Mechanical Isolation of Highly Stable Antimonene under Ambient Conditions

Ares, Pablo; Aguilar-Galindo, Fernando; Rodríguez‐San‐Miguel, David; Aldave, Diego A.; Díaz‐Tendero, Sergio; Alcamı́, Manuel; Martín, Fernando; Gómez-Herrero, Júlio; Zamora, Félix

doi:10.1002/adma.201602128

Cited by 484 publications

(419 citation statements)

References 28 publications

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“…17 layers) hardly show any measurable Raman signal (Figure 4 b). This unexpected dependence of the Raman intensity on the flake thickness is similar to that previously observed for micromechanically exfoliated flakes of antimony and analogous to what has been reported for mica nanosheets 6, 13. Indeed, Figure 4 b shows a series of single‐point spectra measured at different positions, showing decreases in the peak intensities with a decrease in thickness.…”

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confidence: 87%

“…Indeed, theoretical calculations5 have estimated the band gap for a single layer of antimony, or antimonene (we should point out that the name antimonene is not completely correct as there are no double bonds in its structure), to be about 1.2 eV. Antimonene has recently been isolated by mechanical exfoliation, and showed good stability under ambient conditions 6. As for other 2D materials, micromechanical exfoliation provides high‐quality flakes but is unsuitable for mass production.…”

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confidence: 99%

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Few‐Layer Antimonene by Liquid‐Phase Exfoliation

et al. 2016

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We report on a fast and simple method to produce highly stable isopropanol/water (4:1) suspensions of few‐layer antimonene by liquid‐phase exfoliation of antimony crystals in a process that is assisted by sonication but does not require the addition of any surfactant. This straightforward method generates dispersions of few‐layer antimonene suitable for on‐surface isolation. Analysis by atomic force microscopy, scanning transmission electron microscopy, and electron energy loss spectroscopy confirmed the formation of high‐quality few‐layer antimonene nanosheets with large lateral dimensions. These nanolayers are extremely stable under ambient conditions. Their Raman signals are strongly thickness‐dependent, which was rationalized by means of density functional theory calculations.

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confidence: 99%

Few‐Layer Antimonene by Liquid‐Phase Exfoliation

et al. 2016

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“…This unexpected dependence of the Raman intensity on the flake thickness is similar to that previously observed for micromechanically exfoliated flakes of antimony and analogous to what has been reported for mica nanosheets. [6,13] Indeed, Figure 4b shows as eries of single-point spectra measured at different positions,s howing decreases in the peak intensities with adecrease in thickness. Forc omparison, we studied the influence of the laser excitation wavelength on am icromechanically exfoliated flake with as ize of about 5.5 mma nd at hickness of 10 nm, which had previously been analyzed by AFM, after its relocation in aR aman microscope by optical microscopy (see the Supporting Information and Figure S13 for additional information).…”

Section: Zuschriftenmentioning

confidence: 96%

“…Indeed, theoretical calculations [5] have estimated the band gap for asingle layer of antimony,orantimonene (we should point out that the name antimonene is not completely correct as there are no double bonds in its structure), to be about 1.2 eV.Antimonene has recently been isolated by mechanical exfoliation, and showed good stability under ambient conditions. [6] As for other 2D materials,m icromechanical exfoliation provides high-quality flakes but is unsuitable for mass production. Liquid phase exfoliation (LPE) has been successfully applied to generate single-or few-layer (FL) samples of several 2D materials on large scale, [7] including stable suspensions of few-layer BP.…”

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Few‐Layer Antimonene by Liquid‐Phase Exfoliation

