二维磁性材料的物性研究及性能调控

蒋小红; 秦泗晨; 幸子越; 邹星宇; 邓一帆; 王伟; 王琳

doi:10.7498/aps.70.20202146

摘要

以石墨烯和二硫化钼为代表的二维材料, 由于具有良好的电学、热学、光学以及力学性质, 近年来成为了科学界一大研究热点. 而作为二维材料的分支, 二维磁性材料由于具有磁各向异性、单层磁有序等特殊性质, 特别是磁性还可借助多种物理场进行调控, 使其具有丰富的物理特性和潜在的应用价值, 逐渐受到研究者的普遍关注. 本文详细总结了二维磁性材料的种类类型、合成方法、基本特性以及表征手段, 系统归纳了关于二维磁性材料物性调控方面的研究工作, 并对二维磁性材料的未来研究方向和挑战进行简单的展望.

关键词:

Abstract

Two-dimensional (2D) materials represented by graphene and molybdenum disulfide (MoS₂) have attracted much attention in recent years due to their advantages in electrical, thermal, optical and mechanical properties. As a branch of 2D materials, 2D magnetic materials have special properties such as magnetic anisotropy and single-layer magnetic order. Especially, their magnetism can also be controlled by a variety of physical fields, and it possesses various physical properties and potential applications. Therefore, they have received widespread attention of researchers gradually. In this article, we summarize the types, synthesis methods, basic characteristics and characterization methods of 2D magnetic materials in detail, and the magnetism controlling of 2D magnetic materials as well. Finally, a simple outlook on the research directions and future challenges of 2D magnetic materials is given.

Keywords:

作者及机构信息

1.
西北工业大学柔性电子研究院, 西安市柔性电子研究院, 柔性电子材料与器件工业与信息化部重点实验室, 陕西省柔性电子重点实验室, 西安市柔性电子重点实验室, 西安市生物医学材料与工程重点实验室, 西安　710072

2.
南京工业大学先进材料研究院, 江苏省柔性电子重点实验室, 南京　211816

通信作者: 王伟, iamwwang@njtech.edu.cn ; 王琳, iamlwang@njtech.edu.cn

基金项目: 国家重点研发计划青年项目(批准号: 2020YFA0308900)、国家自然科学基金(批准号: 92064010, 61801210, 91833302)、江苏省自然科学基金(批准号: BK20180686)、江苏省特聘教授和江苏省六大人才高峰基金(批准号: XYDXX-021)、中央高校基本科研业务费、陕西省重点研发项目(批准号: 2020GXLH-Z-020, 2020GXLH-Z-027)和西北工业大学硕士研究生创意创新种子基金(批准号: CX2020287)资助的课题

Authors and contacts

1.
Xi’an Key Laboratory of Biomedical Materials & Engineering, Xi’an Key Laboratory of Flexible Electronics, Shanxi Key Laboratory of Flexible Electronics, MIIT Key Laboratory of Flexible Electronics, Xi’an Institute of Flexible Electronics, Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an 710072, China

2.
Key Laboratory of Flexible Electronics, Institute of Advanced Materials, Nanjing Tech University, Nanjing 211816, China

Corresponding author: Wang Wei, iamwwang@njtech.edu.cn ; Wang Lin, iamlwang@njtech.edu.cn

Funds: Project supported by the National Key R&D Program of China (Grant No. 2020YFA0308900), the National Natural Science Foundation of China (Grant Nos. 92064010, 61801210, 91833302), the Natural Science Foundation of Jiangsu Province, China (Grant No. BK20180686), the Funding for “Distinguished Professors” and “High-level Talents in Six Industries” of Jiangsu Province, China (Grant No. XYDXX-021), the Fundamental Research Fund for the Central Universities, China, the Key Research and Development Program of Shaanxi Province, China (Grant Nos. 2020GXLH-Z-020, 2020GXLH-Z-027), and the Creative Innovation Seed Fund of Northwestern Polytechnical University for Postgraduate Students, China (Grant No. CX2020287)

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施引文献

图 1 二维磁性材料的简单分类

Fig. 1. Simple classification of two-dimensional magnetic materials.

