Magnetism and piezoelectricity of hexagonal boron nitride with triangular vacancy

First-principle calculations reveal that the configuration system of hexagonal boron nitride(h-BN) monolayer with triangular vacancy can induce obvious magnetism, contrary to that of the nonmagnetic pristine boron nitride monolayer.Interestingly, the h-BN with boron atom vacancy(VB-BN) displays metallic behavior with a total magnetic moment being 0.46μ_B per cell, while the h-BN with nitrogen atom vacancy(VN-BN) presents a half-metallic characteristic with a total magnetic moment being 1.0μ_B per cell. Remarkably, piezoelectric stress coefficient e_(11) of the VN-BN is about 1.5 times larger than that of pristine h-BN. Furthermore, piezoelectric strain coefficient d_(11)(12.42 pm/V) of the VN-BN is 20 times larger than that of pristine h-BN and also one order of magnitude larger than the value for the h-MoS_2 monolayer, which is mainly due to the spin-down electronic state in the V_N-BN system. Our study demonstrates that the nitrogen atom vacancies can be an efficient route to tailoring the magnetic and piezoelectric properties of h-BN monolayer, which have promising performances for potential applications in nano-electromechanical systems(NEMS) and nanoscale electronics devices.     

六方氮化硼单层中一种(CN)3VB缺陷的第一性原理计算

二维六方氮化硼(hBN)的点缺陷最近被发现可以实现室温下的单光子发射,而成为近年的研究热点.尽管其具有重要的基础和应用研究意义,hBN中发光缺陷的原子结构起源仍然存在争议.本文采用基于密度泛函理论的第一性原理计算,研究hBN单层中一种B空位附近3个N原子被C替代的缺陷(CN)3VB.在hBN的B空位处,3个N原子各自带...     

Deep levels of nitrogen vacancy complexes in graphite-like boron nitride

This paper presents the results of a theoretical study of deep nitrogen vacancy levels and of small clusters of nitrogen di-and trivacancies, including the nearest neighbor defects in one layer of graphite-like boron nitride, made using the model-pseudopotential and supercell methods. The calculated spectra and oscillator strengths were used to interpret the local bands of optical absorption, luminescence, and photoconductivity in pyrolytic boron nitride before and after irradiation by fast neutrons, protons, and carbon ions (50–150 keV). The shallow activation levels of thermally stimulated luminescence and conductivity existing before and arising after irradiation were identified.     

Effect of triangle vacancy on thermal transport in boron nitride nanoribbons

Recently, triangle vacancy in hexagonal boron nitride is observed experimentally. Using nonequilibrium Green’s function method, we investigate thermal transport properties of boron nitride nanoribbons (BNNRs) with a triangle vacancy. The effect of triangle vacancy on the phonon transmission of zigzag-edged BNNRs (Z-BNNRs) is different from that of armchair-edged BNNRs (A-BNNRs). The triangle vacancy induces antiresonant dips in the spectrum of Z-BNNRs. Moreover, the boron-terminated triangle vacancy causes antiresonant zero-transmission dip and the number of the zero-transmission dip increases with the geometrical size of triangle vacancy. For the A-BNNRs with triangle vacancy, except some antiresonant dips, a resonant peak is found in the transmission. The antiresonant and resonant phenomena are explained by analyzing local density of states and local thermal currents. Although the antiresonant dip and the resonant peak are both originated from quasibound states, their distributions of local thermal currents are distinct, which leads to the transport discrepancy. In addition, the thermal conductance of BNNRs decreases linearly with increasing the vacancy size.     

Molecular-dynamics simulation of defect formation energy in boron nitride nanotubes

We investigate the defect formation energy of boron nitride nanotubes (BNNTs) using molecular dynamics simulation. Although the defect with tetragon–octagon pairs (TOP) is favored in the flat BNNTs cap, BN clusters, and the growth of BNNTs, the formation energy of the TOP defect is significantly higher than that of the pentagon–heptagon pairs (PHP) defect in BNNTs. The PHP defect reduces the effect of the structural distortion caused by the TOP defect, in spite of homoelemental bonds. The instability of the TOP defect generates the structural transformation into BNNTs with no defect at about 1500 K. This mechanism shows that the TOP defect is less favored in case of BNNTs.     

Magnetic properties of Ni doped gallium nitride with vacancy induced defect

Investigations have been carried out to study the ferromagnetic properties of transition metal (TM) doped wurtzite GaN from first principle calculations using tight binding linear muffin-tin orbital (TBLMTO) method within the density functional theory. The present calculation reveals ferromagnetism in nickel doped GaN with a magnetic moment of 1.13 μ_B for 6.25% of Ni doping and 1.32 μ_B for 12.5% of nickel doping, there is a decrease of magnetic moment when two Ni atoms are bonded via nitrogen atom. The Ga vacancy (V_Ga) induced defect shows ferromagnetic state. Here the magnetic moment arises due to the tetrahedral bonding of three N atoms with the vacancy which is at a distance of 3.689 Å and the other N atom which is at a distance of 3.678 Å .On the other hand the defect induced by N vacancy (V_N) has no effect on magnetic moment and the system shows metallic character. When Ni is introduced into a Ga vacancy (V_Ga) site, charge transfer occur from the Ni ‘d’ like band to acceptor level of V_Ga and formed a strong Ni–N bond. In this Ni–V_Ga complex with an Ni ion and a Ga defect, the magnetic moment due to N atom is 0.299 μ_B .In case of Ni substitution in Ga site with N vacancy, the system is ferromagnetic with a magnetic moment of 1 μ_B.     

