二维范德瓦耳斯材料的超导物性研究及性能调控

黄佳贝; 廉富镯; 汪致远; 孙世涛; 李明; 张棣; 蔡晓凡; 马国栋; 麦志洪; Andy Shen; 王雷; 于葛亮

doi:10.7498/aps.71.20220638

摘要

超导现象自从1911年被发现以来一直是凝聚态物理领域的热门研究方向. 近年来, 二维范德瓦耳斯材料在超导领域中备受瞩目, 展现出多种新的物理现象, 如伊辛超导体、拓扑超导等, 可以为探索丰富多彩的物理效应和新奇物理现象提供一个非常广阔的研究平台. 本文从二维范德瓦耳斯材料的超导特性入手, 着重论述了二维范德瓦耳斯材料的分类、合成方法、表征和调控手段等方面. 最后指出了一些当前需要解决的问题, 并对二维范德瓦耳斯材料在超导领域的未来前景进行了展望.

关键词:

Abstract

Superconductivity has become a fascinating research field in condensed matter physics since its discovery in 1911. Nowadays, two-dimensional materials exhibit a variety of new physical phenomena, such as Ising superconductivity, topological superconductivity, and unconventional superconductivity. A number of two-dimensional van der Waals crystals exhibit superconductivity, which provide us with a broad research platform for exploring various physical effects and novel phenomena. In this review, we focus our attention on superconducting properties of two-dimensional van der Waals crystals, and highlight the recent progress of the state-of-the-art research on synthesis, characterization, and isolation of single and few layer nanosheets and the assembly of two-dimensional van der Waals superconductors. Finally we conclude the future research directions and prospects in two-dimensional materials with superconductivity.

Keywords:

superconductivity /
two-dimensional van der Waals crystals /
fabrication and characterization /
property manipulation

作者及机构信息

1.
南京大学物理学院, 固体微结构物理国家重点实验室, 南京　210093

2.
南京大学, 人工微结构科学与技术协同创新中心, 南京　210093

3.
湖北九峰山实验室, 武汉　430206

通信作者: 王雷, leiwang@nju.edu.cn ; 于葛亮, yugeliang@nju.edu.cn

基金项目: 国家重点研发计划(批准号: SQ2018YFA030066, SQ2018YFA030143)、国家自然科学基金(批准号: 11974169)、中央高校基本科研业务费(批准号: 020414380087, 020414913201)、江苏省基础研究计划(批准号: BK20190283)和南通市市级基础科学研究和社会民生科技指令性项目(批准号: MS22021021)资助的课题.

Authors and contacts

1.
National Laboratory of Solid State Microstructures (NLSSMs), School of Physics, Nanjing University, Nanjing 210093, China

2.
Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China

3.
Hubei Jiufengshan Laboratory, Wuhan 430206, China

Corresponding author: Wang Lei, leiwang@nju.edu.cn ; Yu Ge-Liang, yugeliang@nju.edu.cn

Funds: Project supported by the National Key R&D Program of China (Grant Nos. SQ2018YFA030066, SQ2018YFA030143), the National Natural Science Foundation of China (Grant No. 11974169), the Fundamental Research Funds for the Central Universities, China (Grant Nos. 020414380087, 020414913201), the Basic Research Program of Jiangsu Province, China (Grant No. BK20190283), and the Science and Technology Plan of Nantong City, China (Grant No. MS22021021).

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施引文献

图 1 铜基材料的结构　(a) Bi₂Sr₂CaCu₂O_8+x的原子结构示意图^[19]; (b) La₂CuO₄的原子结构示意图^[25]

Fig. 1. Structures of copper-based materials: (a) Schematic of the atomic structure of Bi₂Sr₂CaCu₂O_8+x^[19]; (b) schematic of the atomic structure of La₂CuO₄^[25] .

