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Cation ratio and oxygen defects for engineering the magnetic transition of monodisperse nonstoichiometric zinc ferrite nanoparticles

非化学计量比锌铁氧体中阳离子比与氧缺陷对其磁性转变的调控研究

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Abstract

Monodisperse nonstoichiometric zinc ferrite nanoparticles with a tunable size of 4.1–32.2 nm are fabricated via thermal decomposition. An extrinsic impurity phase of the ZnO component is present in the zinc ferrite nanoparticles with a size of <10 nm, but this phase can be eliminated after the air annealing treatment. The atom ratio of Zn/Fe and concentration of oxygen vacancies decrease as the particle size of zinc ferrite increases, causing magnetic transition from superparamagnetism to ferromagnetism. The X-ray magnetic circular dichroism spectra reveal that the spin magnetic moments of Fe3+ are reduced, and the orbital magnetic moments are frozen with the increasing atom ratio of Zn/Fe. Therefore, saturation magnetization decreases. The saturation magnetizations of all the zinc ferrite nanoparticles decrease after the air annealing treatment, suggesting that oxygen vacancies considerably influence the magnetic properties. The air annealing treatment can minimize the number of oxygen defects, which trigger some of the Fe3+-OV-Fe3+ ferrimagnetic couplings to transfer into the Fe3+-O2−-Fe3+ antiferromagnetic couplings. This work provides new insights regarding the magnetic performance of spinel ferrites by tuning the stoichiometric ratio and oxygen defects.

摘要

本文采用热解法制备了粒径在4.1–32.2 nm范围内可调的单分散非化学计量比锌铁氧体纳米颗粒. 当颗粒尺寸小于10 nm时, 样品中含有少量的非本征ZnO杂质相, 且空气退火后该杂质相消失. 锌铁氧体中锌/铁原子比与氧缺陷浓度均随着颗粒尺寸的增大而降低, 导致其从超顺磁性转变为铁磁性. 磁性圆二色谱表明, 随着Zn/Fe比的增加, Fe3+的自旋磁矩减小, 轨道磁矩冻结, 饱和磁化**度降低. 经过空气退火, 所有样品的饱和磁化**度降低, 表明氧缺陷(OV)对其磁性有很大影响. 空气退火会降低氧缺陷含量, 部分Fe3+–OV–Fe3+铁磁耦合转变为Fe3+–O2−–Fe3+反铁磁耦合. 该工作通过调控化学计量比和氧缺陷实现了对锌铁氧体磁性的调节, 为理解和调控铁氧体的磁学性质提供了新的思路.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51572218, 11504293 and 11904275), the Natural Science Foundation of Shaanxi Province (2019JM-138), the Scientific Research Program Funded by Shaanxi Provincial Education Department (18JK0786, 19JK0413 and 20JK0946), and the Key Project of Research and Development of Shaanxi Province (2018ZDCXL-GY-08-05). The staff of Singapore Synchrotron Light Source and beam time from SINS beamline were acknowledged for their assistance.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Physics, Northwest University, **’an, 710069, China

    Yong Sun  (孙勇), Yan Zong  (宗妍), **nghua Li  (**兴华), Juan Feng  (冯娟) & **nliang Zheng  (郑新亮)

  2. State Key Laboratory of Photon Technology in Western China Energy, Northwest University, **’an, 710069, China

    Yan Zong  (宗妍), **nghua Li  (**兴华), Juan Feng  (冯娟) & **nliang Zheng  (郑新亮)

  3. School of Life Science and Electron Microscopy Center of Lanzhou University, Lanzhou University, Lanzhou, 730000, China

    **a Deng  (邓霞)

  4. Key Laboratory of Magnetism and Magnetic Materials of the Ministry of Education, Lanzhou University, Lanzhou, 730000, China

    Junwei Zhang  (张军伟) & Yong Peng  (彭勇)

  5. National University of Singapore, Singapore Synchrotron Light Source, 5 Res Link, Singapore, 117603, Singapore

    **ao Chi  (池啸)

  6. School of Science, **’an Technological University, **’an, 710021, China

    Zhenhua Shi  (史振华)

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  1. Yong Sun  (孙勇)
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Contributions

Author contributions Sun Y performed the experiments and theoretical calculation; Deng X conducted the STEM characterization and QSTEM analysis; Li X, Peng Y, and Zheng X designed the project; Chi X carried out the XMCD characterization and analysis; Zong Y completed the XPS characterization; Deng X and Zhang J performed the EELS analysis; Feng J performed the TEM characterization; Shi Z performed the magnetic analysis; Sun Y, Li X, and Zheng X wrote the draft of manuscript; Li X and Zheng X revised the manuscript. All authors contributed to the general discussion and checked the manuscript.

Corresponding authors

Correspondence to **nghua Li  (**兴华), **ao Chi  (池啸) or Yong Peng  (彭勇).

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Conflict of interest The authors declare no conflict of interest.

Additional information

Yong Sun received his BSc degree from Northwest University in 2011. He is currently a PhD candidate at the School of Physics, Northwest University. He was an exchange student of Nanyang Technological University (NTU) in Singapore (November 2019-April 2020). His research focuses on magnetic materials and microwave absorption materials.

** magneto-related instruments and in situ electron microscopes and characterizing the microstructures and dynamical behaviors of low-dimensional magnetic materials and devices.

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40843_2020_1592_MOESM1_ESM.pdf

Cation ratio and oxygen defects for engineering the magnetic transition of monodisperse nonstoichiometric zinc ferrite nanoparticles

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Sun, Y., Deng, X., Zong, Y. et al. Cation ratio and oxygen defects for engineering the magnetic transition of monodisperse nonstoichiometric zinc ferrite nanoparticles. Sci. China Mater. 64, 2017–2028 (2021). https://doi.org/10.1007/s40843-020-1592-y

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