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.     

Magnetic behavior and clustering effects in Mn-doped boron nitride sheets

Ab initio calculations are performed in the framework of density functional theory on Mn-doped boron nitride sheets, which are candidates for two-dimensional diluted magnetic semiconductors (DMSs). Each type of substitution reveals a qualitatively different magnetic behavior encompassing ferromagnetic, anti-ferromagnetic and spin glass ordering. The ability of formation of these defects is also discussed. We analyze the dependence of the exchange couplings on the distance between impurities and the typical range and distribution are extracted. Multiple-impurity configurations are considered and the results are mapped on an Ising-type Hamiltonian with higher order exchange interactions, revealing deviations from the standard two-spin models. The percolation of interacting magnetic moments is discussed and the critical concentration is determined for the underlying transition from a ferromagnetic to a super-paramagnetic state. We conclude our study by providing the optimal conditions for doping in order to obtain a ferromagnetic DMS.     

Continuum model for low-frequency phonons of boron nitride nanotubes

A continuum model is employed to calculate the low-frequency phonons of boron nitride nanotubes. We find an excellent agreement of the optically active modes calculated within this approach and those from more elaborate calculations within an energy and wavelength window that can be established beforehand, from the choice of the bulk input parameters. We verify that this model describes correctly the dependence of radial breathing mode with the radius, the existence of parabolic modes at small wavevectors, and other general characteristics of the dispersion relations of these systems.     

Rapid communication: Permeability of hydrogen in two-dimensional graphene and hexagonal boron nitride sheets

This paper concerns an application to optimal energy by incorporating thermal equilibrium on MHD-generalised non-Newtonian fluid model with melting heat effect. Highly nonlinear system of partial differential equations is simplified to a nonlinear system using boundary layer approach and similarity transformations. Numerical solutions of velocity and temperature profile are obtained by using shooting method. The contribution of entropy generation is appraised on thermal and fluid velocities. Physical features of relevant parameters have been discussed by plotting graphs and tables. Some noteworthy findings are: Prandtl number, power law index and Weissenberg number contribute in lowering mass boundary layer thickness and entropy effect and enlarging thermal boundary layer thickness. However, an increasing mass boundary layer effect is only due to melting heat parameter. Moreover, thermal boundary layers have same trend for all parameters, i.e., temperature enhances with increase in values of significant parameters. Similarly, Hartman and Weissenberg numbers enhance Bejan number.     

Formation and structure of boron nitride conical nanotubes

Nanotubes exhibiting a novel structure - boron nitride (BN) conical nanotubes whose walls consist of conical layers with their cone axis parallel to the tube axis, as opposed to ordinary nanotubes, composed of concentric cylindrical layers with their normal perpendicular to the tube axis - were synthesized simultaneously with BN nanotubes by using carbon nanotubes (CNTs) as templates. The diameters of the BN conical nanotubes are typically about 15 nm, which is similar to those of the starting CNTs. Apex angles and inner diameters of most BN conical nanotubes are about 40° and 1 nm, respectively. The lengths of the BN conical nanotubes range from 50 nm to up to several micrometers.     

Tuning the electronic and magnetic properties of boron nitride nanotubes

Density Functional Theory is used to investigate the effect of altering the B/N ratio and carbon doping on the electronic and magnetic structure of zigzag, (7, 0) and armchair (5, 5) boron nitride nanotubes. The calculations indicate that increasing the boron content relative to the nitrogen content significantly reduces the band gap to a value typical of a semiconductor. Calculations of carbon doped semiconducting BN tubes, which have more boron atoms than nitrogen atoms have a net spin and a difference in the density of states at the valence band between the spin up and spin down state.     

Synthesis and morphology of boron nitride nanotubes and nanohorns

Boron nitride (BN) nanotubes have been synthesized by evaporating a mixture of boron and gallium oxide in the presence of ammonia gas. The synthesized BN nanotubes exhibit a well-crystallized concentric structure with diameters less than 30 nm, and no carbon contamination or defects could be observed, while the BN nanotubes with large diameters usually show a number of defects. Some BN nanohorn structures could also be observed in the product. The carbon-free growth of BN nanotubes was explained based on the vapor–liquid–solid growth mechanism, and the catalytic activity of liquid gallium for BN one-dimensional growth was also demonstrated. Received: 16 April 2002 / Accepted: 25 May 2002 / Published online: 19 July 2002     

