硼烯化学合成进展与展望

硼烯是由硼原子构成的单原子层厚的二维材料,具有丰富的化学和物理性质。本文集中介绍近年来硼烯在合成方面的理论与实验研究进展,重点分析基底、生长温度、生长前驱物等因素对硼成核选择性的影响,探讨能够促进硼烯成核的潜在方法。进一步将分析硼烯生长机制及理论研究方法,以此展望通过在基底上化学气相沉积合成硼烯的可能途径。本文旨在促进大面积、高质量硼烯样品的制备以推动硼烯的实际应用。     

Epitaxial growth of borophene on substrates

Borophene, a two-dimensional (2D) planar boron sheet, has attracted dramatic attention for its unique physical properties that are theoretically predicted to be different from those of bulk boron, such as polymorphism, superconductivity, Dirac fermions, mechanical flexibility and anisotropic metallicity. Nevertheless, it has long been difficult to obtain borophene experimentally due to its susceptibility to oxidation and the strong covalent bonds in bulk forms. With the development of growth technology in ultra-high vacuum (UHV), borophene has been successfully synthesized by molecular beam epitaxy (MBE) supported by substrates in recent years. Due to the intrinsic polymorphism of borophene, the choice of substrates in the synthesis of borophene is pivotal to the atomic structure of borophene. The different interactions and commensuration of borophene on various substrates can induce various allotropes of borophene with distinct atomic structures, which suggests a potential approach to explore and manipulate the structure of borophene and benefits the realization of novel physical and chemical properties in borophene due to the structure–property correspondence. In this review, we summarize the recent research progress in the synthesis of monolayer (ML) borophene on various substrates, including Ag(1 1 1), Ag(1 1 0), Ag(1 0 0), Cu(1 1 1), Cu(1 0 0), Au(1 1 1), Al(1 1 1) and Ir(1 1 1), in which the polymorphism of borophene is present. Moreover, we introduce the realization of bilayer (BL) borophene on Ag(1 1 1), Cu(1 1 1) and Ru(0 0 0 1) surfaces, which possess richer electronic properties, including better thermal stability and oxidation resistance. Then, the stabilization mechanism of polymorphic borophene on their substrates is discussed. In addition, experimental investigations on the unique physical properties of borophene are also introduced, including metallicity, topology, superconductivity, optical and mechanical properties. Finally, we present an outlook on the challenges and prospects for the synthesis and potential applications of borophene.     

Vibrational Property of α-Borophene Determined by Tip-Enhanced Raman Spectroscopy

We report a Raman characterization of the α borophene polymorph by scanning tunneling microscopy combined with tip-enhanced Raman spectroscopy. A series of Raman peaks were discovered, which can be well related with the phonon modes calculated based on an asymmetric buckled α structure. The unusual enhancement of high-frequency Raman peaks in TERS spectra of α borophene is found and associated with its unique buckling when landed on the Ag(111) surface. Our paper demonstrates the advantages of TERS, namely high spatial resolution and selective enhancement rule, in studying the local vibrational properties of materials in nanoscale.     

The Role of Holes in Borophenes: An Ab Initio Study of Their Structure and Stability with and without Metal Templates

An electron‐counting strategy starting from magnesium boride was used to show the inevitability of hexagonal holes in 2D borophene. The number (hole density, HD) and distribution of the hexagonal holes determine the binding energy per boron atom in monolayer borophenes. The relationship between binding energy and HD changes dramatically when the borophene is placed on a Ag(111) surface. The distribution of holes in borophenes on Ag(111) surfaces depends on the temperature. DFT calculations show that aside from the previously reported S1 and S2 borophene phases, other polymorphs may also be competitive. Plots of the electron density distribution of the boron sheets suggest that the observed STM image of an S2 phase corresponds to a sheet with a HD of 2/15 instead of a sheet with a HD of 1/5. The hole density and the hole distribution echo the distribution of vacancies and extra occupancies in complex β‐rhombohedral boron.     

Ultrastable Crystalline Semiconducting Hydrogenated Borophene

Borophene sheets have been synthesized in recent experiments, but the metallic nature and structural instability of the sheets seriously prevent emerging applications. Hydrogenated borophene has been predicted as an ideal material for nanoelectronic applications due to its high stability as well as excellent electronic and mechanical properties. However, the fabrication of hydrogenated borophene is still a great challenge. Here, we demonstrate that hydrogenated borophenes in large quantities can be prepared without any metal substrates by a stepwise in‐situ thermal decomposition of sodium borohydride under hydrogen as the carrier gas. The borophenes with good crystallinity exhibit superior stability in strong acid or base solvents. The structure of the grown borophene is in good agreement with the predicted semiconducting α‐boron sheet. A fabricated borophene‐based memory device shows a high ON/OFF‐current ratio of 3×10³ and a low operating voltage of less than 0.35 V as well as good stability.     

