二维本征铁电体及其多铁耦合的研究进展

叶倩; 沈阳; 袁野; 赵祎峰; 段纯刚

doi:10.7498/aps.69.20201433

摘要

铁电材料因其具有可被外场调控的电极化状态, 以及在传感器、光电器件和信息存储器件中具有潜在应用前景, 所以一直以来都是凝聚态物理领域的研究热点. 随着微电子集成技术的飞速发展, 电子器件日益趋于微型化、集成化和多功能化. 传统块体铁电材料因受尺寸效应、界面效应等因素影响, 难以满足此发展需求, 因而低维铁电材料引起了学术界的广泛关注. 近年来, 实验上已成功制备出稳定的室温二维铁电材料, 第一性原理计算等理论方法对新材料的预测和设计也促进了二维铁电材料的发展. 同时, 利用二维铁电性与铁谷性、磁性的多铁耦合效应, 可以实现电控谷极化、电控磁性等调控机制. 多重自由度的相互耦合, 会产生如能谷间圆(线)偏振光学选择性、量子自旋霍尔效应等奇异物理特性, 对于自旋电子学、谷电子学及光学的发展具有重大的意义. 本文首先介绍近年来新型二维铁电材料在理论和实验方面的研究进展, 以及二维铁电材料在铁电隧道结、铁电二极管等二维铁电器件中的应用. 其次阐述了二维电控铁谷性和电控磁性的多铁耦合效应及其衍生出的新物理现象和机制. 最后对二维铁电材料和其他物理性质耦合所具有的丰富物理内涵和广阔应用前景, 进行了分析与探讨.

关键词:

二维铁电材料 /
二维铁电器件 /
多铁耦合 /
第一性原理计算

Abstract

Ferroelectric materials have become a research focus of condensed matter physics because of their electric polarization state which can be regulated by external field and has potential applications in sensors, optoelectronic devices and information memory devices. With the rapid development of microelectronic integration technology, electronic devices are becoming more and more miniaturized, integrated and multifunctional. Due to the size effect and interface effect, the traditional bulk ferroelectric materials are difficult to meet the requirements for this development. Therefore, low-dimensional ferroelectric materials have received extensive attention of the academic circle. In recent years, stable room temperature intrinsic two-dimensional ferroelectric materials have been successfully prepared. The prediction and design of new materials in theoretical method such as first principles calculation also promote the development of two-dimensional ferroelectric materials. At the same time, the multiferroic coupling effect of two-dimensional ferroelectricity, ferrovalley and magnetism can be used to realize the electronic valley polarization, electronic magnetic control and other regulatory mechanisms. The coupling of multiple degrees of freedom will produce strange physical properties such as optical selectivity of circular (linear) polarization between energy valleys and quantum spin Hall effect, which is of great significance for developing spintronics, valley electronics and optics. In this paper, the recent progress of theoretical and experimental research of new two-dimensional ferroelectric materials is introduced, and the applications of two-dimensional ferroelectric materials in two-dimensional ferroelectric devices such as ferroelectric tunnel junctions and ferroelectric diodes are presented. Secondly, the multiferroic coupling effect of two-dimensional electrically controlled ferroelectric valley and electronically controlled magnetism and their derived new physical phenomena and mechanisms are described. Finally, the rich physical connotation and broad application prospects of coupling two-dimensional ferroelectric materials with other physical properties are analyzed and discussed.

Keywords:

two-dimensional ferroelectric materials /
two-dimensional ferroelectric devices /
multiferroic coupling /
first-principles caculation

作者及机构信息

叶倩¹,
沈阳¹,
袁野¹,
赵祎峰¹,
段纯刚^1,2

1.
华东师范大学物理与电子科学学院, 极化材料与器件教育部重点实验室, 上海　200241

2.
山西大学, 极端光学协同创新中心, 太原　030006

通信作者: 段纯刚, cgduan@clpm.ecnu.edu.cn

基金项目: 国家重点研发计划(批准号: 2017YFA0303403)、上海市科技创新行动计划(批准号: 19JC1416700)和国家自然科学基金(批准号: 11774092)资助的课题