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图 2 (a) Al₂O₃辅助机械剥离Fe₃GeTe₂薄片的示意图^[32]; (b)在Al₂O₃薄膜上剥落Fe₃GeTe₂薄片的光学图片^[32]; (c) CVD法合成FeTe纳米片的过程示意图^[133]; (d)薄层FeTe纳米片的光学图片^[133]; (e)超声液相剥离二维NiPS₃的原理图^[136]; (f) NiPS₃薄片AFM图^[136]; (g)分子束外延生长VSe₂的原理图^[143]; (h)单层VSe₂的AFM图^[143]

Fig. 2. (a) Schematic of Fe₃GeTe₂ exfoliated by Al₂O₃-assisted mechanical method^[32]; (b) optical image of typical few-layer Fe₃GeTe₂ flakes exfoliated on top of an Al₂O₃ thin film^[32]; (c) schematic illustration of FeTe nanosheet growth route by CVD^[133]; (d) optical image of few-layer FeTe flakes^[133]; (e) schematic illustration of NiPS₃ growth route by liquid exfoliation^[136]; (f) the AFM image of NiPS₃ flakes^[136]; (g) schematic illustration of VSe₂ growth route by molecular beam epitaxy^[143]; (h) the AFM image of monolayer VSe₂^[143].

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图 3 (a)磁圆二色性原理图; (b)和(c)双层和三层CrI₃自旋滤波器磁隧道结隧穿电流和反射磁圆二色性(RMCD)随外磁场(μ₀H_⊥)变化的函数关系曲线, 偏置电压分别为–290 mV和235 mV, 绿色(橙色)曲线表示递减(递增)磁场^[59]; (d)不同温度下, 厚度为48 nm的Fe₃GeTe₂样品RMCD信号随磁场的变化关系^[148]; (e)磁光克尔效应原理图; (f)双层Cr₂Ge₂Te₆在不同温度下的克尔旋转信号^[30]; (g) CrI₃的磁光克尔转角与外加磁场的关系^[31]; (h)不同温度下, Ta₃FeS₆纳米片极向磁光克尔随磁场的变化^[151]; (i)在空气环境4个月前后, Ta₃FeS₆纳米片的MOKE信号随磁场变化^[151]

Fig. 3. (a) Schematic diagram of magnetic circular dichroism; (b) and (c) tunneling current and reflective magnetic circular dichroism (RMCD) as a function of out-of-plane magnetic field (μ₀H_⊥) of double spin-filter magnetic tunnel junctions from bilayer and trilayer CrI₃ at a selected bias voltage –290 mV and 235 mV, respectively, green (orange) curve corresponds to decreasing (increasing) magnetic field^[59]; (d) comparison of RMCD sweeps for Fe₃GeTe₂ of thickness 48 nm as a function of the magnetic field, respectively^[148]; (e) schematic diagram of magneto-optic Kerr effect; (f) Kerr rotation signals of bilayer Cr₂Ge₂Te₆ vary with temperature^[30]; (g) the magneto-optic Kerr signals of different CrI₃ layers as a function of the magnetic field^[31]; (h) the polar MOKE signal of Ta₃FeS₆ nanosheet as a function of magnetic field at different temperatures^[151]; (i) MOKE signal of Ta₃FeS₆ nanosheet as a function of magnetic field acquired before and after 4 months aging under atmospheric conditions^[151].

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图 4 (a)磁力显微镜工作原理图; (b)单层/双层/三层VSe₂薄片的MFM相位图像^[106]; (c)图(b)中白色虚线对应的MFM图像的地形高度和MFM相位剖面图^[106]; (d), (e) Fe₃GeTe₂分别在204和103 K时MFM图像, (d)的插图为300 K时的MFM图像, 图中白色矩形勾画出了相同的区域^[148]; (f) 200 nm厚的CrI₃薄片MFM信号作为磁场的函数图^[155]; (g) 25 nm厚的CrI₃薄片MFM信号作为磁场的函数图^[155]; (h)表层和内层的堆叠顺序和自旋方向机理图^[155]; (i)扫描隧道显微镜原理图^[155]; (j)在热解石墨烯衬底上形成的单层VSe₂扫描隧道显微镜图, 单层VSe₂优先在阶梯边缘成核^[156]; (k)在MoS₂衬底上形成的单层VSe₂扫描隧道显微镜图, VSe₂在MoS₂衬底上形成更均匀的单层膜^[156]; (l) H型双层CrBr₃层间的铁磁性耦合^[61]; (m), (n) R型双层CrBr₃层间的反铁磁性耦合^[61]; (o)八面体的FeCl₆单元(顶图)和六边形1T-FeCl₂结构的示意图(底图)^[157]; (p)具有两种非等边的六边形1T-FeCl₂的STM图像^[157]