The Planar CoB18− Cluster as a Motif for Metallo‐Borophenes

Monolayer‐boron (borophene) has been predicted with various atomic arrangements consisting of a triangular boron lattice with hexagonal vacancies. Its viability was confirmed by the observation of a planar hexagonal B₃₆ cluster with a central six‐membered ring. Here we report a planar boron cluster doped with a transition‐metal atom in the boron network (CoB₁₈^?), suggesting the prospect of forming stable hetero‐borophenes. The CoB₁₈^? cluster was characterized by photoelectron spectroscopy and quantum chemistry calculations, showing that its most stable structure is planar with the Co atom as an integral part of a triangular boron lattice. Chemical bonding analyses show that the planar CoB₁₈^? is aromatic with ten π‐electrons and the Co atom has strong covalent interactions with the surrounding boron atoms. The current result suggests that transition metals can be doped into the planes of borophenes to create metallo‐borophenes, opening vast opportunities to design hetero‐borophenes with tunable chemical, magnetic, and optical properties.     

Universal Scaling of Intrinsic Resistivity in Two‐Dimensional Metallic Borophene

Two‐dimensional boron sheets (borophenes) have been successfully synthesized in experiments and are expected to exhibit intriguing transport properties. A comprehensive first‐principles study is reported of the intrinsic electrical resistivity of emerging borophene structures. The resistivity is highly dependent on different polymorphs and electron densities of borophene. Interestingly, a universal behavior of the intrinsic resistivity is well‐described using the Bloch–Grüneisen model. In contrast to graphene and conventional metals, the intrinsic resistivity of borophenes can be easily tuned by adjusting carrier densities, while the Bloch–Grüneisen temperature is nearly fixed at 100 K. This work suggests that monolayer boron can serve as intriguing platform for realizing tunable two‐dimensional electronic devices.     

Bandgap Engineering of Hydroxy-Functionalized Borophene for Superior Photo-Electrochemical Performance

Two-dimensional (2D) semiconducting boron nanosheets (few-layer borophene) have been theoretically predicted, but their band gap tunability has not been experimentally confirmed. In this study, hydroxy-functionalized borophene (borophene-OH) with tunable band gap was fabricated by liquid-phase exfoliation using 2-butanol solvent. Surface-energy matching between boron and 2-butanol produced smooth borophene, and the exposed unsaturated B sites generated by B−B bond breaking during exfoliation coordinated with OH groups to form semiconducting borophene-OH, enabling a tunable band gap of 0.65–2.10 eV by varying its thickness. Photoelectrochemical (PEC) measurements demonstrated that the use of borophene-OH to fabricate working electrodes for PEC-type photodetectors significantly enhanced the photocurrent density (5.0 μA cm⁻²) and photoresponsivity (58.5 μA W⁻¹) compared with other 2D monoelemental materials. Thus, borophene-OH is a promising semiconductor with great optoelectronic potential.     

Electronic Structures of Polymorphic Layers of Borophane

The search for free-standing 2D materials has been one of the most important subjects in the field of studies on 2D materials and their applications. Recently, a free-standing monolayer of hydrogenated boron (HB) sheet has been synthesized by hydrogenation of borophene. The HB sheet is also called borophane, and its application is actively studied in many aspects. Here, we review recent studies on the electronic structures of polymorphic sheets of borophane. A hydrogenated boron sheet with a hexagonal boron frame was shown to have a semimetallic electronic structure by experimental and theoretical analyses. A tight-binding model that reproduces the electronic structure was given and it allows easy estimation of the properties of the material. Hydrogenated boron sheets with more complicated nonsymmorphic boron frames were also analyzed. Using the symmetry restrictions from the nonsymmorphic symmetry and the filling factor of hydrogenated boron sheets, the existence of a Dirac nodal line was suggested. These studies provide basic insights for research on and device applications of hydrogenated boron sheets.     

Structural Evolution of Boron Clusters on Ag(111) Surfaces – From Atomic Chains to Triangular Sheets with Hexagonal Holes

Unlike graphene and other 2D materials, borophene is 2D polymorphic with diverse hexagonal holes (HHs)-triangles ratios and the concentrations of HHs are highly substrate dependent. Here, we systematically explored the evolution of boron cluster on Ag(111) surface, B_N@Ag(111) (N=1∼36), to understand the nucleation of 2D boron sheet on metal surface. Our calculation showed that, with the size increasing, the structures of most stable B_N clusters undergo an evolution from compact triangular lattice, such as double-chains or triple-chains, to the ones with mixed triangular-hexagonal lattices. The first single-HH appears at N=12 and the first double-HH appears at N=27. The stability of large B_N clusters with mixed structures is derived from the charge transfer between triangular lattice and the HHs, as well as between the substrates and the B_N clusters. Our results provide a deep understanding on the formation of small boron clusters in the initial nucleation stage of borophene growth.     