Authors and contacts

Ye Qian¹,
Shen Yang¹,
Yuan Ye¹,
Zhao Yi-Feng¹,
Duan Chun-Gang^1,2

1.
Key Laboratory of Polarized Materials and Devices of Ministry of Education, School of Physics and Electronic Science, East China Normal University, Shanghai 200241, China

2.
Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan 030006, China

Corresponding author: Duan Chun-Gang, cgduan@clpm.ecnu.edu.cn

Funds: Project supported by the National Key R&D Program of China (Grant No. 2017YFA0303403), the Shanghai Science and Technology Innovation Action Plan, China (Grant No. 19JC1416700), and the National Natural Science Foundation of China (Grant No.11774092)

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施引文献

图 1 (a) CIPS晶体结构侧视图^{[ 31]}; (b) 三维层状1 T′WTe₂的结构示意图^{[ 33]}

Fig. 1. (a) The side view of CuInP₂S₆ (CIPS)^{[ 31]}; (b) structure of three-dimensional 1 T′WTe₂^{[ 33]}.

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图 2 (a) 单层第Ⅳ主族单硫属化合物MX铁电相结构俯视图; (b) 两个等价的极性相B和B′及高对称性非极性相A的侧视图^{[ 34]}; (c) VOCl₂单层结构的俯视图及侧视图^{[ 40]}

Fig. 2. (a) Top view of the structure of monolayer group-IV monochalcogenides; (b) the schematic side views of the two distorted degenerate polar structures (B and B′) and the high symmetry nonpolar phase (A)^{[ 34]}; (c) the top view along the vertical direction and side views of the VOCl₂ monolayer^{[ 40]}.

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图 3 (a) 层状In₂Se₃的三维晶体结构示意图; (b) 沿垂直方向的俯视图; (c)—(h) quintuple layer (QL) In₂Se₃的几种典型结构的侧视图^{[ 42]}

Fig. 3. (a) Three-dimensional crystal structure of layered In₂Se₃; (b) top view of the system along the vertical direction; (c)–(h) side views of several representative structures of one quintuple layer (QL) In₂Se₃^{[ 42]}.

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图 4 (a) 基于α-In₂Se₃薄层铁电二极管示意图; (b) 器件的光学图像; (c), (d) 可切换的有整流特性的铁电二极管的I-V曲线^{[ 46]}

Fig. 4. (a) Schematic and (b) optical image of the device; (c), (d) I-V curves of the ferroelectric diode with switchable rectifying behavior^{[ 46]}.

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图 5 (a) 二维铁电同质FTJ器件模型示意图; (b) 二维FTJ In∶SnSe/SnSe/Sb∶SnSe结构示意图; (c) 二维同质FTJ In∶SnSe/SnSe/Sb∶SnSe中, 系统总能随铁电位移λ变化的关系图^{[ 49]}

Fig. 5. (a) Schematic diagram of a two-dimensional ferroelectric tunnel junction (2D-FTJ) device based on homostructure; (b) the schematic diagram (shaded regions) of 2D-FTJ In∶SnSe/SnSe/Sb∶SnSe; (c) asymmetric potential energy profile as a function of ferroelectric distortions in the 2D-FTJ In∶SnSe/SnSe/Sb∶SnSe^{[ 49]}.

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图 6 (a) 石墨烯的晶格结构及布里渊区; (b) 蜂窝晶格中的电子能带色散图^{[ 51]}; (c)—(e) 2H相TMDS单层能谷K₊与K_–附近的能带结构示意图: (c)不含SOC效应, (d)含SOC效应, (e)同时存在SOC效应与为正的交换场作用, 即对应谷极化情况^{[ 54]}

Fig. 6. (a) Honeycomb lattice and its Brillouin zone; (b) electronic dispersion in the honeycomb lattice^{[ 51]}; (c)–(e) the schematic band structures at valleys K₊ and $ K_- $ of representative 2H-phase TMD monolayers: (c) without SOC effect, (d) with SOC effect and (e) with SOC effect and a positive exchange field, that is, the valley-polarized case^[54].

