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Centimeter-sized single crystal of a lead-free halide double perovskite with ferroelastic phase transition-triggered switchable dielectric properties

厘米级无铅卤化物双钙钛矿单晶实现铁弹性相变触发介电开关性质

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Abstract

Driven by the breakthrough development of lead (Pb)-based halide perovskites, halide double perovskites have also emerged as remarkably multipurpose materials owing to their environmental friendliness, abundant physicochemical properties, and structural tunability. However, despite their recent soaring progress, the realization of switchable dielectrics in this fascinating family remains considerably less explored. In this study, centimeter-sized single crystals of a single-layer halide double perovskite (3-bromopropylaminium)4AgBiBr8 (1) with dimensions up to 20 mm × 17 mm × 5 mm have been successfully synthesized by using the solution cooling method. The single crystal undergoes a ferroelastic phase transition of mmmF2/m defined by the Aizu notation, which is attributed to the synergistic interaction between octahedral distortion and flexible molecular motion according to structural analysis. Noteworthily, it possesses desirable ferroelastic phase transition-triggered switchable dielectric properties near the high temperature of 373 K, which can be switched between two stable dielectric states. Additionally, 1 possesses an indirect-bandgap semiconducting feature and exhibits an X-ray response with a sensitivity of up to 517 µC Gy −1air cm−2 at a 40 V bias voltage. We believe that this study provides another efficient application path for Pb-free halide double perovskites with intelligent functions.

摘要

在铅基卤化物钙钛矿突破性发展的推动下, 卤化物双钙钛矿因其环境友好、 丰富的物理化学性能和结构可调性而成为杰出的多用途材料. 尽管卤化物双钙钛矿的研究取得了飞速的进展, 但在这个吸引人的钙钛矿家族中对可切换电介质的探索仍然很少. 本工作通过溶液冷却法成功地生长了单层卤化物双钙钛矿(3-溴丙胺)4AgBiBr8 (1)的大尺寸单晶, 其尺寸达20 mm × 17 mm × 5 mm. 它经历了由Aizu符号定义的mmmF2/m的铁弹性相变, 通过结构分析可知该铁弹相变是八面体畸变和柔性分子运动协同作用的结果. 值得注意的是, 它在373 K附近具有理想的铁弹性相变触发的可切换电介质性能, 可以在两个稳定的电介质状态之间切换. 而且, 1展现出间接带隙半导体特性和X射线响应, 其中在40 V的偏压下1的灵敏度高达517 µC Gy −1air cm−2). 这项工作为具有智能功能的无铅卤化物双钙钛矿提供了一条有效的应用路径.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22193042, 22125110, 21833010, 22075285, 21875251, 21921001, and U21A2069), the Key Research Program of Frontier Sciences of Chinese Academy of Sciences (ZDBS-LY-SLH024), and the Youth Innovation Promotion of Chinese Academy of Sciences (2020307).

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Authors and Affiliations

  1. College of Chemistry, Fuzhou University, Fuzhou, 350116, China

    Zengshan Yue  (岳增姗), Fafa Wu  (邬发发), Junhua Luo  (罗军华) & Xitao Liu  (刘希涛)

  2. State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Zengshan Yue  (岳增姗), Fafa Wu  (邬发发), Xiaoqi Li  (李霄琪), Yi Liu  (刘艺), Junhua Luo  (罗军华) & Xitao Liu  (刘希涛)

  3. University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100039, China

    Xiaoqi Li  (李霄琪), Yi Liu  (刘艺), Junhua Luo  (罗军华) & Xitao Liu  (刘希涛)

Authors
  1. Zengshan Yue  (岳增姗)
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  2. Fafa Wu  (邬发发)
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  6. Xitao Liu  (刘希涛)
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Contributions

Author contributions Yue Z characterized the microcrystal structures, measured the related properties including dielectric and thermogravimetric performances, and wrote this manuscript. Wu F synthesized the bulk single crystal. Li X and Liu Y measured the electronic properties. Li X and Wu F provided some suggestions for the project. Liu X and Luo J designed and directed this project. All authors discussed and commented on the manuscript.

Corresponding author

Correspondence to Xitao Liu  (刘希涛).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Zengshan Yue received her BS degree from Zhongyuan University of Technology in 2017, majored in materials science and engineering. She is currently pursuing her Master’s degree at Fuzhou University and doing an internship at Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. Her current research interests focus on ferroelectric hybrid halide perovskite materials and photoelectric functional materials.

Xitao Liu joined Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences in July 2014. Before that, he received a PhD degree in materials science under the supervision of Prof. Dong Xu and Prof. Xinqiang Wang at the State Key Laboratory of Crystal Materials, Shandong University. He is a professor of materials physics and chemistry at present, and his current research interests focus on the rational design of ferroic (ferroelectric, ferroelastic and ferromagnetic) semiconducting materials and related physics.

Supplementary information Experimental details and supporting data are available in the online version of the paper.

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40843_2023_2541_MOESM1_ESM.pdf

Centimeter-sized single crystal of a lead-free halide double perovskite with ferroelastic phase transition-triggered switchable dielectric properties

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Yue, Z., Wu, F., Li, X. et al. Centimeter-sized single crystal of a lead-free halide double perovskite with ferroelastic phase transition-triggered switchable dielectric properties. Sci. China Mater. 66, 3977–3983 (2023). https://doi.org/10.1007/s40843-023-2541-8

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