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图 2 过渡金属硫族化合物材料的结构　(a) 2H-NbSe₂的原子结构示意图^[32]; (b) 2H-TaS₂的原子结构示意图^[33]; (c) 1T-MoS₂的原子结构示意图^[34]; (d) 1T-MoS₂电阻率与温度的依赖关系^[34]

Fig. 2. Structures of TMDCs: (a) Schematics of the atomic structure of 2H-NbSe₂^[32]; (b) schematics of the atomic structure of 2H-TaS₂^[33]; (c) schematics of the atomic structure of 1T-MoS₂^[34]; (d) temperature dependence of electrical resistivity of 1T-MoS₂^[34].

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图 3 (a) 石墨烯扭角结构示意图^[44]; (b) 过渡金属碳(氮)化物自上而下剥离过程示意图^[51]

Fig. 3. (a) Schematic of the twist structure of graphene^[44]; (b) schematic for top-down stripping process of transition metal carbon (nitrogen) compounds ^[51].

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图 4 CVD法制备示意图与超导性质　(a) 控制合成3R-TaSe₂原子层的反应腔示意图^[72]; (b) CVD法直接生长graphene/2D α-Mo₂C晶体异质结的过程示意图^[73]; (c) 3R-TaSe₂超导电性, 其超导转变温度T_c = 1.6 K^[72]; (d) 石墨烯/Mo₂C异质结在T = 100 mK时的夫琅禾费衍射图像, 深蓝色区域对应于零电阻状态, 虚线标记临界电流I_c的变化曲线表现磁场的调制作用^[73]

Fig. 4. Schematics of the CVD method and characteristics of 2D superconductors: (a) Schematic of the reaction chamber for the controlled synthesis of TaSe₂ atomic layers^[72]; (b) direct growth of graphene/2D α-Mo₂C heterostructures by CVD method^[73]; (c) superconductivities of 3R-TaSe₂, T_c = 1.6 K^[72]; (d) Fraunhofer-like diffraction pattern of graphene/Mo₂C heterostructure measured at 100 mK. The dark blue regions correspond to the zero-resistance state. The critical current I_c, denoted by the dashed lines, exhibits a modulation as a function of magnetic fields^[73].

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图 5 层状晶体的机械剥离过程示意图^[89]　(a) SiO₂/Si基底和与带有石墨薄片的胶带的光学图像; (b) 氧等离子体清洗SiO₂/Si基底; (c) 石墨胶带与基底表面接触, 然后放在热板上, 在空气中以100 ℃加热2 min; (d) 将基底从热板上移除, 并剥落胶带; (e) 石墨烯剥离后的基底光学图像; (f) 基片上石墨烯薄层的光学显微图, 薄层的厚度在1—4层之间呈阶梯变化

Fig. 5. Illustration of the exfoliation process for layered crystals^[89]: (a) Optical image of the SiO₂/Si substrate and adhesive tape with graphite flakes; (b) oxygen plasma cleaning of the SiO₂/Si substrate; (c) the graphite tape contacts the substrate, and then heat the substrate (with tape) on a hot plate at ～100 ℃ in air for 2 min; (d) removal of the substrate from the hot plate and peeling off of the tape; (e) optical image of the substrate after graphene exfoliation; (f) optical micrograph of one of the graphene flakes on the substrate in panel (e), the flake has a thickness varying in steps between 1–4 layers.

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图 6 STM, AFM和S/TEM的示意图^[92]　(a) 具有H₂功能化的STM示意图, 以及电子隧穿过程, H₂可以提高空间分辨率. (b) 具有 CO 分子功能化的AFM示意图, 以及尖端和样品之间的范德瓦耳斯相互作用曲线. 红色和绿色区域分别对应于排斥作用和吸引作用. (c) STEM和TEM示意图. STEM使用聚焦电子束(紫色), TEM使用准直电子束(粉红色)

Fig. 6. Schematic of STM, AFM and S/TEM^[92]: (a) Schematic of STM with hydrogen functionalization, and electron tunneling process; (b) schematic of AFM with CO molecule functionalization, and the van der Waals interaction between the tip and sample; the red and green regions correspond to repulsive and attractive mode AFM, respectively; (c) schematic of STEM and TEM. STEM utilizes a focused electron beam (purple), whereas TEM uses a collimated beam (pink).

