Experimental synthesis of borophene

Li Wen-Hui; Chen Lan; Wu Ke-Hui

doi:10.7498/aps.71.20220155

Abstract

As the lightest two-dimensional material discovered so far, borophene exhibits rich physical properties, including high flexibility, optical transparency, high thermal conductivity, one-dimensional nearly free electron gas, Dirac fermions, and superconductivity. However, due to the strong interlayer covalent bonding force of bulk boron, it is difficult to obtain the monolayer borophene via mechanical exfoliation. In addition, due to the electron-deficient property of boron atoms, its chemical properties are relatively active, and its bonding is complex, resulting in different boron allotropes, which is different from other two-dimensional materials. For a long time, the research on borophene has been limited to theoretical exploration, and it has been difficult to make breakthroughs in the experimental synthesis of two-dimensional borophene. It has been only successfully prepared by a few research groups in recent years. However, there is still huge space for exploration on the growth, structure and electronic properties of borophene. This paper systematically reviews the preparation methods and different structures of borophene under different substrates, and its growth mechanism is discussed. It provides a research platform for further expanding the physical properties of borophene, and provides ideas for exploring the preparation of borophene nanodevices. It has great potential application prospects in high energy storage, optoelectronic devices, high detection sensitivity, and flexible nanodevices.

Keywords:

Authors and contacts

1.
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China
2.
School of Physical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China
3.
Songshan Lake Materials Laboratory, Dongguan 523808, China

Corresponding author: Chen Lan, lchen@iphy.ac.cn ; Wu Ke-Hui, khwu@iphy.ac.cn

Funds: Project supported by the National Key R&D Program of China (Grant No. 2018YFE0202700), National Natural Science Foundation of China (Grant No. 12134019), and the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB30000000).

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Cited By

图 1 硼烯理论预测和实验制备的研究进展

Figure 1. Research progress on theoretical prediction and experimental synthesis of borophene.

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图 2 (a) 硼元素在元素周期表的位置和原子轨道^[27]; (b) B_n硼团簇依赖尺寸大小, 从平面或准平面结构, 到笼状结构, 再到核壳结构的变化^[29]; (c) ${\rm{B}}_n^- $ (n = 3—38)单阴离子硼团簇的稳定结构以及点群对称性^[37]

Figure 2. (a) The position and atomic orbital of boron in the periodic table^[27]; (b) size-dependent conformation of B_n clusters from planar or quasiplanar, via cagelike to core -shell structures^[29]; (c) stable structure and point group symmetry of monoanionic ${\rm{B}}_n^- $ (n = 3–38) clusters^[37].

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图 3 (a)和(b)分别为六方孔洞结构的α, β相单层硼烯; (c) 硼烯的结合能随六方孔洞密度变化^[40]

Figure 3. (a) and (b) α, β phase monolayer borophene with hexagonal hole structure, respectively; (c) binding energies vs hexagon hole density for borophene with evenly distributed hexagons^[40].

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图 4 理论预言无衬底支撑的各种单层硼烯结构 (a) δ相; (b) χ相; (c) α相; (d) β相. 红色和黄色小球表示硼原子面外或面内运动, 导致硼原子层翘曲^[18]

Figure 4. Various monolayer borophene structures without substrate support by theoretical prediction: (a) δ phase; (b) χ phase; (c) α phase; (d) β phase. Red and yellow balls denote borophene atoms moving outward or inward from the plane, resulting in buckled borophene^[18].

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图 5 不同金属衬底上单层硼烯的基态稳定结构^[45]

Figure 5. Stable structures of monolayer borophene with respect to ground states on different metal substrates^[45].

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图 6 (a) Ag(111)衬底温度为570 K时形成的硼烯薄膜; (b)图(a)的三维立体模式; (c) S1相的高分辨STM图; (d) S1相硼烯的理论模型β₁₂结构; (e) 650 K退火后, 大部分S1相转变为S2相硼烯; (f)图(e)中黑色方框区域的高分辨STM图; (g) S2相的高分辨STM图; (h) S2相硼烯的理论模型χ₃结构^[12]

Figure 6. (a) Experimental STM image of borophene on the Ag (111) substrate at 570 K; (b) 3 D image of (a); (c) high-resolution STM image about S1 phases; (d) theoretical model of the S1 phase borophene considered to be the β₁₂ structure; (e) most of the borophene islands are transformed from S1 phase to S2 phase after annealing at 650 K; (f) STM image of the area of highlight by the rectangle of (e); (g) high-resolution STM image of the S2 phase ; (h) theoretical model of the S2 phase borophene considered to be the χ₃ structure^[12].

