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超高真空构筑新型二维材料及其异质结构

李更 郭辉 高鸿钧

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超高真空构筑新型二维材料及其异质结构

李更, 郭辉, 高鸿钧

Novel two-dimensional materials and their heterostructures constructed in ultra-high vacuum

Li Geng, Guo Hui, Gao Hong-Jun
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  • 由于量子受限效应, 二维材料表现出很多三维材料所不具备的优异电学、光学、热学以及力学性能, 为研究人员所关注. 材料的优异物性离不开高质量材料的制备, 超高真空环境可以减少杂质分子的污染与影响, 提高二维材料的质量与性能. 本文介绍基于超高真空环境的新型二维原子晶体材料的原位制备方法, 包括利用分子束外延构筑新型二维材料、利用石墨烯插层构筑新型二维原子晶体材料异质结构以及利用扫描探针原位操纵构筑二维材料异质结构三大类. 文章回顾利用这三类方法构筑的二维材料及其物理化学性质, 比较三种方法各自的优势与局限性, 对未来二维材料制备提供一定的指引.
    Compared with the three-dimensional bulk materials, two-dimensional (2D) materials exhibit superior electronic, optical, thermal, and mechanical properties due to the reduced dimensionality. The quantum confinement effect of 2D materials gives rise to exotic physical properties, and receives extensive attention of the scientists. Lots of routes to fabricate the 2D materials have been proposed by the material scientists, including the traditional mechanical exfoliation, chemical vapor deposition, molecular beam epitaxy under ultra-high vacuum (UHV), and so on. Among them, fabricating materials under ultra-high vacuum has the advantages of constructing large-scale and high-quality samples, and is therefore widely adopted in the 2D material growth. In this paper, we review three different strategies of growing 2D materials under UHV conditions, including molecular beam epitaxy, graphene intercalation and manual manipulation by nano probes. We compare the advantages and drawbacks among those methods in creating 2D materials, and try to provide some guidance to the community, especially those who are new to the field.
      通信作者: 高鸿钧, hjgao@iphy.ac.cn
    • 基金项目: 国家重点基础研究发展计划(批准号: 2019YFA0308500, 2018YFA0305700)、国家自然科学基金(批准号: 61888102, 51991340, 52072401)和中国科学院(批准号: YSBR-003)资助的课题.
      Corresponding author: Gao Hong-Jun, hjgao@iphy.ac.cn
    • Funds: Project supported by the National Basic Research Program of China (Grant Nos. 2019YFA0308500, 2018YFA0305700), the National Natural Science Foundation of China (Grant Nos. 61888102, 51991340, 52072401), and the CAS Project for Young Scientists in Basic Research (Grant No. YSBR-003).
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  • 图 1  不同基底表面硅烯的分子束外延生长 硅烯在Ag(111)[11] (a) ZrB2(0001)[17] (b) Ir(111)[18] (c) 和Ru(0001)[19] (d)表面生长的STM图像

    Fig. 1.  Molecular beam epitaxial growth of silicene monolayers on different substrates: STM images of silicene monolayer on Ag(111)[11] (a) ZrB2(0001)[17] (b) Ir(111)[18] (c) and Ru(0001)[19] (d), respectively.

    图 2  (a), (b) 单层锗烯在Pt(111)表面外延生长的STM图像(a)和原子模型示意图(b)[24]; (c), (d) 双层锗烯在Cu(111)表面外延生长的STM图像(c)和原子模型示意图(d)[25]

    Fig. 2.  (a), (b) STM image (a) and atomic model (b) of germanene monolayer on Pt(111)[24]; (c), (d) STM image (c) and atomic model (d) of germanene bilayer on Cu(111)[25].

    图 3  锡烯在不同衬底上的分子束外延生长 (a) 单层锡烯在Bi2Te3(111)表面外延生长的STM图像[32]; (b) InSb(111)表面外延生长锡烯和钾掺杂锡烯在Г点附近的能带结构[33]; (c), (d) Cu(111)表面外延生长纯平锡烯的大面积STM图像(c)和原子分辨图像(d)[37]; (e) Ir(111)上外延氮化硼表面生长锡烯的STM图像[40]

    Fig. 3.  Molecular beam epitaxial growth of stanene monolayers on different substrates: (a) STM image of buckled stanene on Bi2Te3(111)[32]; (b) band structure of as-grown and K doped stanene on InSb(111)[33]; (c), (d) large-scale (c) and atomically-resolved (d) STM images of flat stanene on Cu(111)[37]; (e) STM image of stanene on BN/Ir(111)[40].

