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Carrier control in Sn–Pb perovskites via 2D cation engineering for all-perovskite tandem solar cells with improved efficiency and stability

Nature Energy volume 7, pages 642–651 (2022)Cite this article

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Abstract

All-perovskite tandem solar cells are promising for achieving photovoltaics with power conversion efficiencies above the detailed balance limit of single-junction cells, while retaining the low cost, light weight and other advantages associated with metal halide perovskite photovoltaics. However, the efficiency and stability of all-perovskite tandem cells are limited by the Sn–Pb-based narrow-bandgap perovskite cells. Here we show that the formation of quasi-two-dimensional (quasi-2D) structure (PEA)2GAPb2I7 from additives based on mixed bulky organic cations phenethylammonium (PEA+) and guanidinium (GA+) provides critical defect control to substantially improve the structural and optoelectronic properties of the narrow-bandgap (1.25 eV) Sn–Pb perovskite thin films. This 2D additive engineering results in Sn–Pb-based absorbers with low dark carrier density (~1.3 × 1014 cm−3), long bulk carrier lifetime (~9.2 μs) and low surface recombination velocity (~1.4 cm s−1), leading to 22.1%-efficient single-junction Sn–Pb perovskite cells and 25.5%-efficient all-perovskite two-terminal tandems with high photovoltage and long operational stability.

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Fig. 1: Charge carrier dynamics.
Fig. 2: Optoelectronic and morphological comparison.
Fig. 3: X-ray diffraction characterization.
Fig. 4: Single-junction Sn–Pb narrow-bandgap PSCs.
Fig. 5: Monolithic all-perovskite tandem solar cells.

Data availability

The datasets analysed and generated during the current study are included in the paper and its Supplementary Information. Supplementary Data are provided with this paper. Source data are provided with this paper.

References

  1. Hörantner, M. T. et al. The potential of multijunction perovskite solar cells. ACS Energy Lett. 2, 2506–2513 (2017).

    Article  Google Scholar 

  2. 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 

  3. Leijtens, T., Bush, K. A., Prasanna, R. & McGehee, M. D. Opportunities and challenges for tandem solar cells using metal halide perovskite semiconductors. Nat. Energy 3, 828–838 (2018).

    Article  Google Scholar 

  4. Tong, J. et al. Wide-bandgap metal halide perovskites for tandem solar cells. ACS Energy Lett. 6, 232–248 (2021).

    Article  Google Scholar 

  5. De Wolf, S. et al. Organometallic halide perovskites: sharp optical absorption edge and its relation to photovoltaic performance. J. Phys. Chem. Lett. 5, 1035–1039 (2014).

    Article  Google Scholar 

  6. Eperon, G. E. et al. Formamidinium lead trihalide: a broadly tunable perovskite for efficient planar heterojunction solar cells. Energy Environ. Sci. 7, 982–988 (2014).

    Article  Google Scholar 

  7. Green, M. A., Ho-Baillie, A. & Snaith, H. J. The emergence of perovskite solar cells. Nat. Photon. 8, 506–514 (2014).

    Article  Google Scholar 

  8. Noh, J. H., Im, S. H., Heo, J. H., Mandal, T. N. & Seok, S. I. Chemical management for colorful, efficient, and stable inorganic–organic hybrid nanostructured solar cells. Nano Lett. 13, 1764–1769 (2013).

    Article  Google Scholar 

  9. Hao, F., Stoumpos, C. C., Chang, R. P. H. & Kanatzidis, M. G. Anomalous band gap behavior in mixed Sn and Pb perovskites enables broadening of absorption spectrum in solar cells. J. Am. Chem. Soc. 136, 8094–8099 (2014).

    Article  Google Scholar 

  10. Li, Z. et al. Scalable fabrication of perovskite solar cells. Nat. Rev. Mater. 3, 18017 (2018).

    Article  Google Scholar 

  11. Saidaminov, M. I. et al. Conventional solvent oxidizes Sn(II) in perovskite inks. ACS Energy Lett. 5, 1153–1155 (2020).

    Article  Google Scholar 

  12. Kumar, M. H. et al. Lead-free halide perovskite solar cells with high photocurrents realized through vacancy modulation. Adv. Mater. 26, 7122–7127 (2014).

    Article  Google Scholar 

  13. Lee, S. J. et al. Reducing carrier density in formamidinium tin perovskites and its beneficial effects on stability and efficiency of perovskite solar cells. ACS Energy Lett. 3, 46–53 (2018).

