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Magnetic two-dimensional chromium trihalides: structure, properties and modulation

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Abstract

The unique optical and electrical properties of two-dimensional (2D) materials provide a platform for novel van der Waals (vdW) heterojunction devices but the investigation of 2D magnetism is still limited. Recently, the emergence of long-range magnetic order atomically thin crystals expands 2D family, providing possibilities for the study of low-dimensional spin behavior and novel spintronics devices. As a specific member of magnetic van der Waals family, chromium trihalides (CrX3, X = Cl, Br, I) stimulated intensive interests on account of the newfangled magnetic properties. In this review, we briefly introduce the crystal structures, magnetism of the bulk and synthetic methods of 2D CrX3. Subsequently, the physical properties in atomically thin limit and magnetism manipulated by external field are presented. Next, some novel physical phenomena in CrX3 heterojunctions are discussed. Finally, the challenges and future directions are proposed. We focus on the intriguing physical phenomena in 2D magnetic CrX3 by combining related theoretical calculations and experimental results, providing a perspective on these emerging materials.

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摘要

二维材料独特的光学和电学特性为新型的范德华异质结器件提供了平台, 但对二维磁性的研究还很有限。近年来, 长程磁有序原子级薄晶体的出现扩展了二维材料体系, 为低维自旋行为和新型自旋电子器件的研究提供了可能性。三卤化铬(CrX3, X = Cl, Br, I)作为磁性范德华家族的特殊成员, 因其新颖的磁性性质引起了人们的广泛关注。本文简要介绍了二维CrX3的晶体结构、磁性及合成方法。随后探讨了二维极限下的物理性质和外加磁场作用下的磁性质。接着, 讨论了CrX3异质结中的一些新奇的物理现象。最后, 提出了研究中存在的问题和未来的发展方向。本文结合相关的理论计算和实验结果, 重点研究了二维磁性CrX3材料中有趣的物理现象, 为这些新兴材料的研究提供了新的思路.

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Fig. 1
Fig. 2

Reproduced with permission from Ref. [28]. Copyright 2015, American Chemical Society. b CrBr3 crystal. Reproduced with permission from Ref. [51], Copyright 2018, Wiley–VCH. c CrCl3 crystals. Reproduced with permission from Ref. [45]. Copyright 2017, American Physical Society. d Optical microscope (OM) images of 2D CrBr3 cleaved from a bulk crystal in air after different time indicating its stability. Reproduced with permission from Ref. [55]. Copyright 2019, American Chemical Society. e OM images of 2D CrI3 under ambient conditions illuminated with light for different time. Reproduced with permission from Ref. [56]. Copyright 2018, American Chemical Society. f OM images of cleaved CrCl3 down to monolayer. Reproduced with permission from Ref. [45]. Copyright 2017, American Physical Society

Fig. 3

Reproduced with permission from Ref. [8]. Copyright 2017, Springer Nature. MCD versus out-of-plane magnetic field for b monolayer and c bilayer CrI3 at 4 K. Reproduced with permission from Ref. [12]. Copyright 2018, Springer Nature. RMCD versus out-of-plane field for d trilayer and e four-layer CrI3. Reproduced with permission from Ref. [13]. Copyright 2018, American Association for the Advancement of Science

Fig. 4

Reproduced with permission from Ref. [29]. Copyright 2019, Springer Nature. f Polarization patterns of A1g mode at 60 and 15 K of monolayer CrI3; g Co- and cross-polarized Raman spectra taken in an AFM state at a zero applied magnetic field (left) and fully spin-up polarized state at 1.5 T (right) of bilayer CrI3. Reproduced with permission from Ref. [73]. Copyright 2020, Springer Nature. h 247 cm−1 Raman peak position shift as a function of polarization angle for bulk CrCl3 (left) and an exfoliated 17-nm-thick flake (right). Reproduced with permission from Ref. [36]. Copyright 2019, Springer Nature

Fig. 5

Reproduced with permission from Ref. [75]. Copyright 2018, Springer Nature. g Polarization-resolved PL for monolayer CrBr3 at ± 0.5 T; h hysteresis loops at various temperatures for monolayer CrBr3; i polarization as a function of magnetic field for bilayer CrBr3. Reproduced with permission from Ref. [55]. Copyright 2019, American Chemical Society. j LCP and RCP light components of PL from a 5-nm CrCl3. Reproduced with permission from Ref. [24]. Copyright 2019, American Chemical Society