A comparison between the mechanical and thermal properties of single-walled carbon nanotubes and boron nitride nanotubes

Carbon nanotubes (CNTs) are semimetallic while boron nitride nanotubes (BNNTs) are wide band gap insulators. Despite the discrepancy in their electrical properties, a comparison between the mechanical and thermal properties of CNTs and BNNTs has a significant research value for their potential applications. In this work, molecular dynamics simulations are performed to systematically investigate the mechanical and thermal properties of CNTs and BNNTs. The calculated Young’s modulus is about 1.1 TPa for CNTs and 0.72 TPa for BNNTs under axial compressions. The critical bucking strain and maximum stress are inversely proportional to both diameter and length-diameter ratio and CNTs are identified axially stiffer than BNNTs. Thermal conductivities of (10, 0) CNTs and (10, 0) BNNTs follow similar trends with respect to length and temperature and are lower than that of their two-dimensional counterparts, graphene nanoribbons (GNRs) and BN nanoribbons (BNNRs), respectively. As the temperature falls below 200 K (130 K) the thermal conductivity of BNNTs (BNNRs) is larger than that of CNTs (GNRs), while at higher temperature it is lower than the latter. In addition, thermal conductivities of a (10, 0) CNT and a (10, 0) BNNT are further studied and analyzed under various axial compressive strains. Low-frequency phonons which mainly come from flexure modes are believed to make dominant contribution to the thermal conductivity of CNTs and BNNTs.     

Field emission and current-voltage properties of boron nitride nanotubes

We have measured electrical transport properties of boron nitride nanotubes using an in situ manipulation stage inside a transmission electron microscope. Stable currents were measured in a field emission geometry, but in contact the nanotubes are insulating at low bias. At high bias, the nanotubes show stable, reversible breakdown current.     

Structural and electronic properties of sulphur-doped boron nitride nanotubes

First-principles calculations based on density functional theory were performed to study the structural and electronic properties of sulphur substitution-doped boron nitride (BN) nanotubes, using the theory as implemented in SIESTA code, which uses non-conserving pseudo-potentials in fully non-local form and atomic orbitals as the basis set. The generalized gradient approximation (GGA) was used for the exchange–correlation (XC) potential. The tube selected was a (10, 0) BN nanotube that fell in the range of energy gap independent of the tube diameter. The electronic and structural properties for sulphur substitution in the boron and the nitrogen sites were studied. The structural arrangement in equilibrium conditions for S shows an outward radial deformation around the sulphur atom in the tube. The bandgap of the pristine BN nanotubes was found to be significantly modified on doping.     

Two-qubit cells made of boron nitride nanotubes for a quantum computer

The electronic structure of boron nitride nanotubes (8, 0) with intercalated alkali metal atoms and alkaline-earth metal ions is studied. It is shown by calculation that the spin density is localized on individual atoms or ions. The antiferromagnetic state of a linear chain of atoms and ions turns out to be energetically more favorable. Exchange interaction between spins is fairly weak. Such systems are suggested to be used as two-qubit cells for a quantum computer.     

Excitons and many-electron effects in the optical response of single-walled boron nitride nanotubes

We report first-principles calculations of the effects of quasiparticle self-energy and electron-hole interaction on the optical properties of single-walled boron nitride nanotubes. Excitonic effects are shown to be even more important in BN nanotubes than in carbon nanotubes. Electron-hole interactions give rise to complexes of bright (and dark) excitons, which qualitatively alter the optical response. Excitons with a binding energy larger than 2 eV are found in the BN nanotubes. Moreover, unlike the carbon nanotubes, theory predicts that these exciton states are comprised of coherent supposition of transitions from several different subband pairs, giving rise to novel behaviors.     

Isotope effect on the thermal conductivity of boron nitride nanotubes

We have measured the temperature-dependent thermal conductivity kappa(T) of individual multiwall boron nitride nanotubes using a microfabricated test fixture that allows direct transmission electron microscopy characterization of the tube being measured. kappa(T) is exceptionally sensitive to isotopic substitution, with a 50% enhancement in kappa(T) resulting for boron nitride nanotubes with 99.5% 11B. For isotopically pure boron nitride nanotubes, kappa rivals that of carbon nanotubes of similar diameter.     