    Article  Google Scholar 

  14. Leijtens, T., Prasanna, R., Gold-Parker, A., Toney, M. F. & McGehee, M. D. Mechanism of tin oxidation and stabilization by lead substitution in tin halide perovskites. ACS Energy Lett. 2, 2159–2165 (2017).

    Article  Google Scholar 

  15. Yokoyama, T. et al. Overcoming short-circuit in lead-free CH3NH3SnI3 perovskite solar cells via kinetically controlled gas–solid reaction film fabrication process. J. Phys. Chem. Lett. 7, 776–782 (2016).

    Article  Google Scholar 

  16. Zong, Y., Zhou, Z., Chen, M., Padture, N. P. & Zhou, Y. Lewis-adduct mediated grain-boundary functionalization for efficient ideal-bandgap perovskite solar cells with superior stability. Adv. Energy Mater. 8, 1800997 (2018).

    Article  Google Scholar 

  17. Tong, J. et al. Carrier lifetimes of >1 μs in Sn-Pb perovskites enable efficient all-perovskite tandem solar cells. Science 364, 475–479 (2019).

    Article  Google Scholar 

  18. Lin, R. et al. Monolithic all-perovskite tandem solar cells with 24.8% efficiency exploiting comproportionation to suppress Sn(ii) oxidation in precursor ink. Nat. Energy 4, 864–873 (2019).

    Article  Google Scholar 

  19. Xiao, K. et al. All-perovskite tandem solar cells with 24.2% certified efficiency and area over 1 cm2 using surface-anchoring zwitterionic antioxidant. Nat. Energy 5, 870–880 (2020).

    Article  Google Scholar 

  20. Yang, Z. et al. Enhancing electron diffusion length in narrow-bandgap perovskites for efficient monolithic perovskite tandem solar cells. Nat. Commun. 10, 4498 (2019).

    Article  Google Scholar 

  21. Ke, W. et al. Narrow-bandgap mixed lead/tin-based 2D Dion–Jacobson perovskites boost the performance of solar cells. J. Am. Chem. Soc. 142, 15049–15057 (2020).

    Article  Google Scholar 

  22. Kapil, G. et al. Strain relaxation and light management in tin–lead perovskite solar cells to achieve high efficiencies. ACS Energy Lett. 4, 1991–1998 (2019).

    Article  Google Scholar 

  23. Yu, Z. et al. Simplified interconnection structure based on C60/SnO2-x for all-perovskite tandem solar cells. Nat. Energy 5, 657–665 (2020).

    Article  Google Scholar 

  24. Li, C. et al. Low-bandgap mixed tin–lead iodide perovskites with reduced methylammonium for simultaneous enhancement of solar cell efficiency and stability. Nat. Energy 5, 768–776 (2020).

    Article  Google Scholar 

  25. Zhao, D. et al. Efficient two-terminal all-perovskite tandem solar cells enabled by high-quality low-bandgap absorber layers. Nat. Energy 3, 1093–1100 (2018).

    Article  Google Scholar 

  26. 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 

  27. Kirchartz, T., Márquez, J. A., Stolterfoht, M. & Unold, T. Photoluminescence-based characterization of halide perovskites for photovoltaics. Adv. Energy Mater. 10, 1904134 (2020).

    Article  Google Scholar 

  28. Meggiolaro, D., Ricciarelli, D., Alasmari, A. A., Alasmary, F. A. S. & De Angelis, F. Tin versus lead redox chemistry modulates charge trapping and self-doping in tin/lead iodide perovskites. J. Phys. Chem. Lett. 11, 3546–3556 (2020).

    Article  Google Scholar 

  29. Liao, W. et al. Lead-free inverted planar formamidinium tin triiodide perovskite solar cells achieving power conversion efficiencies up to 6.22%. Adv. Mater. 28, 9333–9340 (2016).

    Article  Google Scholar 

  30. Sabba, D. et al. Impact of anionic Br– substitution on open circuit voltage in lead free perovskite (CsSnI3-xBrx) solar cells. J. Phys. Chem. C 119, 1763–1767 (2015).

    Article  Google Scholar 

  31. Rühle, S. Tabulated values of the Shockley–Queisser limit for single junction solar cells. Sol. Energy 130, 139–147 (2016).

    Article  Google Scholar 

  32. Krückemeier, L., Rau, U., Stolterfoht, M. & Kirchartz, T. How to report record open-circuit voltages in lead-halide perovskite solar cells. Adv. Energy Mater. 10, 1902573 (2020).

    Article  Google Scholar 

  33. Liu, Z. et al. Open-circuit voltages exceeding 1.26 V in planar methylammonium lead iodide perovskite solar cells. ACS Energy Lett. 4, 110–117 (2019).