空位缺陷对单层硅烯薄膜力学性能的影响

采用基于分子动力学理论的Forcite模拟软件包对含不同浓度的单、双空位缺陷硅烯薄膜的超晶胞体系进行优化,并对其力学性能进行了计算和分析.结果表明:随着空位缺陷浓度的增加,硅烯薄膜的拉梅常数、泊松比、体弹模量和剪切模量呈线性递减趋势,而由于空位缺陷附近键长的缩减导致硅烯薄膜"硬化"与空位缺陷浓度的增加导致硅烯晶格中硅原子密度降低,两种体制的竞争使得硅烯杨氏模量表现出先升高在降低的趋势.     

半氢化石墨烯与单层氮化硼复合体系的电子结构和磁性的调控

采用密度泛函理论第一性原理的PBE-D_2方法,对半氢化石墨烯与单层氮化硼(H-Gra@BN)复合体系的结构稳定性、电子性质和磁性进行了系统的研究.计算了六种可能的堆叠方式,结果表明:H-Gra@BN体系的AB-B构型是最稳定的,为铁磁性半导体,上、下自旋的带隙分别为3.097和1.798 e V;每个物理学原胞具有约1μB的磁矩,该磁矩主要来源于由未氢化的C_2原子的贡献;在z轴方向压应力的作用下,最稳的H-Gra@BN体系的电子性质由磁性半导体转变为半金属,再转变为非磁性金属;预测了一种能方便地通过应力调控电子性质和磁性质的新型材料,有望应用在纳米器件以及智能建筑材料等领域.     

Adsorption configurations of carbon monoxide on gold monolayer supported by graphene or monolayer hexagonal boron nitride: a first-principles study

Using density functional theory with a semiempirical van der Waals approach proposed by Grimme, the adsorption behavior of carbon monoxide on a gold monolayer supported by graphene or monolayer hexagonal boron nitride has been investigated. Based on the changes in the Dirac cone of graphene and a Bader charge analysis, we observe that the Au(111) monolayer gains a small charge from graphene and monolayer h-BN. The adsorbed CO molecule adopts similar adsorption configurations on Au(111)/graphene and Au(111)/h-BN with Au-C distance 2.17?2.50 Å and Au-C-O angle of 123.9°–139.6°. Moreover, we found that for low CO coverages, bonding to the gold surface is surprisingly energy-favorable. Yet the CO adsorption binding energy diminishes at high coverage due to the repulsive van der Waals interactions between CO molecules.     

Selectively strong molecular adsorption on boron nitride monolayer induced by transition metal substrate

We studied adsorption of several molecules (CO, CO₂, H₂O, N₂O, NO, NO₂, and O₂) on hexagonal boron nitride (h-BN) monolayers supported on transition metal (TM) surfaces, using density functional calculations. We observed that all the molecules bind very weakly on the pristine h-BN, with binding energies in the range of 0.02–0.03 eV. Interestingly, however, when h-BN is supported on the TM surface, NO₂ and O₂ become strongly chemisorbed on h-BN, with binding energies of >1 eV, whereas other molecules still physisorbed, with binding energies of ～0.1 eV at most. The electron transfer from TM to p_z states of h-BN played a substantial role in such strong bindings of NO₂ and O₂ on h-BN, as these molecules possess unpaired electrons that can interact with p_z states of h-BN. Such selective molecular binding on h-BN/TM originates from the peculiar distribution of the spin-polarized highest occupied and lowest unoccupied molecular orbitals of NO₂ and O₂. Strong molecular adsorption and high selectivity would make the h-BN/TM system possible for a variety of applications such as catalysts and gas sensors.     

Nuclear quantum effects on the thermal expansion coefficient of hexagonal boron nitride monolayer

This work examines the importance of vibrational delocalization on a basicthermomechanical property of a hexagonal boron nitride monolayer, namely its thermalexpansion coefficient (TEC). Using a recently parametrized bond-order potential of theTersoff type, the TEC was theoretically obtained from the thermal variations of thelattice parameter a(T) calculated using threedifferent methods: (i) the quasiharmonic approximation; (ii) its anharmonic improvementbased on self-consistent phonons; (iii) fully anharmonic Monte Carlo simulations possiblyenhanced within the path-integral framework to account for nuclear quantum effects. Theresults obtained with the three methods are generally consistent with one another and withother recently published data, and indicate that the TEC is negative at least up to ca.700 K, quantum mechanical effects leading to a significant expansion by about 50% relativeto the classical result. Comparison with experimental data on bulk hexagonal BN suggestssignificant differences, which originate from possible inaccuracies in the model that tendto underestimate the lattice parameter itself, and most likely from the 2D nature of themonolayer and the key contribution of out-of-plane modes. The effects of isotopic purityin the natural abundances of boron are found to be insignificant.     