    图 4  铅烯在不同衬底上的分子束外延生长 (a), (b) 单层铅烯在Pd(111)表面外延生长的大面积(a)和原子分辨(b) STM图像[49]; (c), (d) 单层铅烯在Fe/Ir(111)表面外延生长的原子分辨STM图像(c)和原子结构模型(d)[50]; (e) 单层铅烯在Fe/Ir(111)表面外延生长的大面积STM图像[50]

    Fig. 4.  Molecular beam epitaxial growth of plumbene monolayers on different substrates: (a), (b) Large-scale (a) and atomically-resolved (b) STM image of planar plumbene on Pd(111)[49];(c), (d) atomically-resolved STM image (c) and atomic model of plumbene on monolayer Fe on Ir(111)[50]; (e) large-scale STM image of planar plumbene on monolayer Fe on Ir(111)[50].

    图 5  单层和双层硼烯的分子束外延生长 (a)—(d) 单层硼烯在Ag(111)表面外延生长的STM图像[53,54]; (e), (f) 双层硼烯在Cu(111)表面外延生长的STM图像[55]; (g), (h) 双层硼烯在Ag(111)表面外延生长的STM图像[56]

    Fig. 5.  Molecular beam epitaxial growth of borophene monolayers and bilayers: (a)–(d) STM images of monolayer borophene on Ag(111)[53,54]; (e), (f) STM images of bilayer borophene on Cu(111)[55]; (g), (h) STM images of bilayer borophene on Ag(111)[56].

    图 6  (a), (b) 单层蓝磷在Au(111)表面外延生长的STM图像(a)和原子模型示意图(b)[60]; (c), (d)单层锑烯在PdTe2表面外延生长的STM图像(c)和原子模型示意图(d)[62]; (e) 锑烯单层岛在Cu(111)表面外延生长的STM图像; (f) 跨过锑烯单层岛的扫描隧道谱[63]; (g), (h) 单层铋烯在SiC表面外延生长的STM图像(g)和原子模型示意图(h)[65]

    Fig. 6.  (a), (b) STM image (a) and atomic model (b) of monolayer blue phosphorus on Au(111)[60]; (c), (d) STM image (c) and atomic model (d) of monolayer antimonene on PdTe2[62]; (e) STM image of monolayer antimonene on Cu(111); (f) Waterfall-like dI/dV spectra along the arrow in Fig. (e)[63]; (g), (h) STM image (g) and atomic model (h) of monolayer bismuthene on SiC[65].

    图 7  (a) Ir(111)表面大面积单层铪的STM图像; (b) 原子分辨的单层铪STM图像; (c) 铪烯的STM图像、STM模拟图像以及原子结构示意图[66]

    Fig. 7.  (a) Large-scale STM image of monolayer Hf on Ir(111); (b) Atomically-resolved STM image of monolayer Hf on Ir(111); (c) The STM image, simulated STM image, and atomic model of a Hafnene monolayer on Ir(111), showing honeycomb Hf lattice[66].

    图 8  (a) Au(111)表面单层MoSe2岛的STM图像; (b) MoSe2岛的原子分辨STM图像; (c), (d) 大面积(c)和原子分辨(d)的Mo边界STM图像; (e) MoSe2上不同区域的dI/dV谱线; (f) MoSe2岛边界上不同位置的dI/dV谱线[77]

    Fig. 8.  (a) STM image of monolayer MoSe2 islands on Au(111) substrate; (b) atomic-resolved STM image of single-layer MoSe2 with hexagonal lattice; (c), (d) large-scale (c) and atomically resolved (d) STM image of Mo edge; (e) normalized dI/dV curves obtained on the three different domains of MoSe2 on Au(111); (f) Six normalized dI/dV curves taken on the six edges of one MoSe2 island[77].