Modeling of electronic density of states for single-wall carbon and boron nitride nanotubes

The electronic density of states is calculated for all possible geometric configurations of single-wall carbon and boron nitride nanotubes. The calculation is based on the numerical differentiation of the two-dimensional dispersion relations for graphite and hexagonal boron nitride. The differentiation is performed for all allowed values of the wave vector using the π-electron approximation. For the particular carbon nanotubes chosen as examples, a good agreement is demonstrated between the calculated values of energy spacing of the symmetric van Hove singularities in the density of states and the experimental data obtained from the resonance Raman scattering study.     

Quantum-chemical calculations of the piezoelectric characteristics of boron nitride and carbon nanotubes

The piezoelectric characteristics of boron-nitride and carbon nanotubes were calculated. The electronic structure of nanotubes was studied using the quantum-chemical semiempirical MNDO method within a molecular-cluster model. The piezoelectric constants e _zzz, e _xzz, and e _xxx of boron nitride nanotubes of two structural modifications (n, n) (n = 5, 6, ..., 9) and (n, 0) (n = 6, 7, ..., 12) were calculated. The values of the piezoelectric constants e _zzz of tubular boron nitride are found to be close in order of magnitude to the respective values obtained using nonempirical calculation methods. The piezoelectric constant e _xzz of a (6, 6) carbon nanotube doped with substitutional point defects was calculated.     

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.     

Energetics and structural properties of carbon and oxygen doped hexagonal boron nitride sheets

Energetics and structural properties of carbon and oxygen doped hexagonal boron nitride sheets have been investigated by performing density functional theory calculations. Substitutional doping model has been considered in the neutral charge state. C and O atoms replaced either B or N site in the system as impurities. A systematic study has been performed to see the effect of cell size on the calculated quantities, such as formation energy, relaxation energy, charge and bond length. It has been found that substitution of O atom on the N site in the hexagonal BN sheet is more favorable.     

Novel precursors of solvated electrons in water: evidence for a charge transfer process

Femtosecond midinfrared spectroscopy of water (heavy water) after two photon excitation at 9 eV provides clear evidence for two short-lived precursors of the hydrated electron preceding the well-known "wet electron." The measured first intermediate with peak absorption at 2.9 (4.1) microm is proposed to represent an O(H, D):e(-) complex. The subsequent solvation proceeds via e(-):[(H, D)2O](n) complexes at approximately 1.6 (2.0) microm in the electronic ground state, involving an increasing number of water molecules during the first 200 fs and followed by the wet electron.     

New organometallic salts as precursors for the functionalization of carbon nanotubes with metallic nanoparticles

New organometallic salts were synthesized in aqueous solution and were used as precursors for the functionalization of carbon nanotubes (CNT) by metallic nanoparticles. The precursors were obtained by reaction between HAuCl₄, (NH₄)₂PtCl₆, (NH₄)₂PdCl₆, or (NH₄)₃RhCl₆ with cetyltrimethylammonium bromide (CTAB). The as-obtained (CTA) _n Me _x Cl _y salts (with Me?=?Au, Pt, Pd, Rh) were characterized by Fourier-transform infra-red (FTIR) spectroscopy, ¹H nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis. These precursors were then used to synthesize metallic nanoparticles of Au, Pt, Pd, and Rh over multiwalled carbon nanotubes (MWCNT). Characterization by scanning transmission electron microscopy (STEM) and thermogravimetric analysis under air reveals that the CNT-supported catalysts exhibit high loading and good dispersion of the metallic nanoparticles with small average particle sizes. The present preparation procedure therefore allows obtaining high densities of small metallic nanoparticles at the surface of MWCNT.     

氢气与氮气对硼碳氮纳米管生长的影响

在对不同温度和不同催化剂对硼碳氮(BCN)生长影响研究的基础上，进一步研究了氮气与氢气对高温热解法制备BCN纳米管结构、产量等的影响.实验中发现氮气在制备过程中只对BCN纳米管的产量有微小影响，对所生成的纳米管的结构有一定影响，气流量太小时，乙二胺的转化率低，气流量太大时，会在所生成的BCN纳米管管壁上出现断裂生长现象.与氮气不同的是氢气不仅对所生成的纳米管的结构有很大影响，还对产量有明显影响，当制备过程中没有氢气时，所生成的BCN纳米管有明显的弯曲，甚至出现了急剧的弯折，大部分管壁附着无定形碳，还伴随中 关键词： BCN纳米管 热解 氢气 氮气