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Room-temperature ferroelectricity in magnetically ordered CoH2SeO4 flakes

磁有序CoH2SeO4薄片中的室温铁电性

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Abstract

Here, we demonstrate the existence of magnetic ordering and sliding ferroelectricity in two-dimensional CoH2SeO4 multilayers. The experimental result reveals the antiferromagnetic order in powder sample, and first-principles calculation indicates the antiferromagnetic ground state with TN≈75 K in CoH2SeO4 single layer. The sliding ferroelectricity with an asymmetric triplet potential well is theoretically predicted and experimentally confirmed by 180°-piezoelectric hysteresis loops, switchable domains and second harmonic generation signals in CoH2SeO4 multilayers. The vertically stacked ferroelectric capacitor shows both polarization and capacitance hysteresis loops. A ferroelectric transition temperature of ~370 K is obtained from the temperature-dependent dielectricity. The emergence of sliding ferroelectricity and anti-ferromagnetism points out a new route for obtaining low-dimensional multiferroic materials.

摘要

本文通过第一性原理计算和实验表征证明了二维CoH2SeO4薄膜的磁有序和滑移铁电性. 首先, 实验结果证实了粉末CoH2SeO4样品的反铁磁序. 同时, 第一性原理计算表明单层CoH2SeO4具有反铁磁(AFM-I)基态(TN≈75 K), 且预测了二维CoH2SeO4薄膜具有以不对称的三重势阱态为特征的滑移铁电性, 并在实验中测得了180°压电滞回线、 可反转铁电畴和二次谐波信号. 此外, 在基于二维CoH2SeO4薄膜的电容器中获得铁电材料所特有的电滞回线和蝴蝶状的电容曲线. 介电温谱测试表明二维CoH2SeO4薄膜的铁电转变温度约为370 K. CoH2SeO4中滑移铁电性和反铁磁性的出现为获得低维多铁材料指出了一条新的途径.

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Acknowledgements

This work was supported by National Key Research and Development Program of China (2021YFA1200700), The National Natural Science Foundation of China (No. 52372120, T2222025 and 62174053), Shanghai Science and Technology Innovation Action Plan (21JC1402000 and 21520714100), and the Fundamental Research Funds for the Central Universities.

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Polar Materials and Devices (MOE), Shanghai Center of Brain-inspired Intelligent Materials and Devices, and Department of Electronics, East China Normal University, Shanghai, 200241, China

    Luqiu Chen  (陈璐秋), Bing Yu  (余冰), Yang Shen  (沈阳), Yifei Liu  (刘逸飞), Haonan Wang  (王号南), Guangdi Feng  (冯光迪), Qiuxiang Zhu  (朱秋香), Qingbiao Zhao  (赵庆彪), Bobo Tian  (田博博), Junhao Chu  (褚君浩) & Chungang Duan  (段纯刚)

  2. Zhejiang Lab, Hangzhou, 310000, China

    Luqiu Chen  (陈璐秋), Yifei Liu  (刘逸飞), Haonan Wang  (王号南), Guangdi Feng  (冯光迪), Qiuxiang Zhu  (朱秋香) & Bobo Tian  (田博博)

  3. Laboratory of Solid State Microstructures and Innovation Center of Advanced Microstructures, Nan**g University, Nan**g, 210093, China

    Bing Yu  (余冰), Junming Liu  (刘俊明) & Jianguo Wan  (万建国)

  4. Key Laboratory of Artificial Structures and Quantum Control, School of Physics and Astronomy, Shanghai Jiao Tong University, Shanghai, 200240, China

    Yang Shen  (沈阳) & Weidong Luo  (罗卫东)

  5. School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan, 430205, China

    Qingbiao Zhao  (赵庆彪)

  6. State Key Laboratory of Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, Shanghai, 200083, China

    Junhao Chu  (褚君浩)

  7. Institute of Optoelectronics, Fudan University, Shanghai, 200433, China

    Junhao Chu  (褚君浩)

  8. Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan, 030006, China

    Chungang Duan  (段纯刚)

Authors
  1. Luqiu Chen  (陈璐秋)
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  2. Bing Yu  (余冰)
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  3. Yang Shen  (沈阳)
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  4. Yifei Liu  (刘逸飞)
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  5. Haonan Wang  (王号南)
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  6. Guangdi Feng  (冯光迪)
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  7. Qiuxiang Zhu  (朱秋香)
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  8. Weidong Luo  (罗卫东)
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  9. Junming Liu  (刘俊明)
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  10. Jianguo Wan  (万建国)
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  11. Qingbiao Zhao  (赵庆彪)
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  12. Bobo Tian  (田博博)
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  13. Junhao Chu  (褚君浩)
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  14. Chungang Duan  (段纯刚)
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Contributions

Author contributions Zhu Q, Tian B and Zhao Q conceived and supervised the research. Yu B and Chen L fabricated the devices. Yu B, Chen L, and Liu Y contributed to the electrical and magnetic measurements; Feng G and Wang H carried out materials characterization; Shen Y performed the theoretical calculation. Duan’s supervision. Chu J, Duan C, Liu J, Wan J, and Luo W advised on the experiments and data analysis. Yu B, Chen L, Shen Y, Zhu Q, Tian B and Zhao Q co-wrote the paper. All authors discussed the results and revised the manuscript.

Corresponding authors

Correspondence to Qiuxiang Zhu  (朱秋香), Qingbiao Zhao  (赵庆彪) or Bobo Tian  (田博博).

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Conflict of interest The authors declare no conflict of interest.

Additional information

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

Qiuxiang Zhu is an associate professor in the Department of Electronics, East China Normal University. She obtained a BS degree in Material Physics from Nan**g University in 2010 and received a PhD degree in Material Physics and Chemistry from Shanghai Institute of Ceramics, Chinese Academy of Sciences, in 2015. From 2016 to 2018, she worked as postdoc at Centre national de la recherche scientifique (CNRS)/Thales, France. Her research interests include ferroelectric thin films and devices for nonvolatile memory and neuromorphic computing.

Qingbiao Zhao is a professor in School of Chemistry and Environmental Engineering, Wuhan Institute of Technology. He obtained a BS degree in Chemistry from University of Science and Technology of China in 2006 and received a PhD degree in inorganic chemistry in University of South Carolina, USA. His research interests include magnetic oxide materials and functional inorganic materials.

Bobo Tian is a professor in the Department of Electronics, East China Normal University (ECNU) since 2019. He received a double doctoral degree from the University of Paris-Saclay, France, and the University of Chinese Academy of Sciences, China, in 2016. He held the postdoctor position at ECNU from 2016 to 2019. His research interests include memory and brain-like intelligent devices based on ferroelectric materials.

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Chen, L., Yu, B., Shen, Y. et al. Room-temperature ferroelectricity in magnetically ordered CoH2SeO4 flakes. Sci. China Mater. 67, 1654–1660 (2024). https://doi.org/10.1007/s40843-023-2795-0

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