Fig. 4. (a) Schematic diagram of magnetic force microscope (MFM); (b) MFM phase image of monolayer/bilayer/trilayer VSe₂ flake^[106]; (c) topography height and MFM phase profiles of the MFM image corresponding to the white dashed line in panel (b)^[106]; (d), (e) MFM domain images for Fe₃GeTe₂ at 204 K and 103 K, respectively, inset of (d) is the MFM image at 300 K, and the white rectangles outline the same area^[148]; (f) MFM signal as a function of magnetic field for 200 nm CrI₃ flake; (g) MFM signal as a function of magnetic field for 25 nm CrI₃ flake^[155]; (h) illustration of the stacking orders and spin configurations insurface and inner layers^[155]; (i) schematic diagram of scanning tunneling microscope^[155]; (j) the STM image of VSe₂ monolayer on HOPG, VSe₂ monolayer islands preferentially nucleate at step edges on HOPG^[156]; (k) the STM image of VSe₂ monolayer on MoS₂, the growth of VSe₂ monolayer on MoS₂ is more uniform and gives rise to larger monolayer islands^[156]; (l) ferromagnetic coupling between H-type bilayer CrBr₃ layers^[61]; (m), (n) antiferromagnetic coupling between R-type bilayer CrBr₃ layers^[61]; (o) schematic illustration of an octahedral FeCl₆ unit (top) and a hexagonal island of FeCl₂ with a 1T structure (bottom)^[157]; (p) STM image of 1T-FeCl₂ with two non-equallateral hexagons^[157].

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图 5 (a)少层FePS₃拉曼随温度依赖的mapping图^[89]; (b)不同厚度下, 少层FePS₃的P_1a拉曼峰强度随温度的变化^[89]; (c)薄层Cr₂Ge₂Te₆样品$ {\rm{E}}_{\rm{g}}^{1} $和$ {\rm{E}}_{\rm{g}}^{2} $拉曼峰随温度依赖的mapping图^[158]; (d)不同温度下薄层Cr₂Ge₂Te₆样品的原始拉曼图^[158]; (e)单层CrI₃偏振拉曼光谱随磁场的演化过程^[62]; (f)单层CrI₃的拉曼强度与磁圆二色的结果比较^[62]; (g)双层CrI₃偏振拉曼光谱随磁场的演化过程^[62]; (h)双层CrI₃的拉曼强度与磁圆二色的结果比较^[62]; (i)反常霍尔效应的三种机制; (j)四层Fe₃GeTe₂的剩余霍尔电阻随温度的变化^[32]; (k) 2 K温度下, 不同厚度的Fe₃GeTe₂纳米片的反常霍尔电阻R_xy随磁场的变化关系^[111]; (l)不同温度下, 单个Fe₃GeTe₂的反常霍尔电阻随磁场的变化曲线^[142]; (m)不同温度下, Fe₃GeTe₂/MnTe异质结的反常霍尔电阻随磁场的变化曲线^[142]

