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Photocarrier-induced persistent structural polarization in soft-lattice lead halide perovskites

Nature Nanotechnology (2023)Cite this article

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Abstract

The success of the lead halide perovskites in diverse optoelectronics has motivated considerable interest in their fundamental photocarrier dynamics. Here we report the discovery of photocarrier-induced persistent structural polarization and local ferroelectricity in lead halide perovskites. Photoconductance studies of thin-film single-crystal CsPbBr3 at 10 K reveal long-lasting persistent photoconductance with an ultralong photocarrier lifetime beyond 106 s. X-ray diffraction studies reveal that photocarrier-induced structural polarization is present up to a critical freezing temperature. Photocapacitance studies at cryogenic temperatures further demonstrate a systematic local phase transition from linear dielectric to paraelectric and relaxor ferroelectric under increasing illumination. Our theoretical investigations highlight the critical role of photocarrier–phonon coupling and large polaron formation in driving the local relaxor ferroelectric phase transition. Our findings show that this photocarrier-induced persistent structural polarization enables the formation of ferroelectric nanodomains at low temperature, which suppress carrier recombination and offer the possibility of exploring intriguing carrier–phonon interplay and the rich polaron photophysics.

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Fig. 1: Difference between conventional and ferroelectric large polarons.
Fig. 2: The long-lived photocarriers.
Fig. 3: Photocarrier-induced structural distortion.
Fig. 4: Emergence of local relaxor ferroelectric behaviour under illumination.
Fig. 5: DFT calculations.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding authors upon reasonable request.

Code availability

The custom codes that support the findings of this study are available from the corresponding authors upon reasonable request.

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Acknowledgements

X.D. acknowledges partial support by the Office of Naval Research through grant no. N00014-22-1-2631 for device fabrication and characterization. Y.P. acknowledges support by 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 for the theoretical part of the work. T.J.S. acknowledges the Lawrence Livermore National Laboratory Graduate Research Scholar Program and funding support from Lawrence Livermore National Laboratory LDRD 20-S1-004. Part of this work was performed under the auspices of the US Department of Energy by the Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. The X-ray diffraction measurements used the resources of the Center for Nanophase Materials Sciences and Spallation Neutron Source, which are DOE Office of Science User Facilities. Y.H. acknowledges support by the National Science Foundation EFRI-1433541 for partial support of material preparation. We acknowledge the Nanoelectronics Research Facility at UCLA for device fabrication technical support.

Author information

Author notes

  1. These authors contributed equally: Qi Qian, Zhong Wan, Hiroyuki Takenaka.

  2. Deceased: Hiroyuki Takenaka.

Authors and Affiliations

  1. Department of Chemistry and Biochemistry, University of California, Los Angeles, CA, USA

    Qi Qian, Zhong Wan, Laiyuan Wang, Peiqi Wang, Jingyuan Zhou, Huaying Ren & Xiangfeng Duan

  2. Department of Chemistry and Biochemistry, University of California Santa Cruz, Santa Cruz, CA, USA

    Hiroyuki Takenaka & Yuan Ping

  3. Center for Nanophase Materials Science and Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA

    Jong K. Keum

  4. Department of Physics, University of California Santa Cruz, Santa Cruz, CA, USA

    Tyler J. Smart

  5. Lawrence Livermore National Laboratory, Livermore, CA, USA

    Tyler J. Smart

  6. Department of Materials Science and Engineering, University of California, Los Angeles, CA, USA

    Dong Xu & Yu Huang

  7. California NanoSystems Institute, University of California, Los Angeles, CA, USA

    Yu Huang & Xiangfeng Duan

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Contributions

X.D. conceived the research. Q.Q., Z.W. and X.D. designed the experiments. Q.Q. grew the material, fabricated the devices and performed the optoelectrical measurements. L.W., P.W., D.X. and Y.H. contributed to the device fabrication or characterization. Z.W. contributed to the transport measurements. J.K.K., J.Z. and H.R. contributed to the X-ray diffraction experiments. H.T., T.J.S. and Y.P. conducted the first-principles calculations and wrote the relevant discussions. Q.Q., Z.W. and X.D. conducted the data analysis and wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Yuan Ping or Xiangfeng Duan.

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Nature Nanotechnology thanks Doru Lupascu and Kiyoshi Miyata for their contribution to the peer review of this work.

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Supplementary Figs. 1–11, Table 1 and refs. 1–4.

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Qian, Q., Wan, Z., Takenaka, H. et al. Photocarrier-induced persistent structural polarization in soft-lattice lead halide perovskites. Nat. Nanotechnol. (2023). https://doi.org/10.1038/s41565-022-01306-x

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