    Article  Google Scholar 

  34. Ricciarelli, D., Meggiolaro, D., Ambrosio, F. & De Angelis, F. Instability of tin iodide perovskites: bulk p-doping versus surface tin oxidation. ACS Energy Lett. 5, 2787–2795 (2020).

    Article  Google Scholar 

  35. Daub, M., Haber, C. & Hillebrecht, H. Synthesis, crystal structures, optical properties, and phase transitions of the layered guanidinium-based hybrid perovskites [C(NH2)3]2MI4; M = Sn, Pb. Eur. J. Inorg. Chem. 2017, 1120–1126 (2017).

    Article  Google Scholar 

  36. Jodlowski, A. D. et al. Benign-by-design solventless mechanochemical synthesis of three-, two-, and one-dimensional hybrid perovskites. Angew. Chem. Int. Ed. 55, 14972–14977 (2016).

    Article  Google Scholar 

  37. Soe, C. M. M. et al. New type of 2D perovskites with alternating cations in the interlayer space, (C(NH2)3)(CH3NH3)nPbnI3n+1: structure, properties, and photovoltaic performance. J. Am. Chem. Soc. 139, 16297–16309 (2017).

    Article  Google Scholar 

  38. Liang, C. et al. Ruddlesden–Popper perovskite for stable solar cells. Energy Environ. Sci. 1, 221–231 (2018).

    Google Scholar 

  39. Ke, W. et al. Employing lead thiocyanate additive to reduce the hysteresis and boost the fill factor of planar perovskite solar cells. Adv. Mater. 28, 5214–5221 (2016).

    Article  Google Scholar 

  40. Zhang, R. et al. A potassium thiocyanate additive for hysteresis elimination in highly efficient perovskite solar cells. Inorg. Chem. Front. 6, 434–442 (2019).

    Article  Google Scholar 

  41. Fu, Y. et al. Incorporating large A cations into lead iodide perovskite cages: relaxed Goldschmidt tolerance factor and impact on exciton–phonon interaction. ACS Cent. Sci. 5, 1377–1386 (2019).

    Article  Google Scholar 

  42. Zhang, F. et al. Advances in two-dimensional organic–inorganic hybrid perovskites. Energy Environ. Sci. 13, 1154–1186 (2020).

    Article  Google Scholar 

  43. Chen, X. et al. Impact of layer thickness on the charge carrier and spin coherence lifetime in two-dimensional layered perovskite single crystals. ACS Energy Lett. 3, 2273–2279 (2018).

    Article  Google Scholar 

  44. Wang, J. et al. 16.8% monolithic all-perovskite triple-junction solar cells via a universal two-step solution process. Nat. Commun. 11, 5254 (2020).

    Article  Google Scholar 

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

    Article  Google Scholar 

  46. Palmstrom, A. F. et al. Enabling flexible all-perovskite tandem solar cells. Joule 3, 2193–2204 (2019).

    Article  Google Scholar 

  47. Kim, D. et al. Efficient, stable silicon tandem cells enabled by anion-engineered wide-bandgap perovskites. Science 368, 155–160 (2020).

    Article  Google Scholar 

  48. Zhang, F. et al. Enhanced charge transport in 2D perovskites via fluorination of organic cation. J. Am. Chem. Soc. 141, 5972–5979 (2019).

    Article  Google Scholar 

  49. Perkins, C. L. & Hasoon, F. S. Surfactant-assisted growth of CdS thin films for photovoltaic applications. J. Vac. Sci. Technol. A 24, 497–504 (2006).

    Article  Google Scholar 

  50. 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 

  51. 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 

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

    Article  Google Scholar 

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

    Article  Google Scholar 

  54. Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132, 154104 (2010).

    Article  Google Scholar 

  55. Harvey, S. P., Messinger, J., Zhu, K., Luther, J. M. & Berry, J. J. Investigating the effects of chemical gradients on performance and reliability within perovskite solar cells with TOF-SIMS. Adv. Energy Mater. 10, 1903674 (2020).