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图 7 (a) 硼烯的生长示意图; (b)和(c)分别为硼烯的STM形貌图和电子态密度图, 红色、白色和蓝色箭头分别表示均匀相、条纹相和条纹相纳米带; (d) 条纹相的原子分辨图和理论模型; (e)和(f)分别为均匀相硼烯的STM形貌图和电子态密度图; (g) 均匀相的原子分辨图和理论模型; (h)和(i)分别为铺满衬底单层硼烯的STM形貌图和电子态密度图^[13]

Figure 7. (a) Schematics of synthesizing borophene; (b) and (c) the STM topography and electron density of states of borophene, respectively, the red, white, and blue marks denote homogeneous phase, striped phase, and striped phase nanoribbons, respectively; (d) STM image about atomic level structure and theoretical model of the striped-phase; (e) and (f) the STM topography and electron density of states of homogeneous phase borophene, respectively; (g) STM image about atomic level structure and theoretical model of the homogeneous phase; (h) and (i) represent the STM topography and electron density of states of monolayer borophene covered the substrate, respectively^[13].

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图 8 (a) 在Ag(110)表面生长的硼烯纳米带; (b)—(e) P1—P4相硼烯纳米带的高分辨率STM图像; (f)—(i)P1—P4相硼烯的理论模型^[49]

Figure 8. (a) Synthesis borophene nanoribbons on Ag(110) ; (b)–(e) high-resolution STM images of the P1–P4 phase borophene, respectively ; (f)–(i) theoretical model of the P1–P4 phase borophene, respectively^[49].

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图 9 (a) Ag(100)衬底上硼烯制备示意图; (b)和(c) 硼烯有A, B, C三种不同链状结构; (d)—(f) A, B, C三种硼烯相的高分辨STM图; (g)—(i)对应(d)—(f)中的三种硼烯相的原子结构模型. 其中A相(g)和C相(i)是典型的准一维原子链混合相结构^[50]

Figure 9. (a) Schematics of synthesizing borophene on Ag(100); (b) and (c) three different chain structures of A, B, and C phase borophene; (d)–(f) high-resolution STM image of the A, B, and C phase borophene, respectively ; (g)–(i) theoretical models of different phases borophene of (d)–(f), respectively. the phase (g) and C phase (i) are typical quasi-one-dimensional atomic chain mixed different phases^[50].

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图 10 (a) 蜂窝状结构硼烯的示意图; (b)—(d) Al(111)衬底上硼烯薄膜的 STM图, 其中(d)图显示出三角形的周期性起伏结构; (e) Al(111)衬底上硼烯薄膜的原子结构模型图^[52]

Figure 10. (a) Schematic of the honeycomb structure of borophene; (b)–(d) STM images of borophene on Al(111), which shows the periodic triangle undulating structure in (d); (e) atomic structure model of borophene on Al(111)^[52].

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图 11 (a) Au(111)表面鱼骨状条纹的STM图像; (b)沉积硼后, Au(111)表面鱼骨状条纹被调制为三角网格; (c) 硼烯v_1/12相的理论模型; (d) 室温沉积硼B 1s能级峰; (e) 随着硼含量增大, Au(111)三角网格破裂, 硼烯岛长大; (f) 硼烯生长动态示意图; (g) 硼在Au(111)上扩散的最小能量路径^[54]

Figure 11. (a) STM image of Au(111) surface that shows herringbone stripes; (b) following boron deposition, the herringbone reconstruction was modified to a trigonal network ; (c) atomic structure of the borophene v_1/12 computationally modeled; (d) B 1s core-level spectra for room-temperature B deposition; (e) increasing boron dose results in the breakdown of the trigonal network and growth of larger borophene islands; (f) schematic illustration of borophene growth dynamics; (g) minimum energy path for boron diffusion on Au(111)^[54].

