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具有磁各向异性的二维磁性材料可在有限温度下和单层极限下形成磁有序, 其宏观磁性与层数、堆叠形式等密切相关且其磁交换作用可被多种外场调控. 这些新奇特性赋予了二维磁性材料丰富的物理内涵和潜在的应用价值, 受到了研究者的广泛关注. 本文着重介绍近年来二维磁体在实验和理论计算两方面的研究进展, 首先从几种二维磁性材料中常见的磁交换机制出发, 随后以组分作为分类依据, 详细介绍一些主要二维磁体的几何和电子结构以及它们的磁耦合方式; 在此基础上, 再讨论如何通过外部(外场和界面)和内部(堆叠和缺陷)两类方式调控二维磁体的电子结构和磁性; 继而探讨如何利用这两类调控方式, 将上述材料应用于实际自旋电子学器件以及磁存储等方面的潜力; 最后总结和展望了目前二维磁性材料遇到的困难和挑战以及未来可能的研究方向.Two-dimensional (2D) magnetic materials with magnetic anisotropy can form magnetic order at finite temperature and monolayer limit. Their macroscopic magnetism is closely related to the number of layers and stacking forms, and their magnetic exchange coupling can be regulated by a variety of external fields. These novel properties endow 2D magnetic materials with rich physical connotation and potential application value, thus having attracted extensive attention. In this paper, the recent advances in the experiments and theoretical calculations of 2D magnets are reviewed. Firstly, the common magnetic exchange mechanisms in several 2D magnetic materials are introduced. Then, the geometric and electronic structures of some 2D magnets and their magnetic coupling mechanisms are introduced in detail according to their components. Furthermore, we discuss how to regulate the electronic structure and magnetism of 2D magnets by external (field modulation and interfacial effect) and internal (stacking and defect) methods. Then we discuss the potential applications of these materials in spintronics devices and magnetic storage. Finally, the encountered difficulties and challenges of 2D magnetic materials and the possible research directions in the future are summarized and prospected.
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Keywords:
- two-dimensional magnetic materials /
- magnetic mechanism /
- external field modulation /
- magnetic tunneling junction /
- spintronics
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图 2 二维磁体典型的几种磁构型 (a)—(d) 二维六角晶格的铁磁、stripy反铁磁、ZZ反铁磁和Néel反铁磁; (e)—(h) 二维四方晶格的铁磁、双共线(bicollinear)反铁磁、stripy反铁磁和Néel反铁磁; (i)—(k) 三角晶格的铁磁、stripy反铁磁和ZZ反铁磁; (l) 层间A型反铁磁
Fig. 2. Typical magnetic configurations of 2D magnetism: (a)–(d) FM, stripy-AFM, ZZ-AFM, Néel-AFM of a 2D hexagonal lattice; (e)–(h) FM, bicolliear-AFM, stripy-AFM and Néel -AFM of a 2D tetragonal lattice; (i)–(k) FM, stripy-AFM and ZZ-AFM of a 2D triangular lattice; (l) schematic for an interlayer A-type AFM state.
图 6 过渡金属卤化物的结构及其磁性 (a) 单层CrI3的原子结构; (b)单层和(c)双层CrBr3的扫描隧道显微镜图[56]; (d)垂直平面外磁场下自旋极化的隧穿谱; (e) dI/dV信号和外磁场的关系; (f) NiI2的三角晶格结构[77]; (g)块体NiI2的螺磁序; (h)块体NiI2的磁化率与温度之间的关系; (i) 30 K和(j) 70 K下块体NiI2角度相关的二次谐波产生强度; (k) 在选定的方位角上与温度相关的二次谐波产生强度
Fig. 6. Structural and magnetic properties of transition metal halides: (a) Atomic structure of monolayer CrI3; (b), (c) scanning tunneling microscopy of (b) monolayer and (c) bilayer CrBr3[56]; (d) spin-polarized tunneling spectra under out-of-plane magnetic field; (e) dI/dV signal as a function of the magnetic field; (f) layered triangular crystalline structure of NiI2[77]; (g) cycloidal order of magnetic moments in bulk NiI2; (h) temperature-dependent magnetic susceptibility of the bulk NiI2; (i), (j) angle-dependent second-harmonic generation (SHG) intensity of bulk NiI2 at 30 K and 70 K; (k) temperature-dependent S intensity at the selected azimuth angle.