    Article  Google Scholar 

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Acknowledgements

The work at the National Renewable Energy Laboratory was supported by the US Department of Energy under contract no. DE-AC36-08GO28308 with Alliance for Sustainable Energy, Limited Liability Company, the manager and operator of the National Renewable Energy Laboratory. We acknowledge the support for perovskite synthesis, device fabrication and characterization from the De-risking Halide Perovskite Solar Cells programme of the National Center for Photovoltaics (J.T., Q.J., A.F.P., F.Z., S.P.D., A.E.L., R.M.F., M.Y., J.F.G., J.J.B. and K.Z.) and the support for TRPL characterization and analysis from award no. 34361 (A.J.F. and D.K.) funded by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies Office. We also acknowledge the support for time-resolved microwave conductivity and Hall effect measurement and analysis from the Center for Hybrid Organic Inorganic Semiconductors for Energy, an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, Office of Science within the US Department of Energy (J.H., H.L. and M.C.B.). Contributions from S.A.J. and M.D.M. were supported by the US Department of Energy’s Office of Energy Efficiency and Renewable Energy under Solar Energy Technologies Office agreement no. DE-EE0008551. The views expressed in the article do not necessarily represent the views of the US Department of Energy or the US government.

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Author notes

  1. These authors contributed equally: Jinhui Tong, Qi Jiang.

Authors and Affiliations

  1. Chemistry and Nanoscience Center, National Renewable Energy Laboratory, Golden, CO, USA

    Jinhui Tong, Qi Jiang, Andrew J. Ferguson, Ji Hao, Haipeng Lu, Ryan M. France, Fei Zhang, John F. Geisz, Michael D. McGehee, Matthew C. Beard, Darius Kuciauskas & Kai Zhu

  2. Materials Science Center, National Renewable Energy Laboratory, Golden, CO, USA

    Axel F. Palmstrom, Sean P. Dunfield, Amy E. Louks, Steven P. Harvey, Mengjin Yang & Joseph J. Berry

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

    Xiaoming Wang, Chongwen Li & Yanfa Yan

  4. Materials Science and Engineering Program, University of Colorado, Boulder, CO, USA

    Sean P. Dunfield, Samuel A. Johnson & Michael D. McGehee

  5. Renewable and Sustainable Energy Institute, University of Colorado, Boulder, CO, USA

    Sean P. Dunfield, Michael D. McGehee, Matthew C. Beard & Joseph J. Berry

  6. Department of Chemical and Biological Engineering, University of Colorado, Boulder, CO, USA

    Michael D. McGehee

  7. Department of Physics, University of Colorado, Boulder, CO, USA

    Joseph J. Berry

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  1. Jinhui Tong
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Contributions

K.Z. and J.T. conceived the idea and designed the experiment. J.T. and Q.J. developed the tandem solar cell structure and fabrication process. J.T. and Q.J. fabricated and characterized the perovskite devices. J.T. conducted the X-ray diffraction measurement. A.J.F. and D.K. performed the TRPL characterization and analysis. A.F.P. conducted atomic layer deposition with support from S.A.J. under the guidance of M.D.M.; F.Z. characterized the surface and cross-section morphology of the perovskite films and devices. J.H. conducted the Hall effect measurement and analysis. M.Y. participated in the tandem solar cell efficiency measurement. S.P.D. conducted the XPS measurement and analysis with guidance from J.J.B.; A.E.L. and J.J.B. conducted the long-term device stability measurement and analysis. H.L. conducted time-resolved microwave conductivity characterization and analysis under the guidance of M.C.B.; R.M.F. and J.F.G. supported the tandem EQE and J–V measurements. X.W. and C. L. conducted density functional theory calculations and PL measurement, respectively, under the guidance of Y.Y.; S.P.H. conducted the time-of-flight secondary-ion mass spectrometry study and analysis. J.T. and K.Z. wrote the first draught of the manuscript. All authors discussed the results and contributed to the revision of the manuscript. K.Z. supervised the project.

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Correspondence to Jinhui Tong or Kai Zhu.

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Competing interests

M.D.M. is an advisor to Swift Solar. J.T., Q.J. and K.Z. are inventors on a pending provisional patent (US patent application number 63/227,415; by Alliance for Sustainable Energy) related to the 2D cation engineering of Sn-Pb perovskites for tandem solar cell application as discussed in this manuscript.

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Nature Energy thanks Jia Zhu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–22, Tables 1–4 and references.

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Supplementary Data 1

Source data of Supplementary Fig. 9a–d.

Supplementary Data 2

Source data of Supplementary Fig. 19a–d.

Source data

Source Data Fig. 4

Source data of statistical PV parameters of Sn–Pb narrow-bandgap PSCs in Fig. 4b.

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Tong, J., Jiang, Q., Ferguson, A.J. et al. Carrier control in Sn–Pb perovskites via 2D cation engineering for all-perovskite tandem solar cells with improved efficiency and stability. Nat Energy 7, 642–651 (2022). https://doi.org/10.1038/s41560-022-01046-1

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