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大面积二维磁性材料的制备及居里温度调控

王海宇 刘英杰 寻璐璐 李竞 杨晴 田祺云 聂天晓 赵巍胜

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大面积二维磁性材料的制备及居里温度调控

王海宇, 刘英杰, 寻璐璐, 李竞, 杨晴, 田祺云, 聂天晓, 赵巍胜

Research progress of preparation of large-scale two-dimensional magnetic materials and manipulation of Curie temperature

Wang Hai-Yu, Liu Ying-Jie, Xun Lu-Lu, Li Jing, Yang Qing, Tian Qi-Yun, Nie Tian-Xiao, Zhao Wei-Sheng
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  • 当前, 尽管集成电路制造工艺水平不断提高, 但受到量子效应的限制, 器件尺寸的缩小使业界遇到了可靠性低、功耗大等瓶颈, 微电子行业延续了近50年的“摩尔定律”将难以持续. 2004年二维材料—石墨烯的问世, 为突破集成电路的功耗瓶颈带来了新的机遇. 由于低维特性, 二维材料在一层或者几层原子厚度中表现出丰富多样的电学、磁学、力学和光学等物理特性. 其中, 铁磁性在信息处理、存储等技术上有着广泛的应用价值. 然而, 目前在实验上合成的具有铁磁性的二维材料屈指可数. 同时, 在二维系统中长程有序磁态会因为热涨落的因素在有限温度内受到强烈的抑制, 无法在室温下保持铁磁性, 这为后续工作带来了不可忽视的限制与挑战. 因此实现二维磁性材料室温下的铁磁有序及其调控是现阶段需要解决的重大问题. 本综述详细地介绍了二维磁性材料的发展过程、制备方法及其优越性能, 并着重阐述了调控二维磁性材料居里温度的方法. 最后, 扼要地分析并展望了二维磁性材料在未来的应用前景.
    To date, despite the continuous improvement of integrated circuit manufacturing technology, it has been limited by quantum effects and the shrinking of device size has caused the industry to encounter bottlenecks such as low reliability and high power consumption. The “Moore’s Law” that has lasted for nearly 50 years in the microelectronics industry will not be sustainable. In 2004, the advent of graphene, a two-dimensional (2D) material, brought new opportunities to break through the power consumption bottleneck of integrated circuits. Due to the low dimensionality, 2D materials exhibit a variety of fasinatingly electrical, ferromagnetic, mechanical, and optical properties at an atomic level. Among them, ferromagnetism has a wide range of applications in information processing, magnetic memory and other technologies. However, only a few 2D ferromagnetic materials are successfully synthesized. Meanwhile, the magnetic long-range order will be strongly suppressed within a limited temperature range due to thermal fluctuations, and thus bringing non-ignorable limitations and challenges to subsequent work. Therefore, the realization and control of room-temperature ferromagnetism in 2D magnetic materials is the major concern at this stage. In light of the above, this review first introduces the development process, preparation methods and superior properties of 2D magnetic materials in detail, and then focuses on the methods of manipulating the Curie temperature of 2D magnetic material. Finally, we briefly give an outlook of the application prospects in the future.
      通信作者: 聂天晓, nietianxiao@buaa.edu.cn
    • 基金项目: 国家自然科学基金(批准号: 61774013)、国家重点研发计划(批准号: 2018YFB0407602)和国家科技重大专项(批准号: 2017ZX01032101)资助的课题
      Corresponding author: Nie Tian-Xiao, nietianxiao@buaa.edu.cn
    • Funds: Project supported by the National Natural Science Foundation of China (Grant No. 61774013), the National Key R&D Program of China (Grant No. 2018YFB0407602), and the National Science and Technology Major Project of the Ministry of Science and Technology of China (Grant No. 2017ZX01032101)
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  • 图 1  单层石墨烯机械剥离流程[36]

    Fig. 1.  Mechanical peeling process of single-layer graphene[36].

    图 2  (a) 分子束外延生长腔示意图; (b) 薄膜生长过程示意图

    Fig. 2.  (a) Schematic diagram of molecular beam epitaxial growth cavity; (b) schematic diagram of film growth process.