图 7 过渡金属硫化物的结构及其磁性 (a) 1T相过渡金属硫化物的原子结构[81]; (b) 不同层厚CrSe2的原子力显微镜图[100]; (c) CrSe2的磁相图随着层数和温度的变化[100]; (d) Cr3Te4/graphene异质结的理论计算, 包括自旋电荷密度、差分电荷密度、界面处的静电势及分态密度[103]
Fig. 7. Structural and magnetic properties of transition metal sulfides: (a) Atomic structure of transition metal sulfides in 1T phase[81]; (b) atomic force microcopy images of CrSe2 nanosheets with different thickness[100]; (c) magnetic phase diagram for CrSe2 of layer number versus temperature[100]; (d) theoretical calculations for Cr3Te4/graphene heterostructure, including spin density, differential charge density, in-plane average electrostatic potential across the interface and partial density of states (PDOS)[103].
图 9 三元过渡金属化合物 (a) Cr2Ge2Te6和(b) Fe3GeTe2的原子结构[37]; (c) M-X-Y 化合物(M = Cr, Mn; X = O, S, Se, Te; Y = Cl, Br, I)的原子结构、自旋密度和原子差分电荷密度[142]; (d)范德瓦耳斯材料CrPS4的磁性[154]
Fig. 9. Ternary transition metal compounds: Atomic structures of (a) Cr2Ge2Te6 and (b) Fe3GeTe2[37]; (c) atomic structure, spin density and atomic differential charge density of M-X-Y (M = Cr, Mn; X = O, S, Se, Te; Y = Cl, Br, I) compounds[142]; (d) magnetic properties of van der Waals CrPS4[154].
图 11 二维磁体中几种常见的调控手段 (a) Fe3GeTe2的居里温度随施加压强的变化[171]; (b)自旋垂直和平行于单层CrI3的能带结构[69]; (c)双层CrI3的磁矩在外加电场下的变化示意图[67]; (d)双层CrI3的层间交换能与层间相对平移的关系[31]
Fig. 11. Several common manipulation methods in 2D magnets: (a) The Curie temperature of Fe3GeTe2 as a function of pressure[171]; (b) band structures of CrI3 monolayer with spin perpendicular and parallel to CrI3 plane[69]; (c) schematic diagram of spin configuration of bilayer CrI3 under external field[67]; (d) interlayer exchange energy of bilayer CrI3 as a function of in-plane shifts[31]
图 12 (a) 二维磁性的界面工程[201]; (b)光学手段调控WSe2/CrI3异质结的磁近邻效应[203]; (c) CrI3/MoTe2之间提供额外的超交换通道来提高磁耦合[207]; (d)块体半导体衬底的近邻效应调控高温相双层CrI3的居里温度[206]
Fig. 12. (a) Interfacial engineering of 2D magnets[201]; (b) optically tuning the magnetic proximity effect in WSe2/CrI3 heterostructure[203]; (c) improving magnetic coupling of CrI3/MoTe2 heterostructure by extra spin superexchange paths[207]; (d) increasing Curie temperature of bilayer CrI3 in high-temperature phase on bulk semiconducting substrate[206].
图 14 (a), (b)两边电极平行排列磁隧道结的示意图及其能带; (c), (d)两边电极反平行排列磁隧道结的示意图及其能带; (e)—(g)三种基于磁隧道结的可能自旋电子学器件应用[290]
Fig. 14. (a), (b) Schematic diagram of a magnetic tunneling junction in parallel configuration and its band structure; (c), (d) schematic diagram of a magnetic tunneling junction in antiparallel configuration and its band structure; (e)–(g) three types of potential applications of magnetic tunneling junction[290].
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