椭圆截面金纳米管的局域表面等离激元共振特性研究

基于时域有限差分方法研究了几何形状、入射电场偏振方向、管壁厚度及内核和包埋介质的变化对椭圆截面金纳米管局域表面等离激元共振特性的影响.研究发现,当长轴固定时,短轴的减小将导致纳米管消光峰红移;入射电场偏振方向与椭圆长轴夹角的增大将导致消光峰红移;当颗粒整体尺寸不变时,管壁厚度减小同样会使得消光峰红移.此外,内核及包埋介质介电常数的增大均导致消光峰红移.利用等离激元杂化理论及自由电子和振荡电子竞争机理对上述现象进行了理论分析. 关键词： 消光光谱 局域表面等离激元共振 金纳米管 时域有限差分方法     

Tunable plasmon resonance wavelength of the periodic gold film with converging and diverging shaped slits and grooves

We investigate a periodic slit-groove metal array with converging and diverging shaped channels by using the finite-difference time-domain (FDTD) method. We show that the peaks and dips of the transmission spectra can be tuned by the geometry parameters of the groove. And the resonance modes are strongly correlated with the groove depth and width of both ends of the groove, and the transmission dip between the resonance modes can be modulated by these parameters. However, the distance between the slit and the groove has little influence on the transmission. We show that the periodic slit-groove with diverging and converging shaped channels is useful for the design of plasmonic devices.     

Localized surface plasmon resonance enhanced blue light-emission of polyfluorene copolymer

Polyfluorene-based blue light-emitting devices suffer from the shortcomings of low stability, drastic loss of quantum yield and poor color purity. To find out the solution, we use silver nanoparticles for enhancement of photoluminescence of polyfluorene copolymer (PCFOz) through localized surface plasmon resonance (LSPR) coupling effect. The photoluminescence from PCFOz can be concentrated down to nanoscale, realizing a high spatial selectivity of the fluorescence enhancement process. PL emission of conjugated polymer is blueshifted about 8 nm from the peak emission of 433 nm for the neat PCFOz film to around 425 nm for the Ag/PCFOz composite film. The full width at half maximum of PCFOz is reduced from 88 to 60 nm. Absorbance spectra and time resolved photoluminescence measurements further demonstrate that both absorption intensity and recombination rate of PCFOz increase due to strong LSPR-excitons coupling. Optical properties of such plasmon-enhanced organic light emitters were also studied by temperature-dependent PL spectroscopy from 10 to 200 K. In comparison with bare PCFOz, the LSPR induced emission enhancement ratio significantly increases with increasing temperature. These results are believed to be important for the development of highly efficient blue organic light-emitting devices based on all-solution processing.     

Energetics and stability of vacancies in carbon nanotubes

In this work we present ab initio calculations of the formation energies and stability of different types of multi-vacancies in carbon nanotubes. We demonstrate that, as in the case of graphene, the reconstruction of the defects has drastic effects on the energetics of the tubes. In particular, the formation of pentagons eliminates the dangling bonds thus lowering the formation energy. This competition leads to vacancies having an even number of carbon atoms removed to be more stable. Finally the appearance of magic numbers indicating more stable defects can be represented by a model for the formation energies that is based on the number of dangling bonds of the unreconstructed system, the pentagons and the relaxation of the final form of the defect formed after the relaxation.     

On the existence and stability of double-walled armchair silicon carbide nanotubes

A systematic study of type 1 armchair double-walled SiC nanotubes (DWNTs) (n,n)@(m,m) (3≤n≤6;7≤m≤12) using the finite cluster approximation is presented. The geometries of the tubes have been spin optimized using the hybrid functional B3LYP (Becke’s three-parameter exchange functional and the Lee-Yang-Parr correlation functional) and the all-electron 3-21G* basis set. The study indicates that the stabilities of the double-walled SiC nanotubes are of the same order as those of single-walled SiC nanotubes suggesting the possibilities of experimental synthesis of both single-walled and double-walled SiC nanotubes. The binding energy per atom or the cohesive energy of the double-walled nanotubes depends not only on the number of atoms but also on the coupling of the constituent single-walled nanotubes. The formation energy of the DWNTs is found to be maximum when the interlayer separation is about 3.5 Å. The DWNTs (n,n)@(n+4,n+4) are found to have large formation energies. In particular, (5,5)@(9,9) DWNT is the most stable tube in our study with a binding energy per atom of 5.07 eV, the largest formation energy of 12.39 eV, an interlayer separation of 3.58 Å and a “band gap” of 1.97 eV. All double-walled SiC nanotubes are found to be semiconductors, with the band gaps decreasing from single-walled nanotubes to double-walled nanotubes.     