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图 12 (a) Cu(111)衬底上硼烯的生长动态过程; (b) 硼烯的STM原子分辨图; (c) 理论计算硼烯的恒隧穿电流等能面; (d) 硼烯的原子结构^[55]

Figure 12. (a) Growth dynamics of the borophene on the Cu(111) surface; (b) high resolution STM of borophene; (c) DFT-simulated constant tunnelling current isosurface of the borophene; (d) atomic structure of borophene^[55].

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图 13 (a) Ir(111)衬底上生长硼烯示意图; (b) STM显示硼烯的3个等价方向畴界; (c) 洁净Ir(111)表面的LEED图案; (d) 硼烯/Ir(111)的LEED图案; (e) 硼烯波浪条纹状; (f) 硼烯单胞结构; (g)和(h) Ir(111)衬底上的χ₆硼烯结构及电荷分布^[57]

Figure 13. (a) Schematics of synthesizing borophene on Ir(111); (b) STM image of borophene domains on Ir(111) showing three equivalent orientations; (c) LEED pattern from clean Ir(111); (d) LEED pattern from borophene/Ir(111); (e) undulated-stripe appearance of borophene; (f) unit cell structure of borophene; (g) and (h) optimized structure of χ₆ borophene on Ir(111) surface and charge redistribution^[57].

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图 14 (a) 双层硼烯的晶格结构, 体相硼的基本结构单元为B₁₂正二十面体; (b) Ag(111)上生长的双层硼烯; (c)双层硼烯的STM原子分辨; (d)双层硼烯的CO-STM图像; (e) 双层硼烯与单层v_1/5相的界面; (f) Ag(111)衬底上双层硼烯的理论模型结构; (g) 双层硼烯与Ag(111)形成的摩尔条纹; (h)和(i) 双层硼烯的CO-STM与CO-AFM图像^[74]

Figure 14. (a) Lattice structure of bilayer borophene, schematic of the B₁₂ icosahedron unit that is the basis of bulk boron polymorphs; (b) growth of BL borophene on Ag(111); (c) atomic-scale imaging of BL borophene; (d) CO-STM image of BL borophene; (e) CO-STM image of the interface between BL borophene and v_1/5 borophene; (f) the atomic structure of BL borophene on Ag(111); (g) illustration of the moiré superlattice formed between BL borophene and Ag(111); (h) and (i) experimental CO-STM and CO-AFM images of BL borophene, respectively^[74].

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图 15 (a) 单层与双层硼烯共存的形貌图; (b) Cu(111)上生长的双层硼烯; (c) 双层硼烯退火后形成较大的畴; (d) 双层硼烯的STM原子图像; (e)和(f)分别为双层硼烯的第1层和第2层硼烯原子模型结构; (g)双层硼烯的电荷密度分布; (h)和(i)分别为双层硼烯与单层硼烯的XPS谱^[75]

Figure 15. (a) Coexisting monolayer (ML) and bilayer (BL) borophene; (b) grow BL borophene on Cu(111); (c) BL borophene with a large single-phase domain after annealing; (d) high-resolution STM images of BL borophene; (e) and (f) atomic structures of the first and second layers of BL borophene; (g) charge distribution between BL borophene and the Cu(111) substrate; (h) and (i) the XPS spectra of bilayer and monolayer borophene, respectively^[75].

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图 16 CVD法在Ir(111)衬底上制备硼烯以及硼烯-氮化硼异质结　(a) Ir(111)衬底上用B₂H₆生长硼烯的模型图; (b) 硼烯-氮化硼水平异质结的模型图; (c) 硼烯-氮化硼垂直异质结的模型图; (d) 硼烯的STM原子图像; (e)和(f)分别为硼烯-氮化硼水平和垂直异质结的原子图像; (g) 硼烯的电子隧道谱; (h) 覆盖hBN与未覆盖hBN时硼烯的XPS谱^[76]

Figure 16. CVD growth of borophene and borophene-hBN heterostructures on Ir(111): (a) Schematic of diborane dosage on the preheated Ir(111) surface to obtain borophene; (b) schematic of borophene-hBN lateral heterostructures; (c) schematic of borophene-hBN vertical heterostructures; (d) STM image of borophene; (e) and (f) high-resolution STM image of borophene-hBN lateral and vertical heterostructures ; (g) dI/dV spectra taken on borophene and hBN; (h) XPS spectra of B1s measured on hBN-covered and uncovered borophene, respectively^[76].

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