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Research Article

Evidence for polarization-induced phase transformations and degradation in CH3NH3PbI3

Aleksei Yu. Grishko1( ), Maria A. Komkova2, Ekaterina I. Marchenko3, Alexandra V. Chumakova4, Alexey B. Tarasov3, Eugene A. Goodilin2,3, Andrei A. Eliseev1,3( )
Department of Materials Science, MSU-BIT University, Shenzhen 517182, China
Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia
Department of Materials Science, Lomonosov Moscow State University, Moscow 119991, Russia
European Synchrotron Radiation Facility, F-38042 Grenoble, France
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Graphical Abstract

The transformation of light-absorbing β-CH3NH3PbI3 (β-MAPbI3) into intermediate metastable δ-MAPbI3 polymorph caused by the alignment of polar organic cation in the electric field is revealed using in situ nanofocus X-ray diffraction. Electromigration of both I− and MA+ and consequent formation of gradient structure consisting of methylammonium-rich MAPbI3−y (y < 0.6) and iodine-rich MA1−xPbI3 (x < 0.3) domains are verified.

Abstract

In solar cells, hybrid halide perovskites operate under constant bias, thus their stability towards electric field-induced degradation is of key importance. Here we report on evidence of previously unidentified electric field-induced transitions and degradation path of CH3NH3PbI3 (MAPbI3) using elemental and phase mapping. Thin films of MAPbI3 were deposited onto 1–2 µm-pitch interdigitated electrodes and subjected to direct current (DC)-polarization. The MAPbI3 layer polarized with < 0.8 V/µm DC electric field undergoes pronounced ion redistribution to methylammonium-rich MAPbI3−y (y < 0.6) and iodine-rich MA1−xPbI3 (x < 0.3) regions. Polarization-induced loss of both methylammonium and iodine provokes degradation of MAPbI3. Using nanofocus grazing-incidence wide-angle X-ray scattering (GIWAXS), we unambiguously showed that the bias voltage induces the transformation of β-MAPbI3 to metastable δ-MAPbI3 polymorph via alignment of polar organic cation with the electric field. This transformation is partially reversible upon field removal. However, once formed, δ-MAPbI3 disrupts the morphology of pristine film and undergoes decomposition to β-MAPbI3 (β-MAPI) and PbI2. With the aforementioned compositional and phase changes, only MA-rich part serves as the charge separation layer, while the I-rich excitation is blocked with the PbI2 barrier serving as holes trapping layer. These observations reveal the intermediate steps in electric-field-driven degradation of halide perovskites and show the role of polar cations in the process, which is instructive for further material design with higher stability metrics.

Keywords

halide perovskitesstabilitydegradationelectric fieldionic conductivitystoichiometry

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Nano Research
Volume 16 Issue 7,
July 2023
Pages 9435-9442
DOI: 10.1007/s12274-023-5652-8
Cite this article:
Grishko AY, Komkova MA, Marchenko EI, et al. Evidence for polarization-induced phase transformations and degradation in CH3NH3PbI3. Nano Research, 2023, 16(7): 9435-9442. https://doi.org/10.1007/s12274-023-5652-8
Topics:
Perovskite solar cells

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Received: 06 September 2022
Revised: 06 March 2023
Accepted: 08 March 2023
Published: 05 May 2023
© Tsinghua University Press 2023
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