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图 7 WS₂的结构示意图和原子力显微镜图像^[97]　(a) 通过杂质原子Sn的辅助调控得到的WS₂示意图以及两种WS₂样品的光镜图, 有Sn原子, 表现出60°堆叠, 无Sn原子, 表现出0°堆叠, 比例尺为10 μm; (b) 1L—6L WS₂的AFM图像, 比例尺为5 μm

Fig. 7. Schematics of WS₂structure and AFM images^[97]: (a) Schematics of the regulated growth of 0° stacking WS₂ without Sn and 60° stacking WS₂ with Sn and optical images of 0° and 60° stacking bilayer WS₂. Scale bar: 10 μm^[97]. (b) AFM images of 1L to 6L WS₂. Scale bar: 5 μm.

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图 8 透射电子显微镜图像^[73]　(a) 三角形、六角形、八角形和非角形2D α-Mo₂C晶体的石墨烯异质结构的亮场透射电子显微镜图像(比例尺为200 nm); (b) 2D α-Mo₂C样品区域的电子衍射图案, 显示存在两组六角周期结构, 红点对应2D α-Mo₂C晶体, 绿圈对应单层石墨烯, 比例尺为200 nm

Fig. 8. Schematics of TEM: (a) Bright-field TEM images of the heterostructures of graphene with triangular, hexagonal, octagonal, and nonagonal 2D α-Mo₂C crystals (Scale bars: 200 nm)^[73]; (b) selected area electron diffraction patterns taken from the regions with 2D α-Mo₂C in (a), showing two sets of patterns corresponding to 2D α-Mo₂C (marked by red dots) and monolayer graphene (marked by green circles) with the same lattice orientation (marked by red arrows) for each case, scale bars: 200 nm^[73].

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图 9 不同叠加模式下的SHG响应^[97]　(a) 0°和60°叠加WS₂的SHG图像, 插图为相应的光学图像, 比例尺为5 μm; (b) 激发功率相关的SHG强度; (c) 拟合斜率为1.99的双对数图; (d) 0和60°堆叠WS₂的SHG强度随层数的变化

Fig. 9. SHG responses corresponding to the different stacking modes^[97]: (a) SHG images of 0° and 60° stacking WS₂ ( Inset: the corresponding optical images. Scale bars: 5 μm); (b) excitation power-dependent SHG intensity; (c) double logarithmic plot with the fitting slope of 1.99; (d) SHG intensity of 0° and 60° stacking WS₂ as a function of layer number.

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图 10 MoS₂薄层的超导相变^[129]　(a) 双栅极器件及输运测试结构; (b) MoS₂超导相图, 横坐标表示载流子浓度

Fig. 10. Superconductivity transition of MoS₂ flakes^[129]: (a) Dual-gate device and transport measurement configuration; (b) the phase diagram showing super-conductivity of MoS₂, where horizontal axis represents the carrier density.

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图 11 FeSe薄膜基底的影响^[134]　(a) K/FeSe/STO的STM形貌图, 该样品是以SrTiO₃(001)为基底, 通过K原子掺杂的2 UC FeSe薄膜, K的覆盖率是0.163 ML (monolayer, ML), 插图为K/FeSe/STO的典型隧穿dI/dV曲线, 显示存在较大的超导间隙(～15 meV); (b) 在SrTiO₃和石墨化的SiC基底上的FeSe薄膜, 得到的超导间隙随薄膜厚度的演化, 间隙的大小取自不同位置的5—10个谱线的平均, 绿线显示块体FeSe的超导间隙

Fig. 11. Effects of substrate on the superconductivity of epitaxial FeSe films^[134]: (a) Topographic images of K/FeSe/STO sample, the K doped 2 UC FeSe films is grown on SrTiO₃ (001) substrates, the K coverage is 0.163 ML; Insert: Typical tunneling conductance (dI/dV) curves taken on the 2 UC FeSe/SrTiO₃ films indicates a optimized superconducting gap (～15 meV); (b) evolution of optimal SC gaps for different thickness of FeSe films on SrTiO₃ and graphitized SiC. The gap size is obtained by averaging 5–10 spectra taken at different locations. Green dashed line indicates the SC gap of bulk FeSe (2.2 meV).

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