Tunable optical transmission through square-core metallic nanotube arrays

We propose a square-core metallic nanotube array and investigate its optical transmission property theoretically. We find that the transmission spectra can be tuned by the width of square-core edge, the intertube spacing and the dielectric constants of the core and the embedding medium between the nanotubes. We show that there is a band gap over a wide optical wavelength, and its width, number and position are sensitive to the tunable parameters. We also discuss the situation of the rectangular-core nanotube arrays and present that modification of the size of internal holes leads to redshift of the transmission spectra. Based on the localized nature of the field distributions, we show that there are local plasmonic resonant modes that originate from multipolar plasmon polaritons and a large number of opposing surface charges build up in the gap between adjacent nanotubes.     

Selective suppression of extinction within the plasmon resonance of gold nanoparticles

We present extinction measurements on rectangular two-dimensional arrays of gold nanoparticles on a dielectric waveguide. The spectra exhibit spectrally narrow bands of suppressed extinction within the particle–plasmon resonance, resulting from destructive interference between the incident light field and the excited waveguide modes. The dependence of the spectral position of these high-transmission bands on different waveguide modes is investigated in detail. Received: 3 July 2001 / Published online: 10 October 2001     

金银三层纳米管局域表面等离激元共振特性研究

相对于单一金属纳米材料,二金属复合纳米材料具有更大的潜在应用价值.基于时域有限差分方法,研究了SiO₂-Ag-Au和SiO₂-Au-Ag二金属三层纳米管的消光光谱,并对其局域表面等离激元共振(Localized Surface Plasmon Resonance,LSPR)特性进行了分析.研究发现,内核尺寸变大将导致上述两种金属纳米管LSPR峰红移;内层金属及外层金属壳层厚度增大均会导致其LSPR峰蓝移.银壳厚度变化对纳米管LSPR的调制作用大于金壳厚度变化造成的影响.上述现象可以利用等离激元杂化理论及自由电子和振荡电子变化的竞争机制进行分析.     

Characterization of protein-conjugating kinetics based on localized surface plasmon resonance of the gold nanoparticle

The gold nanoparticle exhibits optical property of localized surface plasmon resonance (LSPR), which dynamically alters as the surface adsorbs new ligands. We carried out a semi-quantitative analysis with the method of multivariate curve resolution, observing that the adsorption of serum albumin on gold nanoparticle was best deciphered as two-mode competitive kinetics. Interestingly, for human serum albumin, the slower mode contributed considerably to the LSPR response of protein-conjugated surfaces, while in the case of bovine serum albumin the faster mode overwhelmed the slower one at high protein concentrations. The kinetic patterns were rationalized with diversity of biomolecular orientations on the nanoparticle surface. The simple but efficient protocol supports semi-quantitative analysis combining UV-vis spectroscopy with chemometrics method for distinguishing conjugation kinetics of different types of proteins on the surface of nanoparticles at nanomolar concentration.     

Activation behavior and dielectric relaxation in polyvinyl alcohol and multiwall carbon nanotube composite films

The dc and ac electrical transport property of Polyvinyl Alcohol-Multiwall Carbon Nanotubes (PVA-MWNT) composites has been investigated within a temperature range and in the frequency range 20Hz-1MHz. The temperature variation of dc conductivity gives the presence of two different activation energies. The dielectric properties of the samples have been explained in terms of electric modulus vector.The dielectric relaxation has been explained in terms of interfacial polarization occurring in between the insulating PVA matrix and MWNT conductive filler. The variation of the relaxation time with temperature also indicates the presence of two different activation energies.     

A DFT studies of structural and quadrupole coupling constants properties in C-doped BeO nanotubes

In the framework of density functional theory (DFT), we calculated the electronic structures and the quadrupole coupling constants (CQ) in the pristine and carbon doped (C-doped) beryllium oxide nanotubes (BeONTs) for the first time. The pristine and C-doped forms of representative (10, 0) zigzag and (5, 5) armchair models of BeONTs were considered in this study. The structures are allowed to relax by performing all atomic optimization. Formation energies indicate that C-doping of Be atom (CBe form) could be more favorable than C-doping of O atom (CO form) in both zigzag and armchair BeONTs. Gap energies and dipole moments detected the effects of dopant in the (5, 5) armchair models; however, those parameters did not detect any significant changes in the C-doped (10, 0) zigzag BeONT models. The calculated nuclear quadrupole coupling constant for the Be and O nuclei reveal that the pristine models can be divided into layers of nuclei with an equivalent electrostatic environment such that those nuclei at the ends of tubes end up in a strong electrostatic environment when compared to the other nuclei along the length of tubes. Comparison with the available data on the pristine BeONTs reveals the influence of C-doping on the CQ parameters of Be and O atoms in the C-doped structures. For most lattice sites, the degree of influence on the CQ parameters of the zigzag model is larger than that of the armchair model. The calculations were performed based on the B3LYP DFT method and 6-31G^∗ standard basis sets using the Gaussian 09 program package.     