Fig. 5. (a) Temperature dependent Raman mapping of few layers FePS₃ temperature dependent^[89]; (b) the Raman intensity as a function of temperature for different thickness FePS₃ of P_1a mode^[89]; (c) temperature dependent Raman spectra mapping for Cr₂Ge₂Te₆ of the $ {\rm{E}}_{\rm{g}}^{1} $ and $ {\rm{E}}_{\rm{g}}^{2} $ modes^[158]; (d) the original Raman diagram of few layer Cr₂Ge₂Te₆ at different temperatures^[158]; (e) the evolution process of polarization Raman spectra for monolayer CrI₃ with magnetic field^[62]; (f) comparison of Raman strength and MCD for monolayer CrI₃^[62]; (g) the evolution process of polarization Raman spectra of bilayer CrI₃ with magnetic field^[62]; (h) comparison of Raman strength and MCD for bilayer CrI₃^[62]; (i) the mechanism of anomalous Hall effect; (j) the remanent Hall resistance ${R}_{xy}^{\rm r}$ as a function of temperature for four-layer Fe₃GeTe₂^[32]; (k) the R_xy as a function of magnetic field for different thickness Fe₃GeTe₂ nanosheet at 2 K^[111]; (l) the R_xy as a function of magnetic field for Fe₃GeTe₂ heterojunction at different temperatures^[142]; (m) the R_xy as a function of magnetic field for Fe₃GeTe₂/MnTe heterojunction at different temperatures^[142]

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图 6 (a)顶部: 双栅极双层CrI₃场效应器件的示意性侧视图, 其中双分子层CrI₃被封装在少层石墨烯中, 石墨烯作为平面外输运测量的源极和漏极; 底部: 单双层样品器件的光学显微图. 左下图, 用于单层CrI₃的磁化率测量的电极结构, 比例尺为50 μm; 右下图, 用于双层CrI₃的磁化率测量的电极结构, 比例尺为20 μm; 红色虚线为双层样品的边界^[51]. (b)单层CrI₃的磁性随栅极电压(底轴)和诱导掺杂密度(顶轴)变化的函数^[51]. (c)双层CrI₃中, 在4 K下掺杂密度-磁场相图^[51]. (d)少数层h-BN/Cr₂Ge₂Te₆/h-BN范德瓦耳斯异质结器件^[94]. (e) 40 K, 负门电压下磁光克尔角随磁场的变化^[94]. (f) 40 K, 正门电压下磁光克尔角随磁场的变化^[94]

Fig. 6. (a) Top: A schematic side view of a dual-gate bilayer CrI₃ field-effect device. Bilayer CrI₃ is encapsulated in few-layer graphene, which also serves as source and drain electrodes for out-of plane transport measurements. Bottom: An optical micrograph for monolayer and bilayer CrI₃ sample devices. Scale bars, 50 μm (left panel) and 20 μm (right panel). The metallic ring structure (left panel) is used to create a magnetic field for the susceptibility measurement for monolayer CrI₃. The electrode structure (right panel) is used for the susceptibility measurement for bilayer CrI₃, the red dashed line marks the boundary of a bilayer sample in the right panel^[51]. (b) The magnetic properties of monolayer CrI₃ as a function of gate voltage (bottom axis) and induced doping density (top axis)^[51]. (c) Doping density-magnetic field phase diagram at 4 K for monolayer CrI₃^[51]. (d) Schematic diagram of a few-layered h-BN/Cr₂Ge₂Te₆/h-BN heterojunction^[94]. (e) Kerr angle as a function of magnetic field at 40 K for negative gate voltages^[94]. (f) Kerr angle as a function of magnetic field at 40 K for positive gate voltages^[94].

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图 7 (a) Fe₃GeTe₂的磁结构随厚度和温度的变化^[32]; (b)在三层Fe₃GeTe₂样品中获得的电导与门电压的关系, 测试温度为330 K, 插图为Fe₃GeTe₂离子场晶体管^[32]示意图, 其中S, D分别代表源电极和漏电极, V_n表示探测电压, 固态栅极覆盖了样品和周围电极^[32]; (c)三层Fe₃GeTe₂在特定栅压下(T = 10 K和T = 240 K)的反常霍尔电阻随磁场的变化曲线^[32]; (d)三层Fe₃GeTe₂温度和栅压的相图^[32]; (e)在栅极电压V_g = 2.1 V时, 四层Fe₃GeTe₂在室温附近的反常霍尔电阻随磁场的变化^[32]

