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Large tunable photoeffect on ion conduction in halide perovskites and implications for photodecomposition

Nature Materials volume 17, pages 445–449 (2018)Cite this article

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Abstract

In the same way as electron transport is crucial for information technology, ion transport is a key phenomenon in the context of energy research. To be able to tune ion conduction by light would open up opportunities for a wide realm of new applications, but it has been challenging to provide clear evidence for such an effect. Here we show through various techniques, such as transference-number measurements, permeation studies, stoichiometric variations, Hall effect experiments and the use of blocking electrodes, that light excitation enhances by several orders of magnitude the ionic conductivity of methylammonium lead iodide, the archetypal metal halide photovoltaic material. We provide a rationale for this unexpected phenomenon and show that it straightforwardly leads to a hitherto unconsidered photodecomposition path of the perovskite.

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Fig. 1: Schematic of the direct experimental methods used to study ionic conduction in the dark and under light.
Fig. 2: Electronic and ionic conductivities of MAPbI3 thin films as a function of light intensity.
Fig. 3: Absorbance of iodine extracted from MAPI thin films immersed in toluene.
Fig. 4: Schematic of the photodecomposition path.

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Acknowledgements

The authors are grateful to H. Hoier and G. Maier for XRD measurements, J. Na for his help with the Hall-effect experiments and A. Güth (Nanostructuring Lab in the Max Planck Institute for Solid State Research) for his help with electrode deposition. They are indebted to K. Müller from the Scientific Facility for Interface Analysis (headed by U. Starke) for XPS measurements. The authors also thank E. Kotomin, R. Evarestov, J. Fleig and, in particular, R. Merkle for many helpful discussions. This work was performed within the framework of the Max Planck-EPFL Center for Molecular Nano-science and Technology.

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Authors and Affiliations

  1. Max Planck Institute for Solid State Research, Stuttgart, Germany

    Gee Yeong Kim, Alessandro Senocrate, Tae-Youl Yang, Giuliano Gregori, Michael Grätzel & Joachim Maier

  2. Laboratory of Photonics and Interfaces, Ecole polytechnique Fédérale (EPFL) de Lausanne, Lausanne, Switzerland

    Alessandro Senocrate & Michael Grätzel

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Contributions

G.Y.K. was responsible for the sample preparation and characterization. G.Y.K., A.S., T.-Y.Y., G.G. and J.M. designed the experiments. J.M. supervised the work. G.Y.K., A.S., M.G. and J.M. discussed the results and wrote the manuscript.

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Correspondence to Joachim Maier.

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Supplementary text (9 sections), Figures S1–S10, 17 references

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Kim, G.Y., Senocrate, A., Yang, TY. et al. Large tunable photoeffect on ion conduction in halide perovskites and implications for photodecomposition. Nature Mater 17, 445–449 (2018). https://doi.org/10.1038/s41563-018-0038-0

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