Boron Nitride Nanosheets Improve Sensitivity and Reusability of Surface‐Enhanced Raman Spectroscopy

Surface enhanced Raman spectroscopy (SERS) is a useful multidisciplinary analytic technique. However, it is still a challenge to produce SERS substrates that are highly sensitive, reproducible, stable, reusable, and scalable. Herein, we demonstrate that atomically thin boron nitride (BN) nanosheets have many unique and desirable properties to help solve this challenge. The synergic effect of the atomic thickness, high flexibility, stronger surface adsorption capability, electrical insulation, impermeability, high thermal and chemical stability of BN nanosheets can increase the Raman sensitivity by up to two orders, and in the meantime attain long‐term stability and extraordinary reusability not achievable by other materials. These advances will greatly facilitate the wider use of SERS in many fields.     

Recent Progresses in the Investigation of Rare-earth Boron Inverse Sandwich Clusters

While rare-earth borides represent a class of important materials in modern industries, there are few fundamental researches on their electronic structures and physicochemical properties. Recently, we have performed combined experimental and theoretical studies on rare-earth boron clusters and their cluster-assembled complexes, revealing a series of rare-earth inverse sandwich clusters with fascinating electronic structures and chemical bonding patterns. In this overview article, we summarize recent progresses in this area and provide a perspective view on the future development of rare-earth boride clusters. Understanding the electronic structures of these clusters helps to design materials of f-element(lanthanide and actinide) borides with critical physiochemical properties.     

Influence of Neighboring Layers on Interfacial Energy of Adjacent Layers

The binding energy and generalized stacking-fault energy (GSFE) are two critical interface properties of two dimensional layered materials, and it is still unclear how neighboring layers affect the interface energy of adjacent layers. Here, we investigate the effect of neighboring layers by comparing the differences of binding energy and GSFE between trilayer heterostructures (graphene/graphene/graphene, graphene/graphene/boron nitride, boron nitride/graphene/boron nitride) and bilayer heterostructures (graphene/graphene, graphene/boron nitride) using density functional theory. The binding energy of the adjacent layers changes from -2.3% to 22.55% due to the effect of neighboring layer, with a very small change of the interlayer distance. Neighboring layers also make a change from -2% to 10% change the GSFE, depending on the property of the interface between adjacent layers. In addition, a new simple expression is proven to describe the GSFE landscape of graphene-like structure with high accuracy.     

Large Hexagonal Bi‐ and Trilayer Graphene Single Crystals with Varied Interlayer Rotations

Bi‐ and trilayer graphene have attracted intensive interest due to their rich electronic and optical properties, which are dependent on interlayer rotations. However, the synthesis of high‐quality large‐size bi‐ and trilayer graphene single crystals still remains a challenge. Here, the synthesis of 100 μm pyramid‐like hexagonal bi‐ and trilayer graphene single‐crystal domains on Cu foils using chemical vapor deposition is reported. The as‐produced graphene domains show almost exclusively either 0° or 30° interlayer rotations. Raman spectroscopy, transmission electron microscopy, and Fourier‐transformed infrared spectroscopy were used to demonstrate that bilayer graphene domains with 0° interlayer stacking angles were Bernal stacked. Based on first‐principle calculations, it is proposed that rotations originate from the graphene nucleation at the Cu step, which explains the origin of the interlayer rotations and agrees well with the experimental observations.     

Anisotropic Boron–Carbon Hetero-Nanosheets for Ultrahigh Energy Density Supercapacitors

A 2D boron nanosheet that exhibits high theoretical capacitance, around four times that of graphene, is a significant supercapacitor electrode. However, its bulk structure with low interlaminar conduction and porosity restricts the charge transfer, ion diffusion, and energy density. Herein, we develop a new 2D hetero-nanosheet made of anisotropic boron–carbon nanosheets (ABCNs) by B−C chemical bonds via gas-phase exfoliation and condensation bottom-up strategy. The ABCNs are constructed into high flexible supercapacitor electrode by microfluidic electrospinning. The ABCN electrode greatly promotes smooth migration and excessive storage of electrolyte ions due to large interlayer conductivity, ionic pathways, and accessible surfaces. The flexible supercapacitor delivers ultrahigh volumetric energy density of 167.05 mWh cm⁻³ and capacitance of 534.5 F cm⁻³. A wearable energy-sensor system is designed to stably monitor physiological signals.     