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图 7 铁电GeSe单层(a) p_x相和(b) p_y相的能带结构; (c) p_x相和(d) p_y相GeSe单层中, 在$ \widehat{x} $ 和$ \widehat{y} $线偏振光激发下的复介电函数虚部ε₂; (e) 基于铁谷GeSe单层提出的电控起偏器工作原理示意图^[55]

Fig. 7. The band structure of ferroelectric phase GeSe monolayer in (a) p_x and (b) p_y state; the imaginary parts of complex dielectric function ε₂ excited by linearly x-polarized light and y-polarized light of ferrovalley GeSe monolayer of (c) p_x and (d) p_y state; (e) proposed electrically tunable polarizer based on the ferrovalley GeSe monolayer^{[ 55]}.

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图 8 (a), (b) CuInP₂S₆/MnPS₃异质结构图; (c)—(e) 不同铁磁序和铁电序异质结的能带图; (f), (g) 异质结中左旋圆偏振光σ₊和右旋圆偏振光σ_–激发下的复介电函数虚部ε₂; (h), (i) CuInP₂S₆/MnPS₃异质结构的电控谷自由度器件^{[ 56]}

Fig. 8. (a), (b) Structure configurations of CuInP₂S₆/MnPS₃ heterostructures; (c)–(e) band structures of CuInP₂S₆/MnPS₃ heterostructures; the imaginary parts of complex dielectric function ε₂ for CuInP₂S₆/MnPS₃ heterostructure with (f) downward and (g) upward ferroelectric polarization; electrical switch of valley degree in CuInP₂S₆/MnPS₃ heterostructures in (h) upward ferroelectricity and (i) downward ferroelectricity^{[ 56]}.

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图 9 (a) 考虑SOC作用时, 使用PBE泛函和HSE06泛函计算的单层弱铁电WO₂Cl₂的能带图; (b) [110] Dresselhaus型自旋分裂能带CBM处的能量分布图, 其中上方图对应“外”分支, 下方图对应“内”分支; (c)不同极化方向的单层WO₂Cl₂的三种自旋分量S_x, S_y和S_z在kx, ky平面内的自旋织构分布图, 能量截面位于CBM+0.2 eV处^{[ 65]}

Fig. 9. (a) Electronic band structures of the WFE WO₂Cl₂ monolayer in the PBE and HSE06 approximations with SOC; (b) DFT energy profiles for the CBM outer (top) and inner (bottom) branches of the [110] Dresselhaus-type spin split bands; (c) out-of-plane and in-plane spin component distributions with different ferroelectric polarizationon the constant energy contours corresponding to a cut at 0.2 eV above the CBM^{[ 65]}.

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图 10 (a) 分别有向上和向下的垂直电偶极矩的In₂Se₃单层的Cr₂Ge₂Te₆/ In₂Se₃二维异质结构图; (b) Cr₂Ge₂Te₆/ In₂Se₃二维异质结构中Cr₂Ge₂Te₆的磁晶各向异性与范德瓦耳斯层间距离的关系图; (c) 接近Cr₂Ge₂Te₆的表面(Se1)和次表面(In1)原子层的自旋状态密度; (d) 由磁邻近效应引起的原子Se1和原子In1自旋磁矩随层间距的变化图^{[ 75]}

Fig. 10. (a) Heterostructure side views with the In₂Se₃ ferroelectric dipole moment directed upward and downward (P_up and P_dn), respectively; (b) calculated magnetocrystalline anisotropy of Cr₂Ge₂Te₆ in the heterostructure versus the van der Waals interlayer distance; (c) projected spin density of states for the surface (Se1) and subsurface (In1) atomic layers close to Cr₂Ge₂Te₆; (d) interlayer distance dependence of the proximity-induced Se1 and In1 spin moments^{[ 75]}.

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