et al. 2016

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We report on af ast and simple method to produce highly stable isopropanol/water (4:1) suspensions of few-layer antimonene by liquid-phase exfoliation of antimony crystals in aprocess that is assisted by sonication but does not require the addition of any surfactant. This straightforwardm ethod generates dispersions of few-layer antimonene suitable for on-surface isolation. Analysis by atomic force microscopy, scanning transmission electron microscopy, and electron energy loss spectroscopyc onfirmed the formation of highquality few-layer antimonene nanosheets with large lateral dimensions.T hese nanolayers are extremely stable under ambient conditions.T heir Raman signals are strongly thickness-dependent, which was rationalized by means of density functional theory calculations.Currently,two-dimensional (2D) materials represent one of the most active research areas.[1] Apart from various wellstablished 2D materials,s uch as graphene,h -BN,a nd MoS 2 , black phosphorus (BP) has received considerable attention over the last two years.[2] This is due to the fact that whereas graphene is an on-band-gap material and transition-metal dichalcogenides have ar elatively large band gap for certain optoelectronic applications (1.5-2.5 eV), [3] the direct band gap of few-and single-layer BP is approximately 1.5 eV, [4] and this material therefore has appealing properties for electronic and ultrafast optoelectronic applications.H owever,i solated layers of BP are extremely sensitive to the surroundings,and strongly degrade upon air exposure,w hich limits their application.[2b] Thus the discovery of new 2D materials with an appropriate band gap and stability under ambient conditions is ac hallenge of utmost importance. Along this front, antimony is ag ood candidate as it is in the same group in the periodic table as phosphorus and exhibits an allotrope closely related to BP (Figure 1a). Indeed, theoretical calculations [5] have estimated the band gap for asingle layer of antimony,orantimonene (we should point out that the name antimonene is not completely correct as there are no double bonds in its structure), to be about 1.2 eV.Antimonene has recently been isolated by mechanical exfoliation, and showed good stability under ambient conditions.[6] As for other 2D materials,m icromechanical exfoliation provides high-quality flakes but is unsuitable for mass production. Liquid phase exfoliation (LPE) has been successfully applied to generate single-or few-layer (FL) samples of several 2D materials on large scale, [7] including stable suspensions of few-layer BP.[8]Herein, we demonstrate that sonication of antimony crystals in a4 :1 isopropanol/water mixture without any surfactant produces av ery stable suspension of micrometerlarge FL antimonene over weeks,e ven under ambient conditions (see the Supporting Information for details). High-quality,f ew-layer antimonene nanosheets can thus be produced by liquid-phase exfoliation. Remarkably,t he FL antimonene suspensions and the layers isolated on surfaces are very stable,...

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“…6. Graphene (C), phosphorene (P), arsenene (As), and antimonene (Sb) have all been reported as 2D materials experimentally and/or theoretically [36][37][38][39], but very little work has been done to isolate or characterize bismene (Bi) nanosheets. The exfoliation energy of bismene is 273 meV/atom, similar to that of 2D Sb (236 meV/atom).…”

Section: Density-functional Theory (Dft)mentioning

confidence: 99%

Topology-Scaling Identification of Layered Solids and Stable Exfoliated 2D Materials

et al. 2017

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The Materials Project crystal structure database has been searched for materials possessing layered motifs in their crystal structures using a topology-scaling algorithm. The algorithm identifies and measures the sizes of bonded atomic clusters in a structure's unit cell, and determines their scaling with cell size. The search yielded 826 stable layered materials that are considered as candidates for the formation of two-dimensional monolayers via exfoliation. Density-functional theory was used to calculate the exfoliation energy of each material and 680 monolayers emerge with exfoliation energies below those of already-existent two-dimensional materials. The crystal structures of these two-dimensional materials provide templates for future theoretical searches of stable twodimensional materials. The optimized structures and other calculated data for all 826 monolayers are provided at https://materialsweb.org.The combination of modern computational tools and the growing number of available crystal structure databases with high-throughput interfaces have accelerated recent efforts to map the materials genome. One of the most recently discovered branches of the materials genome is the class of two-dimensional (2D) materials, which generally have properties that are markedly different from their three-dimensional counterparts. The canonical example is the graphite/graphene system, but monolayers have been exfoliated from many other layered compounds as well [1][2][3][4]. Stable 2D materials can also be obtained by deposition [5][6][7][8] or chemical exfoliation [9,10]. Because the contribution of interlayer interactions to these materials free energies is typically quite small, the existence of a mechanically exfoliable bulk precursor generally indicates the relative stability of a freestanding single layer, regardless of how it is synthesized.In an effort to discover novel 2D materials, two recent studies searched the inorganic crystal structure database (ICSD) for compounds with large interlayer spacings, which are characteristic of weak interlayer bonding that could be overcome by mechanical exfoliation [11,12]. They used the intuitive criteria of a low packing fraction based on the covalent radii of the atoms and an interlayer gap larger than the sum of the covalent radii of atoms at the layers' surfaces along the c-axis to identify layered compounds in the ICSD. They discovered almost 100 layered phases, nearly half of which had monolayers that had not been the subject of any prior publications.Here, we extend their method to identify a large number of layered compounds that were missed using the packing factor and c-axis interlayer gap criteria. We further add the constraint that a bulk material must be thermodynamically stable to be of interest during our search. Therefore, we use the Materials Project (MP) database [13], an online repository of crystallographic and thermodynamic data for over 65,000 compounds calculated with density-functional theory (DFT). Our algorithm is designed to correctly identify ad...

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Mechanical Isolation of Highly Stable Antimonene under Ambient Conditions

Cited by 484 publications

References 28 publications

Few‐Layer Antimonene by Liquid‐Phase Exfoliation

Few‐Layer Antimonene by Liquid‐Phase Exfoliation

Few‐Layer Antimonene by Liquid‐Phase Exfoliation

Topology-Scaling Identification of Layered Solids and Stable Exfoliated 2D Materials

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