Evidence for polarization-induced phase transformations and degradation in CH3NH3PbI3
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Andrei A. Eliseev1,3(
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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.
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Evidence for polarization-induced phase transformations and degradation in CH3NH3PbI3
), Andrei A. Eliseev1,3(
)
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.
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Acknowledgements
Authors acknowledge the assistance of Andrei Chumakov and Stephan V. Roth from Deutsches Elektronen-Synchrotron PETRA III (P03 beamline, DESY, Hamburg, Germany), Anton Davydok and Christina Krywka from Helmholtz-Zentrum Hereon (Institute of Materials Physics, Hamburg, Germany) for GIWAXS data acquisition. AYG, EIM, ABT, EAG acknowledge the support of Russian Science Foundation (No. 19-73-30022). EAA acknowledges the support of the Russian Fund for Basic Research project (No. 18-29-19105) in part of nanofocus GIWAXS methodology development. The authors are thankful to the M.V. Lomonosov Moscow State University Program of Development and DESY research centre (PETRA III synchrotron) for the instrumental support of research studies.
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