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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

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.

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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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Authors and Affiliations

Authors

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 JV 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.

Corresponding authors

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

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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 (2022). https://doi.org/10.1038/s41560-022-01046-1

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