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Progress in Chemistry 2019, Vol. 31 Issue (12): 1696-1711 DOI: 10.7536/PC190424 Previous Articles   Next Articles

Theoretical and Experimental Research of Boron Nanostructures

Rui Wang1,2, Guoan Tai1,**(), Zenghui Wu1, Wei Shao1, Chuang Hou1, Jinqian Hao1   

  1. 1. State Key Laboratory of Mechanics and Control of Mechanical Structure, Key Laboratory for Intelligent Nano Materials and Devices of the Ministry of Education, Institute of Nano Science, College of Aerospace Engineering, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
    2. College of Material Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, China
  • Received: Online: Published:
  • Contact: Guoan Tai
  • About author:
    ** E-mail:
  • Supported by:
    National Natural Science Foundation of China(61474063); National Natural Science Foundation of China(61774085); Six Talent Peaks Project in Jiangsu Province(XCL-046); Fundamental Research Funds for the Central Universities(NE2017101); Priority Academic Program Development of Jiangsu Higher Education Institutions
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Boron, the only non-metallic element in the third main group, has special electron-deficient properties, which results in a complex bonding mechanism. It has both the normal two-center-two-electron bonds and the multi-center-two-electron bonds for keeping balance of the electron distribution of the system, which makes it have a wide variety of allotropes. In contrast to the bulk counterparts, low-dimensional boron nanostructures have unique structures and special properties, so they have attracted extensive interests in recent years. In this paper, we systematically introduce the theoretical and experimental progress on zero-dimensional boron clusters, one-dimensional boron nanotubes/nanowires and two-dimensional boron nanostructures. The structure, properties and potential applications of the boron nanostructures have been summarized and discussed. Although, there are still great challenges in the controllable preparation and stability of the nanostructures, they will be expected to have exceptionally inherent properties to make them play an important role in the future nano-devices and electrochemical catalysis.

Key words: borophene, nanoclusters, nanotubes, nanowires, two-dimensional material
Fig. 1 Summary of the minimum-energy structures, point group symmetries and electronic state of Bn-clusters(n=3~30 and 35~38)[13]. Copyright 2017, Springer Nature
Fig. 2 Schematic diagram of quasiplanar, convex structures and boron nanotubes, following the “Aufbau principle” for forming the boron clusters[9]. Copyright 1997, American Physical Society
Fig. 3 Relationship between B36 and borphene[8]. Copyright 2014, Springer Nature
Fig. 4 Atomic models of boron nanostructures:(a) the structure of boron sheet;(b) the structure of boron nanotubes[33]. Copyright 2008, American Physical Society
Fig. 5 TEM images of boron nanotubes:(a) bright field HRTEM image of boron nanotubes;(b) dark field HRTEM image [45]. Copyright 2004, American Chemical Society.(c) low-resolution TEM image of boron nanotubes. The inset is the corresponding SAED pattern;(d) cross-section HRTEM image of a single boron nanotube [46]. Copyright 2010, Royal Society of Chemistry
Fig. 6 SEM images of boron nanowires:(a) low-magnification SEM images of large-area BNW patterns;(b) side-view of uniform BNW patterns on the Si substrate;(c,d) side-view of BNWs at the edge and at the inner portion of the pattern;(e,f) SEM images at the tip and the end of BNWs. The white circles refer to the catalysts’ site[58]. Copyright 2013, John Wiley and Sons
Fig. 7 Experimental results of boron nanowires:(a) a typical SEM image of boron nanowires on Si(111) substrate;(b) TEM image of single boron nanowire. The inset is the corresponding SAED pattern that can be indexed to β-rhombohedral boron;(c~f) SEM images showing mechanical bending process[60]. Copyright 2008, AIP Publishing
Fig. 8 SEM and TEM images of boron nanostructures:(a) Overall view of the puffy ball;(b) Scrolled nanostructures. The inset shows the cross-section of one “nano-scroll” of thickness 17±2 nm;(c) “Grass-like” nanoribbons. The inset shows that the nanoribbons are easily twisted and some have “zigzag” edges;(d) “Palm-leaf like” nanostructures. Nanoribbons have split ends, forming smaller nanostructures;(e) TEM micrograph of several twisted nanoribbons at lower magnification;(f,g) corresponding SAED pattern[64]. Copyright 2004, American Chemical Society
Fig. 9 Theoretical predications of α-sheet:(a) The structure of α-sheet;(b) LDA Eb vs hexagon hole density η for sheets with evenly distributed hexagons[32]. Copyright 2007, American Physical Society
Fig. 10 Configurational energy spectra of 2D B on Au, Ag, Cu, and Ni substrates. The inset in each column illustrates the three most stable structures. Energies versus the ground states and the corresponding v are provided below each inset[80]. Copyright 2015, John Wiley and Sons
Fig. 11 Experimental results of 2D γ-B28:(a) Schematic representation of the two-zone furnace for synthesizing atomically thin 2D γ-B28 film via CVD;(b,c) Schematic diagram of the 2D γ-B28 structure;(d) Optical image of the film on Cu substrate;(e) UV-vis absorption spectrum of monolayer γ-B28 film;(f) Photoluminescence spectra of a monolayer γ-B28 film and bulk β-rhombohedral boron. The blue line is the corresponding Gaussian fit[87]. Copyright 2015, John Wiley and Sons
Fig. 12 Theoretical predications of γ-B28 monolayer:(a) The structural model of monolayer γ-B28 with B and H surface passivation; the additional B atoms are highlighted in yellow color and hydrogen atoms in white color;(b) the electronic band structure of B and H surface passivated the monolayer film;(c) the bandgap variation with the film thickness[88]. Copyright 2016, Royal Society of Chemistry
Fig. 13 Experimental results of borophenes on Ag(111) substrate:(a) The schematic diagram of MBE growth of borophene;(b) AES spectra of clean Ag(111) before and after boron deposition;(c~h) large-scale STM topography(left) and closed-loop dI/dV(right) images of borophene sheets[89]. Copyright 2015, The American Association for the Advancement of Science
Fig. 14 Experimental realization of boron monolayer on Ag(111) substrates:(a) STM topographic image of boron structures on Ag(111) with a substrate temperature of ~570 K during the growth;(b) Three-dimensional image of(a);(c) high-resolution STM image of S1 phases;(d) STM image of boron structures under a substrate temperature of 650 K.The two different phases are labelled ‘S1’ and ‘S2’. Most boron islands are transformed into the S2 phase, but the S1 phase still remains in small parts of the islands;(e) STM image obtained on the area marked by the black rectangle in(d);(f) high-resolution STM image of the S2 phase[91]. Copyright 2016, Springer Nature
Fig. 15 Experimental results of borphene on the Cu(111) surface:(a) The sequence of bright-field LEEM images at different time intervals at T=770 K;(b) Topographic AFM image at around a 0.1 ML coverage.(c) The line profile corresponding to the black line in(b) shows a 2.8 ? atomic step of the Cu substrate;(d) The line profile corresponding to the blue line in(b) shows that the thickness of the borophene sheet in ambient conditions is around 3.0 ?;(e) Ex-situ XPS spectra of a B/Cu(111) sample[93]. Copyright 2018, Springer Nature
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