Fig. 7. (a) Phase diagram of Fe₃GeTe₂ (FGT) as a function of layer number and temperature^[32]. (b) conductance as a function of gate voltage V_g measured in a trilayer FGT device. Data are obtained at T = 330 K, the inset shows a schematic of the FGT device structure and measurement setup, S and D label the source and drain electrodes, respectively, and V_n labels the voltage probes. The solid electrolyte covers both the FGT flake and the side gate^[32]. (c) R_xy as a function of external magnetic field recorded at representative gate voltages obtained at T = 10 K and T = 240 K^[32]; (d) the phase diagram of the trilayer FGT sample as a function of the gate voltage and temperature^[32]; (e) R_xy of four-layer FGT as a function of magnetic field under a gate voltage of V_g = 2.1 V at room temperature^[32].

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图 8 (a) CrI₃晶体结构, 分别为单斜相(左)和六方相(右)^[164]; (b) CrI₃隧道结的光学图片^[164]; (c) CrI₃隧道结的侧面示意图^[164]; (d), (e) 在施加压力前(d)后(e)两个2层(2L)和两个5层(5L)区域, 在3.5 K时, MCD随磁场的变化^[164]; (f)双层CrI₃隧道结中, 不同压力下, 隧道电流随磁场的变化^[165]; (g)双层CrI₃隧道结施加压力前后RMCD信号随磁场的变化^[165]; (h)高压实验装置示意图^[165]; (i), (j), (k)三层CrI₃中其中任意三点的RMCD随磁场的变化^[165]

Fig. 8. (a) Crystal structure of CrI₃, the monoclinic phase (left) and the hexagonal phase (right)^[164]; (b) the optical image of CrI₃ tunnel junction^[164]; (c) the side view of the CrI₃ tunnel junction^[164]; (d), (e) the MCD for 2L and 5L CrI₃ before (d) and after (e) pressured as a function of the magnetic field under the temperature of 3.5 K^[164]; (f) the tunnel current for bilayer CrI₃ as a function of the magnetic field under different pressures^[165]; (g) the RMCD signal for bilayer CrI₃ tunnel junction as a function of the magnetic field before and after pressured^[165]; (h) schematic of high-pressure experimental set-up^[165]; (i), (j), (k) the RMCD signal for any three points of trilayer CrI₃ as a function of the magnetic field^[165].

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图 9 (a) Fe₃GeTe₂及FePS₃/Fe₃GeTe₂异质结的克尔旋转角随磁场的变化曲线^[168]; (b) Fe₃GeTe₂及FePS₃/Fe₃GeTe₂/FePS₃异质结的克尔旋转角随磁场的变化曲线^[168]; (c)双层反铁磁/铁磁异质结FePS₃/Fe₃GeTe₂和(d)三层反铁磁/铁磁/反铁磁异质结FePS₃/Fe₃GeTe₂/FePS₃表现出的交换偏置现象^[168]; (e) Fe₃GeTe₂及FePS₃/Fe₃GeTe₂异质结的克尔旋转角随温度的变化曲线^[168]; (f) Fe₃GeTe₂及FePS₃/Fe₃GeTe₂/FePS₃异质结的克尔旋转角随温度的变化曲线^[168]

Fig. 9. (a) The Kerr rotations as a function of magnetic field for Fe₃GeTe₂ (FGT, yellow curves) and FePS₃/Fe₃GeTe₂ (FPS/FGT, green curves)^[168]; (b) the Kerr rotations as a function of magnetic field for FGT (yellow curves) and FePS₃/Fe₃GeTe₂/FePS₃ (FPS/FGT/FPS, green curves)^[168]; the exchange bias phenomenon for (c) bilayer antiferromagnetic/ferromagnetic heterojunction FPS/FGT and (d) trilayer antiferromagnetic/ferromagnetic/antiferromagnetic heterojunction FPS/FGT/FPS under the different external magnetic fields^[168]; (e) the Kerr rotations as a function of the temperature for FGT (red curve) and FPS/FGT (blue curve)^[168]; (f) the Kerr rotation as a function of the temperature for FGT (red curve) and FPS/FGT/FPS (blue curve)^[168].

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