    图 9  (a) 双层石墨烯/碳化硅衬底上生长的大面积多层PdTe2[80]; (b) 双层石墨烯/碳化硅衬底上生长的单层MoSe2[81]; (c) 石墨烯化碳化硅衬底上生长的PdSe2; (d) 在跨过单层和双层石墨烯/碳化硅衬底上连续生长的双层PdSe2上测得的扫描隧道谱[82]; (e) 石墨烯化碳化硅衬底上生长的Pd2Se3[83]; (f) 跨过单层和双层Pd2Se3台阶测得的扫描隧道谱[84]

    Fig. 9.  (a) Multi-layer PdTe2 on bilayer graphene on SiC substrate[80]; (b) monolayer MoSe2 on bilayer graphene on SiC substrate[81]; (c) bilayer PdSe2 on bilayer graphene on SiC substrate; (d) dI/dV spectra taken on bilayer PdSe2 on top of mono- and bi- layer graphene substrate[82]; (e) Pd2Se3 on bilayer graphene on SiC substrate[83]; (d) dI/dV spectra taken across mono- and bi- layer Pd2Se3[84]

    图 10  (a), (b) 1T/1H相的PtSe2三角图案的结构示意图与STM图像[87]; (c), (d) Cu(111)表面CuSe的周期性三角孔洞结构[87]; (e)—(g) CuSe的扫描透射电镜图像、电镜模拟图像以及原子结构示意图[87]

    Fig. 10.  (a), (b) The schematic and STM image of the triangular pattern of 1T/1H phase PtSe2 on Pt(111)[87]; (c), (d) large-scale and zoom-in STM images of the periodic triangle holes in CuSe monolayer[87]; (e)–(g) scanning transmission electron microscopy image, the simulated image and atomic model of monolayer CuSe on Cu(111)[87].

    图 11  (a) 插层硅烯纳米片段的STM图像[107]; (b) 插层单层硅烯的STM图像[107]; (c) 石墨烯/硅烯异质结构的电子局域函数计算[107]; (d) 石墨烯/硅烯异质结构的整流效应[107]

    Fig. 11.  (a) STM image of the intercalated silicene nano flakes[107]; (b) STM image of the intercalated silicene monolayer[107]; (c) electron localization function calculation of the graphene/silicene heterostructure[107]; (d) rectifying effect of the graphene/silicene heterostructure[107].

    图 12  (a), (b) Ru(0001)表面双层石墨烯/硅烯异质结构筑示意图[138]; (c), (d) 分别是硅烯插层前后的LEED图像[138]; (e), (f) 分别是硅烯插层前后的STM图像[138]; (g) Ru(0001)表面硅烯插层前后的单层石墨烯及双层石墨烯的Raman光谱对比[138]; (h) 硅烯插层后双层石墨烯的2D特征峰的分析拟合[138]

    Fig. 12.  (a), (b) Schematic of the fabrication process of BLG/silicene heterostructure on Ru(0001)[138]; (c), (d) LEED patterns of BLG/Ru and BLG/silicene/Ru, respectively[138]; (e), (f) corresponding STM images for BLG/Ru and BLG/silicene/Ru, respectively[138]; (g) comparison of Raman spectra of SLG/Ru (black), SLG/silicene/Ru (green), BLG/Ru (red) and BLG/silicene/Ru (blue) [138]; (h) 2D band of BLG/silicene/Ru well fitted with four narrow Lorentzian components[138].

    图 13  (a) 硅烯插层之后的双层石墨烯的ARPES谱[138]; (b) 优化后的起伏双层石墨烯/硅烯/Ru的原子结构模型[138]; (c) 基于图(b)中结构模型计算的能带结构, 红点组成了投影到双层石墨烯上的能带结构[138]; (d) 仅考虑来自硅烯/Ru衬底的掺杂效应时双层石墨烯的能带结构[138]; (e) 仅考虑双层石墨烯起伏/应力情况下的能带结构[138]; (f) 同时考虑掺杂和起伏/应力时双层石墨烯的能带结构[138]

    Fig. 13.  (a) ARPES intensity map of the BLG after silicene intercalation[138]; (b) an optimized structure model of rippled BLG on Ru(0001) after silicene intercalation[138]; (c) calculated band structure based on the structure model in (b). The red dots are the band projected on the BLG[138]; (d) a structure model of flat BLG on silicene/Ru and the corresponding calculated band structure[138]; (e) a structure model of rippled BLG and the corresponding calculated band structure[138]; (f) a structure model of Li-doped rippled BLG and the calculated band structure[138].

