adv. Colloid Interface Sci. 171172, 53–65 (2012).

    Article  Google Scholar 

  42. Pathak, A. et al. Disorder-derived, strong tunneling attenuation in bis-phosphonate monolayers. J. Phys. Condens. Matter 28, 094008 (2016).

    Article  Google Scholar 

  43. Aktas, E. et al. Understanding the perovskite/self-assembled selective contact interface for ultra-stable and highly efficient p–i–n perovskite solar cells. Energy Environ. Sci. 14, 3976–3985 (2021).

    Article  Google Scholar 

  44. Aktas, E. et al. Role of terminal group position in triphenylamine-based self-assembled hole-selective molecules in perovskite solar cells. ACS Appl. Mater. Interfaces 14, 17461–17469 (2022).

    Article  Google Scholar 

  45. Aktas, E., Jiménez-López, J., Azizi, K., Torres, T. & Palomares, E. Self-assembled Zn phthalocyanine as a robust p-type selective contact in perovskite solar cells. Nanoscale Horiz. 5, 1415–1419 (2020).

    Article  Google Scholar 

  46. Ullah, A. et al. Novel phenothiazine-based self-assembled monolayer as a hole selective contact for highly efficient and stable p-i-n perovskite solar cells. Adv. Energy Mater. 12, 2103175 (2022).

    Article  Google Scholar 

  47. 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 

  48. Deng, Y. et al. Tailoring solvent coordination for high-speed, room-temperature blading of perovskite photovoltaic films. Sci. Adv. 5, eaax7537 (2019).

    Article  Google Scholar 

  49. Vidal, R. et al. Assessing health and environmental impacts of solvents for producing perovskite solar cells. Nat. Sustain. 4, 277–285 (2021).

    Article  Google Scholar 

  50. Yun, H.-S. et al. Ethanol-based green-solution processing of α-formamidinium lead triiodide perovskite layers. Nat. Energy 7, 828–834 (2022).

    Article  Google Scholar 

  51. Zhao, Q. et al. High efficiency perovskite quantum dot solar cells with charge separating heterostructure. Nat. Commun. 10, 2842 (2019).

    Article  Google Scholar 

  52. Unold, T. & Gütay, L. in Advanced Characterization Techniques for Thin Film Solar Cells (eds Abou-Ras, D., Kirchartz, T. & Rau, U.) 151–175 (Wiley-VCH, 2011).

    Google Scholar 

  53. 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 

  54. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    Article  Google Scholar 

  55. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

    Article  Google Scholar 

  56. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    Article  Google Scholar 

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Acknowledgements

This work was authored in part by the National Renewable Energy Laboratory, operated by Alliance for Sustainable Energy, for the US Department of Energy (DOE) under contract no. DE-AC36-08GO28308. This work was primarily supported as part of 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 DOE. The scalable manufacturing work carried out at the NREL was supported by the US DOE’s Office of Energy Efficiency and Renewable Energy (EERE) under the Solar Energy Technologies Office (SETO) Advanced Perovskite Cells and Modules program of the National Center for Photovoltaics. The work at City University of Hong Kong was supported by the Innovation and Technology Fund (GHP/102/20GD, Hong Kong). The work at École Polytechnique Fédérale de Lausanne (EPFL) was supported by an NPRP grant (NPRP11S-1231-170150) from the Qatar National Research Fund (a member of the Qatar Foundation) and the Valais Energy Demonstrators Fund. T.L., H.P. and K.R.G. acknowledge funding from the National Science Foundation under award nos. OIA-1929131 (T.L. and K.R.G) and 2102257 (H.P. and K.R.G). The work at Brown University was supported by the Office of Naval Research (grant no. N00014-20-1-2574) and the US DOE’s EERE through SETO award no. DE-0009511. The views expressed in the article do not necessarily represent the views of the US DOE or the US Government.

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Contributions

X.Z. and J.M.L. conceived the idea and designed the experiments. J.M.L. and Z.Z. supervised the project. X.Z. and Z.L. fabricated the devices and conducted the characterizations. Y.Z., D.G. and C.Z. participated in device fabrication. M.C., J.B.P., D.K., R.A.S., D.M. and B.M.W. performed optical spectroscopy and analysis. T.L. and H.P. carried out XPS and UPS measurements. C.X. conducted and analysed the KPFM and C-AFM measurements. S.P.H. performed TOF-SIMS measurements. Z.L., Z.D. and N.P.P. contributed to the device MPP stability test. X.W. and Y.Y. performed and interpreted the DFT calculations. A.M., A.R.K., N.P.P., K.R.G., Y.Y., M.K.N. and M.D.M. contributed to the analysis and provided advice. X.Z. and J.M.L. wrote the initial draft and all authors contributed to the final paper.

Corresponding authors

Correspondence to Zonglong Zhu or Joseph M. Luther.

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Competing interests

X.Z. and J.M.L. are inventors on a pending provisional patent (US application no. 63/363,327, filed on 21 April 2022 by Alliance for Sustainable Energy) related to the one-step solution method co-deposition of hole-selective contact and absorber for perovskite solar cells as discussed in this manuscript. M.D.M. is an advisor to Swift Solar. All other authors declare no competing interests.

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Zheng, X., Li, Z., Zhang, Y. et al. Co-deposition of hole-selective contact and absorber for improving the processability of perovskite solar cells. Nat Energy 8, 462–472 (2023). https://doi.org/10.1038/s41560-023-01227-6

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