Thermal stability of cubic boron nitride films deposited by chemical vapor deposition

Thermal stability of well-crystallized cubic boron nitride (cBN) films grown by chemical vapor deposition has been investigated by cathodoluminescence (CL), Raman spectroscopy, and scanning electron microscopy (SEM) with the cBN films annealed at various temperatures up to 1,300 degrees C. The crystallinity of the cBN films further improves, as indicated by a reduction of the relevant Raman line width, when the annealing temperature exceeds 1,100 degrees C. Structural damage or amorphization was observed on the grain boundaries of the cBN crystals when annealing temperature reaches 1,300 degrees C. The CL spectra are found to be unchanged up to 1,100 degrees C after annealing at 500 degrees C, showing the stability of the cBN films in electronic properties up to this temperature. New features were observed in the CL spectra when annealing temperature reaches 1,200-1,300 degrees C.     

Gate‐Voltage Control of Borophene Structure Formation

Boron nanostructures are easily charged but how charge carriers affect their structural stability is unknown. We combined cluster expansion methods with first‐principles calculations to analyze the dependence of the preferred structure of two‐dimensional (2D) boron, or “borophene”, on charge doping controlled by a gate voltage. At a reasonable doping level of 3.12×10¹⁴ cm⁻², the hollow hexagon concentration in the ground state of 2D boron increases to 1/7 from 1/8 in its charge‐neutral state. The numerical result for the dependence of hollow hexagon concentration on the doping level is well described by an analytical method based on an electron‐counting rule. Aside from in‐plane electronic bonding, the hybridization among out‐of‐plane boron orbitals is crucial for determining the relative stability of different sheets at a given doping level. Our results offer new insight into the stability mechanism of 2D boron and open new ways for the control of the lattice structure during formation.     

Root-growth mechanism for single-walled boron nitride nanotubes in laser vaporization technique

We present a detailed study of the growth mechanism of single-walled boron nitride nanotubes synthesized by laser vaporization, which is the unique route known to the synthesis of this kind of tube in high quantities. We have performed a nanometric chemical and structural characterization by transmission electron microscopy (high-resolution mode (HRTEM) and electron energy loss spectroscopy) of the synthesis products. Different boron-based compounds and other impurities were identified in the raw synthesis products. The results obtained by the TEM analysis and from the synthesis parameters (temperature, boron, and nitrogen sources) combined with phase diagram analysis to provide identification of the fundamental factors determining the nanotube growth mechanism. Our experiments strongly support a root-growth model that involves the presence of a droplet of boron. This phenomenological model considers the solubility, solidification, and segregation phenomena of the elements present in this boron droplet. In this model, we distinguish three different steps as a function of the temperature: (1) formation of the liquid boron droplet from the decomposition of different boron compounds existing in the hexagonal boron nitride target, (2) reaction of these boron droplets with nitrogen gas present in the vaporization chamber and recombination of these elements to form boron nitride, and (3) incorporation of the nitrogen atoms at the root of the boron particle at active reacting sites that achieves the growth of the tube.     

The Registry Index: A Quantitative Measure of Materials′ Interfacial Commensurability

Nanoscale tribology is an active and rapidly developing area of research that poses fundamental scientific questions that, if answered, may offer great technological potential in the fields of friction, wear, and lubrication. When considering nanoscale material′s junctions, surface commensurability often plays a crucial rule in dictating the tribological properties of the interface. This Review surveys recent theoretical work in this area, with the aim of providing a quantitative measure of the crystal lattice commensurability at interfaces between rigid materials and relating it to the tribological properties of the junction. By considering a variety of hexagonal layered materials, including graphene, hexagonal boron nitride, and molybdenum disulfide, we show how a simple geometrical parameter, termed the “registry index” (RI), can capture the interlayer sliding energy landscape as calculated using advanced electronic structure methods. The predictive power of this method is further demonstrated by showing how the RI is able to fully reproduce the experimentally measured frictional behavior of a graphene nanoflake sliding over a graphite surface. It is shown that generalizations towards heterogeneous junctions and non‐planar structures (e.g., nanotubes) provide a route for designing nanoscale systems with unique tribological properties, such as robust superlubricity. Future extension of this method towards nonparallel interfaces, bulk‐material junctions, molecular surface diffusion barriers, and dynamic simulations are discussed.     

TiO_2/蒙脱石层间化合物的制备及层间原位反应过程研究

基于蒙脱石层间域的二维纳米反应器属性,通过溶剂化作用,将氧化钛前躯体钛酸丁酯引入有机季铵盐阳离子插层的蒙脱石层间域中,并使其在蒙脱石层间域中水解、成核和相变结晶.采用XRD、原位升温Raman光谱、TEM分析手段研究了钛酸丁酯进入蒙脱石层间域过程,以及钛酸丁酯在蒙脱石层间域中水解和TiO2成核及相转变过程.结果表明钛酸...