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Suppression of atomic vacancies via incorporation of isovalent small ions to increase the stability of halide perovskite solar cells in ambient air

Nature Energy volume 3, pages 648–654 (2018)Cite this article

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Abstract

The degradation of perovskite solar cells in the presence of trace water and oxygen poses a challenge for their commercial impact given the appreciable permeability of cost-effective encapsulants. Point defects were recently shown to be a major source of decomposition due to their high affinity for water and oxygen molecules. Here, we report that, in single-cation/halide perovskites, local lattice strain facilitates the formation of vacancies and that cation/halide mixing suppresses their formation via strain relaxation. We then show that judiciously selected dopants can maximize the formation energy of defects responsible for degradation. Cd-containing cells show an order of magnitude enhanced unencapsulated stability compared to state-of-art mixed perovskite solar cells, for both shelf storage and maximum power point operation in ambient air at a relative humidity of 50%. We conclude by testing the generalizability of the defect engineering concept, demonstrating both vacancy-formation suppressors (such as Zn) and promoters (such as Hg).

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Fig. 1: Characterization of CsMAFA single crystals.
Fig. 2: Formation energies of antisites and Schottky vacancies.
Fig. 3: Mechanisms of lattice relaxation.
Fig. 4: Characterization of CsMAFA perovskite films with and without dopants.
Fig. 5: Performance of CsMAFA PSCs with and without dopants.

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Acknowledgements

This publication is partly based on work supported by an award (KUS-11-009-21) from the King Abdullah University of Science and Technology, by the Ontario Research Fund and by the Natural Sciences and Engineering Research Council of Canada. M.I.S. acknowledges the support of the Banting Postdoctoral Fellowship Program, administered by the Government of Canada. The work of A. Jain is supported by the IBM Canada Research and Development Center through the Southern Ontario Smart Computing Innovation Platform (SOSCIP) postdoctoral fellowship. DFT calculations were performed on the IBM BlueGene Q supercomputer with support from the SOSCIP. H.T. acknowledges the Netherlands Organization for Scientific Research (NWO) for a Rubicon grant (680-50-1511) in support of his postdoctoral research at the University of Toronto. We thank R. Wolowiec, D. Kopilovic, L. Levina and E. Palmiano for their help during the course of the study.

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  1. These authors contributed equally to this work: Makhsud I. Saidaminov, Junghwan Kim.

Authors and Affiliations

  1. Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

    Makhsud I. Saidaminov, Junghwan Kim, Ankit Jain, Rafael Quintero-Bermudez, Hairen Tan, Guankui Long, Furui Tan, Andrew Johnston, Yicheng Zhao, Oleksandr Voznyy & Edward H. Sargent

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Contributions

M.I.S. and J.K. conceived the idea, grew crystals, fabricated all devices and characterized them. A. Jain and O.V. performed DFT calculations. A. Johnston assisted in PL measurements. H.T. and F.T. assisted in solar cell fabrication and testing. R.Q.B. performed XPS. G.L., Y.Z. and H.T. assisted with the experiments and discussions. O.V. and E.H.S directed the overall research. M.I.S., J.K., O.V. and E.H.S. wrote the manuscript. All authors read and commented on the manuscript.

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Correspondence to Edward H. Sargent.

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Supplementary Tables 1–6, Supplementary Figures 1–19, Supplementary References

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Supplementary Data 1

Representative VASP input files for the DFT simulations

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Saidaminov, M.I., Kim, J., Jain, A. et al. Suppression of atomic vacancies via incorporation of isovalent small ions to increase the stability of halide perovskite solar cells in ambient air. Nat Energy 3, 648–654 (2018). https://doi.org/10.1038/s41560-018-0192-2

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