    图 14  Ru(0001)表面外延大面积、高质量石墨烯的SiO2插层及原位器件的制备 (a)—(d) SiO2插层过程及原位器件构筑示意图[108]; (e)—(g) 不同制备阶段样品的LEED表征[108]; (h) 石墨烯Hall器件的Raman mapping[108]

    Fig. 14.  Synthesis of insulating SiO2 between graphene and a Ru(0001) substrate enabling electronic-device fabrication: (a)–(d) Schematic of the SiO2 intercalation and finally device fabrication processes[108]; (e)–(g) LEED patterns and corresponding structure models for sample in preparation stages (a)–(c), respectively[108]; (h) graphene G-peak intensity mapping, showing the skeleton of the graphene Hall-bar device in Fig. (d)[108].

    图 15  (a) 薄层晶态二氧化硅插层样品的大面积截面STEM图像[108]; (b) 高分辨STEM图像显示晶态二氧化硅的双层结构[108]; (c) 界面处的EELS谱[108]; (d) 晶态二氧化硅表面石墨烯的STM图像[108]; (e) 晶态二氧化硅插层之后石墨烯的Raman光谱[108]

    Fig. 15.  (a) Large-scale aberration-corrected bright-field STEM image of the bilayer-silica intercalated sample[108]; (b) high resolution STEM image taken at the red box in Fig. (a) clearly shows the atomic structure of the interfacial silica[108]; (c) EELS of Si-L2, 3 edge taken at the intercalation layer[108]; (d) atomic-resolution STM image of the graphene overlayer[108]; (e) Raman spectra of the graphene after intercalation of the crystalline SiO2[108].

    图 16  (a) 厚层二氧化硅插层样品的界面STEM图像, 显示界面处厚层二氧化硅的厚度达到1.8 nm, 具有非晶态结构[108]; (b) X射线光电子能谱[108]; (c) 低偏压(< 10 mV)下, 对不同厚度二氧化硅插层的样品在垂直方向输运性质测试[108]; (d) 不同温度下的SdH振荡[108]; (e) 2 K下磁阻Rxx以及霍尔电阻Rxy随磁场的变化[108]; (f) 不同温度下纵向电导率在低场范围的变化规律, 与石墨烯的弱反局域理论很好的拟合[108]

    Fig. 16.  (a) STEM image showing an amorphous SiO2 film with thickness of 1.8 nm between graphene and Ru substrate[108]; (b) XPS of the Si 2p and O 1s core levels; (c) vertical transport measurements at small bias (< 10 mV) for Gr/Ru, Gr/1.1 nm-silica/Ru and Gr/1.8 nm-silica/Ru samples[108]; (d) SdH oscillations at different temperatures[108]; (e) magnetoresistance Rxx and Hall resistance Rxy measured at 2 K[108]; (f) corrections of low field conductivity (△σxx) at different temperatures, showing good agreement with the weak antilocalization theory of graphene[108].

    图 17  石墨烯“折纸术”的示意图以及STM图像[142]. 利用扫描探针显微镜针尖, 可以对石墨烯纳米岛进行折叠[142]. 利用纳米岛中的一维晶界, 可以构筑具有手性异质结构的一维碳纳米管结构[142]

    Fig. 17.  Schematic and STM images of the graphene origami[142]. The graphene nanoislands can be folded by STM tip[142]. By taking advantage of the natural 1D domain boundaries in the nanoislands, heterostructure of 1D carbon nanotubes with different chirality can be constructed[142].

    图 18  三种二维材料构筑方式的比较.

    Fig. 18.  Comparison among the three construction methods of 2D materials.

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出版历程
  • 收稿日期:  2021-12-28
  • 修回日期:  2022-01-22
  • 上网日期:  2022-02-10
  • 刊出日期:  2022-05-20

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