含空位二维六角氮化硼电子和磁性质的密度泛函研究

基于密度泛函理论的第一性原理计算, 研究了含B原子空位(V_B), N原子空位(V_N), 以及含B–N键空位 (V_B+N)缺陷的二维氮化硼(h-BN)的电子和磁性质. 在微观结构上, V_B体系表现为在空位附近的N原子重构成等腰三角形, V_N体系靠近空穴的B 原子形成等边三角形, V_B+N体系靠近空穴处的B和N原子在h-BN平面上重构为梯形. 三种空位缺陷都使h-BN的带隙类型从直接带隙转变为间接带隙. V_B体系的总磁矩为1.0 μ_B, 磁矩全部由N原子贡献. 其中空穴周围的三个N原子磁矩方向不完全一致, 存在着铁磁性和反铁磁性两种耦合方式. 对于V_N 体系, 整个晶胞内的总磁矩也为1.0 μ_B, 磁矩在空穴周围区域呈现一定的分布. 关键词： 二维h-BN 空位 电子结构 磁性     

Formation and atomic structures of boron nitride nanohorns encaging boron nitride cluster

Boron nitride (BN) nanohorns were synthesized by arc-melting YB₆ powders. Method, and atomic structure models for BN nanohorns encaging Y@B₃₆N₃₆ were proposed from high-resolution electron microscopy. The molecular mechanics calculation indicated that BN clusters with metal atoms would be stabilized by being encaged in double-walled BN nanohorns.     

Excitons in boron nitride nanotubes: dimensionality effects

We show that the optical absorption spectra of boron nitride (BN) nanotubes are dominated by strongly bound excitons. Our first-principles calculations indicate that the binding energy for the first and dominant excitonic peak depends sensitively on the dimensionality of the system, varying from 0.7 eV in bulk hexagonal BN via 2.1 eV in the single sheet of BN to more than 3 eV in the hypothetical (2, 2) tube. The strongly localized nature of this exciton dictates the fast convergence of its binding energy with increasing tube diameter towards the sheet value. The absolute position of the first excitonic peak is almost independent of the tube radius and system dimensionality. This provides an explanation for the observed "optical gap" constancy for different tubes and bulk hexagonal BN.     

Polycrystalline cubic boron nitride prepared with cubic-hexagonal boron nitride under high pressure and high temperature

Polycrystalline cubic boron nitride(Pc BN) compacts, using the mixture of submicron cubic boron nitride(c BN) powder and hexagonal BN(h BN) powder as starting materials, were sintered at pressures of 6.5–10.0 GPa and temperature of1750℃ without additives. In this paper, the sintering behavior and mechanical properties of samples were investigated.The XRD patterns of samples reveal that single cubic phase was observed when the sintering pressure exceeded 7.5 GPa and h BN contents ranged from 20 vol.% to 24 vol.%, which is ascribed to like-internal pressure generated at grain-to-grain contact under high pressure. Transmission electron microscopy(TEM) analysis shows that after high pressure and high temperature(HPHT) treatments, the submicron c BN grains abounded with high-density nanotwins and stacking faults, and this contributed to the outstanding mechanical properties of Pc BN. The pure bulk Pc BN that was obtained at 7.7 GPa/1750℃ possessed the outstanding properties, including a high Vickers hardness(～ 61.5 GPa), thermal stability(～ 1290℃ in air),and high density(～ 3.46 g/cm~3).     

Symmetry breaking in boron nitride nanotubes

We have imaged boron nitride nanotubes with atomic scale resolution using scanning tunneling microscopy. While some nanotubes show the expected triangular lattice pattern, the majority of the nanotubes show unusual stripe patterns which break the underlying symmetry of the boron nitride lattice. We identify the origin of the symmetry breaking and demonstrate that conventional STM imaging analysis is inadequate for boron nitride nanotubes.     

Luminescence centers in cubic boron nitride

Complex and multiband photoluminescence spectra for GB and HBN centers in single crystals of cubic boron nitride (cBN) were recorded in the wavelength ranges 385–400 nm and 365–395 nm and the nature of these centers was studied. The use of models involving resonance vibrations and strongly shifted configuration diagrams for the electronic ground state and excited state made it possible to associate formation of the GB-1 center with the presence of tungsten impurity in cBN. It was established that the HBN band in the 300–350 nm range of the cathodoluminescence spectra of cBN polycrystals, single crystals, and micropowders is associated with luminescence centers present in microinclusions of graphite-like boron nitride (hBN). The nature of the hBN band is tentatively interpreted within the model of recombination of donor and acceptor defects in hBN: respectively nitrogen vacancies and carbon atoms in positions substituting for nitrogen. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 241–246, March–April, 2007.