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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The data that support the plots within this paper and other findings of this study are available from the corresponding authors upon reasonable request.
The custom codes that support the findings of this study are available from the corresponding authors upon reasonable request.
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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.
The authors declare no competing interests.
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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