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Controllable volatile-to-nonvolatile memristive switching in single-crystal lead-free double perovskite with ultralow switching electric field

具有超低开关电场的可控的易失性至非易失性单晶 无铅双钙钛矿忆阻器

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Abstract

All-inorganic lead-free double perovskite offers a potential material platform for electronic or optoelectronic memory devices owing to its ionic migration-based electrical transport, high photosensitivity, low toxicity, and environmental stability. However, the commonly used polycrystalline perovskite films severely restrict device performance. Herein, we demonstrate a high-performance memristor based on single-crystal double perovskite Cs2AgBiBr6 with an ultralow switching electric field of 6.67 × 104 V m−1 and a high current on/off ratio of 107. Remarkably, the resistive switching of Cs2AgBiBr6 is found to be thickness-dependent, which evolves from volatile threshold to nonvolatile resistance switching with the crystal thickness from 100 to 800 nm. Elemental analysis reveals that the formation of conductive channels in Cs2AgBiBr6 is associated with the migration of Br vacancies with low activation energy. In addition, the formed conductive channels can be annihilated by light illumination with controlled wavelength and intensity, which leads to the realization of optoelectronic memories with separate electrical-writing and optical-erasing processes. Our findings provide deep insights into the ionic migration in single-crystal perovskite and pave the way for its future application in electronic and optoelectronic memory devices.

摘要

全无机无铅双钙钛矿由于其优异的电子传输能力、高光敏性、 低毒性和环境稳定性, 为电子/光电存储器件提供了潜在的材料. 然而, 钙钛矿薄膜的多晶性质严重限制了器件性能. 在此, 我们展示了一种基 于单晶双钙钛矿Cs2AgBiBr6的高性能忆阻器, 其具有6.67 × 104 V m−1的 超低开关电场和107的高电流开/关比. 值得注意的是, Cs2AgBiBr6的电 阻开关行为与单晶钙钛矿的厚度相关, 当单晶厚度从100到800 nm变化 时, 忆阻器从易失性的阈值开关行为演变为非易失性的忆阻开关行为. 元素分析表明, Cs2AgBiBr6中导电通道的形成与具有低活化能Br空位 的迁移有关. 此外, 形成的导电通道可以被具有不同波长和强度的光照 湮灭, 从而实现具有单独的电写入和光擦除的光电存储器. 我们的研究 结果为单晶钙钛矿中的离子迁移提供了深刻的见解, 并为其在未来的 电子和光电存储器中的应用提供了理论基础.

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Acknowledgements

Shi Y and Han C acknowledge the financial support from the National Natural Science Foundation of China (61874074 and 62004128), the Fundamental Research Foundation of Shenzhen (JCYJ20190808152607389), and the (Key) Project of Department of Education of Guangdong Province (2016KZDXM008). Li H acknowledges the support from Guangdong Basic and Applied Basic Research Foundation (General Program, 2022A1515012055), the Natural Science Foundation of Shenzhen University (2017011) and the Technology and Innovation Commission of Shenzhen (20200810164814001). This project was also funded by Shenzhen Peacock Plan (KQTD2016053112042971). The authors thank the technical support from the Instrumental Analysis Center and the Photonics Center of Shenzhen University.

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Authors and Affiliations

  1. International Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen, 518060, China

    Qi You  (游琪), Fu Huang  (黄富), Jiaqi Zhu  (祝家齐), Yue Zheng  (郑越) & Cheng Han  (韩成)

  2. College of Electronics and Information Engineering, Shenzhen University, Shenzhen, 518060, China

    Feier Fang  (房菲儿), Shaofan Fang  (方绍帆), Bo Zhou  (周勃), Henan Li  (李贺楠) & Yumeng Shi  (时玉萌)

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  1. Qi You  (游琪)
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  2. Fu Huang  (黄富)
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  9. Cheng Han  (韩成)
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  10. Yumeng Shi  (时玉萌)
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Contributions

You Q designed and engineered the experiments; Huang F and Fang F performed the material synthesis; Zhu J, Zheng Y, Fang S, Zhou B, and Li H participated in the characterizations and revised the manuscript; You Q wrote the paper with support from Han C and Shi Y. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Cheng Han  (韩成) or Yumeng Shi  (时玉萌).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Qi You is currently a doctoral candidate at the Institute of Microscale Optoelectronics, Shenzhen University (SZU, China). His research interests mainly focus on the electronic memory devices based on transition metal dichalcogenides and metal halide perovskites.

Cheng Han is currently a tenured associated professor at the Institute of Microscale Optoelectronics of SZU. He received his PhD degree in physics from the National University of Singapore (NUS, Singapore) in 2014. His research interests include the fabrication and interface engineering of low-dimensional materials-based electronic and optoelectronic devices.

Yumeng Shi is currently a full professor at the College of Electronics and Information Engineering, SZU. He received his PhD degree in materials science and engineering from Nanyang Technological University (NTU, Singapore) in 2011. He is a “Global Highly Cited Researcher” by Clarivate Analytics and Elsevier. His current research interests include the synthesis of low-dimensional materials and their applications in optoelectronics.

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40843_2022_2113_MOESM1_ESM.pdf

Controllable volatile-to-nonvolatile memristive switching in single-crystal lead-free double perovskite with ultralow switching electric field

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You, Q., Huang, F., Fang, F. et al. Controllable volatile-to-nonvolatile memristive switching in single-crystal lead-free double perovskite with ultralow switching electric field. Sci. China Mater. 66, 241–248 (2023). https://doi.org/10.1007/s40843-022-2113-y

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