    图 3  (a) Cr2Ge2Te6的原子结构视图[25], 其中蓝色、黄色和橘色的球分别代表Cr, Ge和 Te原子. (b) 单层CrI3的平面内原子结构视图, 其中灰色和紫色的球分别代表Cr和I原子[26]. (c) Fe3GeTe2的面内和面外原子结构视图, 其中黄色、紫色和绿色的球分别代表Fe, Ge和 Te原子[55]

    Fig. 3.  (a) Atomic structure view of Cr2Ge2Te6. The blue, yellow, and orange balls represent Cr, Ge, and Te atoms, respectively[25]. (b) In-plane atomic structure view of a single layer of CrI3. The gray and purple balls represent Cr and I atoms, respectively[26]. (c) In-plane and out-of-plane atomic structure views of Fe3GeTe2. The yellow, purple and green balls represent Fe, Ge and Te atoms, respectively[55].

    图 4  (a), (b) FGT薄膜的居里温度随厚度的依赖关系[56,57]; (c)不同温度下30 nm FGT/O-FGT薄膜器件的反常霍尔电阻与垂直磁场的关系, 其中在90 K温度下出现负的剩磁[58]; (d) FGT薄膜的能斯特信号横向电压与垂直磁场的关系, 温度梯度分别为$\nabla {T_x} = 1.3\;{\rm{K}} \cdot {{\text{μ} }}{{\rm{m}}^{ - 1}}$$\nabla {T_x} = - 1.1\;{\rm{K}} \cdot {\text{μ} }{{\rm{m}}^{ - 1}}$[59]; (e) Fe3–xGeTe2薄膜的磁晶各向异性能与磁化强度随掺杂浓度变化的关系[60]

    Fig. 4.  (a), (b) Thickness-dependent Curie temperature of FGT films for critical analysis[56,57]; (c) relationship between the anomalous Hall resistance of 30 nm thick FGT/O-FGT device and the perpendicular magnetic field under different temperatures, where the negative remanence magnetization appears at 90 K[58]; (d) relationship between the transverse voltage of the Nernst signal of FGT film and the perpendicular magnetic field with temperature gradient of $\nabla {T_x} = 1.3\;{\rm{K}} \cdot {\text{μ} }{{\rm{m}}^{ - 1}}$ and $\nabla {T_x} = - 1.1\;{\rm{K}} \cdot {\text{μ} }{{\rm{m}}^{ - 1}}$, respectively[59]; (e) change of the magnetocrystalline anisotropy of Fe3–xGeTe2 film and the magnetization with doping concentration[60]

    图 5  (a) 在μ0H = 0.78 T时, RMCD强度与顶栅电压和背栅电压的关系, 可以看出在双层CrI3中利用静电门控制的磁性转变[63]; (b) 4 K时双层CrI3中栅极电压-掺杂密度-磁场相位图, 可以看出双层CrI3中利用电子掺杂控制的磁性转变[64]

    Fig. 5.  (a) RMCD signals under the top gate and back gate voltage at μ0H = 0.78 T. Magnetic transition can be controlled by electrostatic gate in double-layer CrI3[63]. (b) Gate voltage-electron doping density-magnetic field phase diagram in double layer CrI3 at 4 K. Magnetic transition can be controlled by electron doping in double-layer CrI3[64].

    图 6  (a) HOPG上单层VSe2在300 K处的面内和面外磁滞回线[66]; (b) MnSex在300 K处的面外磁滞回线[67]

    Fig. 6.  (a) In-plane and out-of-plane hysteresis loops of a single layer of VSe2 on HOPG at 300 K[66]; (b) out-of-plane hysteresis loops of MnSex at 300 K[67].

    图 7  (a) CGT薄膜在不同栅电压下的场效应曲线[68]; (b)静电掺杂的CGT薄膜器件在不同栅电压下居里温度的变化[69]; (c)栅电压调控的四层FGT薄膜的霍尔曲线[33]

    Fig. 7.  (a) Field-effect Ids curves of CGT film[68]; (b) variation of Curie temperature of CGT device with electron doping under different voltages[69]; (c) gate-voltage controlled Hall curves of four-layer FGT flake[33].