Fig. 6

Reproduced with permission from Ref. [76]. Copyright 2019, American Association for the Advancement of Science. c MFM signal as a function of magnetic field; d illustration of stacking orders and spin configurations in surface and inner layers of CrI3; e MFM images of a 200-nm CrI3 flake. Reproduced with permission from Ref. [77]. Copyright 2020, American Chemical Society. f Spin-polarized tunneling spectra and g dI/dV curves as a function of magnetic field of monolayer CrBr3; spin-polarized tunneling and atomic structure of h H-type and i R-type bilayer CrBr3. Reproduced with permission from Ref. [61]. Copyright 2019, American Association for the Advancement of Science

Fig. 7

Reproduced with permission from Ref. [85]. Copyright 2019, Springer Nature

Fig. 8

Reproduced with permission from Ref. [90]. Copyright 2018, American Association for the Advancement of Science. Tunneling current (It) as a function of out-of-plane magnetic field at a selected bias voltage (left) through d bilayer, e trilayer, f 4-layer and corresponding sf-TMR ratio as a function of bias (right). Reproduced with permission from Ref. [13]. Copyright 2018 American, Association for the Advancement of Science

Fig. 9

Reproduced with permission from Ref. [17]. Copyright 2019, Springer Nature. d Schematic illustration of typical high-pressure experimental equipment; e tunnel current (It) versus applied magnetic field of a bilayer CrI3 at a series of pressures. Reproduced with permission from Ref. [16]. Copyright 2019, Springer Nature

Fig. 10

Reproduced with permission from Ref. [15]. Copyright 2018, Springer Nature. d Intensity of MOKE signal of a non-encapsulated bilayer CrI3 device as a function of both gate voltage and applied magnetic field; e selected horizontal line from d; f gate-driven transition from AFM to FM states; g schematic illustration depicting a potential difference between two layers. Reproduced with permission from Ref. [14]. Copyright 2018, Springer Nature. h Schematic illustration of dual-gate bilayer CrI3 field-effect device; i conductance of bilayer CrI3 as a function of gate voltage at 4 K; j MCD versus magnetic field at different doping levels; k coercive force (Hc), saturation magnetization (Ms) (both at 4 K) and Curie temperature (TC) at zero gate voltage as a function of gate voltage. Reproduced with permission from Ref. [12]. Copyright 2018, Springer Nature

Fig. 11

Reproduced with permission from Ref. [104]. Copyright 2020, American Chemical Society

Fig. 12

Reproduced with permission from Ref. [110]. Copyright 2019, Wiley–VCH. d Schematic illustration of vdW heterostructure of WSe2/CrI3; e schematic depicting spin orientation–dependent charge hopping between WSe2 and CrI3; f degree of circular polarization as a function of magnetic field of monolayer WSe2 with bilayer CrI3. Reproduced with permission from Ref. [113]. Copyright 2017, American Association for the Advancement of Science. g Gate dependence of linear conductance (G) of a CrI3/WTe2 device (left) and temperature dependence of minimum conductance (right); h second-harmonic current (I2f) versus magnetic field. Reproduced with permission from Ref. [120]. Copyright 2020, Springer Nature

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Acknowledgements

This study was financially supported by the National Key R&D Program of China (No. 2017YFA0206301), the National Natural Science Foundation of China (Nos. 51631001 and 52027801), the Natural Science Foundation of Beijing Municipality (No. 2191001) and the China-German Collaboration Project (No. M-0199).

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  1. Beijing Innovation Centre for Engineering Science and Advanced Technology, Beijing Key Laboratory for Magnetoelectric Materials and Devices, School of Materials Science and Engineering, Peking University, Beijing, 100871, China

    Biao Zhang, Yi Zeng, Zi-Jing Zhao, Da-Ping Qiu, Teng Zhang & Yang-Long Hou

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  1. Biao Zhang
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Zhang, B., Zeng, Y., Zhao, ZJ. et al. Magnetic two-dimensional chromium trihalides: structure, properties and modulation. Rare Met. 41, 2921–2942 (2022). https://doi.org/10.1007/s12598-022-02004-2

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