    图 8  (a), (b), (c) 改变Fe的浓度调控FGT薄膜居里温度的变化[55,48,70]; (d) 改变Ga的曝光时间调控FGT薄膜居里温度的变化[71]

    Fig. 8.  (a), (b), (c) Changing the concentration of Fe to regulate Curie temperature of FGT films[55,48,70]; (d) exposure time of Ga-controlled Curie temperature of FGT film[71].

    图 9  (a) 图形诱导FGT薄膜铁磁性的变化[72]; (b) 应变诱导CGT薄膜居里温度的变化[32]

    Fig. 9.  (a) Pattern induces the variation of ferromagnetism of FGT film[72]; (b) strain induces the variation of Curie temperature of CGT film[32].

    图 10  (a) 反铁磁MnTe增强Fe3GeTe2铁磁性[55]; (b) 反铁磁CrSb近邻效应诱导居里温度的变化[73]; (c) EuS/Bi2Se3界面增强居里温度[77]

    Fig. 10.  (a) Antiferromagnetic MnTe induced Fe3GeTe2 ferromagnetism enhancement[55]; (b) antiferromagnetic CrSb proximity-induced Curie temperature increase[73]; (c) EuS/Bi2Se3 interfacial-enhanced Curie temperature[77].

    图 11  (a) Bi2Te3(8)/FGT(5)异质结构随温度变化的电阻率; (b), (c) 不同温度下的面外反常霍尔曲线; (d) 不同温度下的面内反常霍尔曲线; (e) 阿罗特图来精准表征居里温度; (f) 300 K下异质结构的磁光克尔信号; (g), (h), (i) 不同厚度下异质结构的居里温度表征[31]

    Fig. 11.  (a) Resistivity of Bi2Te3(8)/FGT(5) heterostructure with the variation of temperature; (b), (c) out-of-plane anomalous Hall curves under different temperatures; (d) in-plane anomalous Hall curves under different temperatures; (e) Arrott plot for characterizing the Curie temperature; (f) magneto-optical Kerr signal of the heterostructure at 300 K; (g), (h), (i) thickness-dependent Curie temperature[31].

    表 1  部分二维磁性材料的汇总[65]

    Table 1.  Summary of some two-dimensional (2D) magnetic materials[65].

    2D材料/异质结构$ {T_{\rm{c}}}/K $计算/制造方法
    VSe2/MoS2和VSe2/HOPE
    vdW heterostructure
    > 300MBE
    VS2/WS2 vdW heterostructure487DFT
    VS2/MoS2 vdW heterostructure485DFT
    VTe2128DFT
    MnSe2/GaSe和MnSe2/SnSe2
    vdW heterostructure
    > 300MBE
    MnSe2286DFT
    MnS2253DFT
    MnI215DFT
    NiI263DFT
    CrSCI150DFT
    CrSBr160DFT
    CrSI170DFT
    CrI345机械剥离法
    CrI3161DFT
    CrI395DFT
    CrCl349DFT
    CrBr373DFT
    CrF341DFT
    CrTe371DFT
    NiCl3400DFT
    CrGeTe330机械剥离法
    CrGeTe3314DFT
    CrGeTe3130DFT
    CrSiTe3214DFT
    CrSiTe390DFT
    CrSiTe3170DFT
    Cr3Te42057DFT
    Fe3GeTe220—300机械剥离法
    Fe3GeTe2270—300机械剥离法
    Cr3C > 300DFT
    下载: 导出CSV

    表 2  FGT和Bi2Te3/FGT磁性相互交换作用

    Table 2.  Magnetic interaction of FGT and Bi2Te3/FGT.

    E0EFM
    /eV
    EAFM-In
    /eV
    EAFM-L
    /eV
    J1
    /meV
    J2
    /meV
    J3
    /meV
    Pure FGT0–11.441–10.703–11.2723.675–1.8170.663
    Bi2Te3/FGT0–16.400–15.196–15.7425.906–2.9231.064
    下载: 导出CSV
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  • 收稿日期:  2021-01-29
  • 修回日期:  2021-02-25
  • 上网日期:  2021-06-18
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