Heat conduction in extended X-junctions of single-walled carbon nanotubes

Non-equilibrium molecular dynamics (NEMD) simulations are employed to investigate the longitudinal thermal conductivity of non-orthogonal extended X-junction (EX-junction) of single-walled carbon nanotubes (SWCNTs). Different from standard junctions of SWCNTs, two distinct jumps in the temperature profile around the EX-junction are observed, which are responsible for the larger temperature gradient and reduction in thermal conductivity when compared to standard X-junction. Quantum corrected results show that the longitudinal thermal resistance of the X-junction and EX-junction decreases monotonically with increasing temperature which makes the longitudinal thermal conductivity of the tube with junction less sensitive to temperature above 400 K comparing with the individual pristine tube. The origin of the significant decrease of thermal conductivity of EX-junction is discussed through phonon spectra analysis.     

Excitons in optical spectra of boron-nitride (BN) nanotubes

Exciton effects are studied in single-wall boron-nitride nanotubes. The Coulomb interaction dependence of the band gap, the optical gap, and the binding energy of excitons are discussed. The optical gap of the (5,0) nanotube is about 6 eV at the on-site interaction U=2t with the hopping integral t=1.1 eV. The binding energy of the exciton is 0.50 eV for these parameters. This energy agrees well with that of other theoretical investigations. We find that the energy gap and the binding energy are almost independent of the geometries of nanotubes. This novel property is in contrast with that of the carbon nanotubes, which show metallic and semiconducting properties depending on the chiralities.     

Plasmon resonance coupling in strongly coupled gold nanotube arrays with structural defects

We theoretically investigate the transmission spectra and the field distributions with different defects in the gold nanotube arrays by using the finite-difference time-domain method.It is found that the optical properties of the nanotube arrays are strongly influenced by different defects.When there are no defects in the central nanotube,the values of peaks located at both sides of the photonic band gap have their maxima.Based on the distributions of electric field component E x and the total energy distribution of the electric and the magnetic field,we show that mainly a dipole field distribution is exhibited for the plasmon mode at the long-wavelength edge of the band gap but higher order modes of the composite are excited at the short-wavelength edge of the band gap.The plasmon resonant modes can also be controlled by introducing defects.     

粒子等离子共振对有机半导体共混体系中激发复合体荧光发射的作用

研究了具有局域等离子共振特性的金纳米岛状结构阵列对高分子材料共混体系中激发复合体荧光发射特性的影响.实验结果表明,当粒子等离子共振发生在激发复合体荧光光谱区时,其荧光发射的强度得到了显著增强,且荧光寿命也得以延长.可以认为,粒子等离子共振诱发的局域场增加了激子的扩散距离,利于在相分离界面处激发复合体的形成. 关键词： 金纳米岛状结构 粒子等离子共振局域场增强效应 聚合物共混体系 激发复合体     

金纳米环双体尺寸和耦合效应对表面等离子体共振特性的影响

采用离散偶极子近似方法系统地研究了金纳米环双体的消光光谱及其电场分布. 计算结果表明, 金纳米环双体在耦合作用下的共振消光峰对应着不同振动模式, 改变金纳米环双体的排列方式、 间距和尺寸大小, 其表面等离子体共振消光峰发生红移或蓝移. 因此可以通过对金纳米环双体结构参数和排列方式的设定, 调节其表面等离子体共振消光峰的位置. 电场分布表明, 水平排列的金纳米环双体较单个金纳米环产生更强的局部表面增强电场. 适当的小间距, 较大的内外半径的金纳米环水平阵列更适合做表面增强拉曼散射的衬底, 在生物分子检测等领域具有潜在的应用.     

Effects of an electric field on the electronic and optical properties of zigzag boron nitride nanotubes

We have investigated the electro-optical properties of zigzag BNNTs, under an external electric field, using the tight binding approximation. It is found that an electric field modifies the band structure and splits the band degeneracy. Also the large electric strength leads to coupling the neighbor subbands which these effects reflect in the DOS and JDOS spectrum. It has been shown that, unlike CNTs, the band gap of BNNTs can be reduced linearly by applying a transverse external electric field. Also we show that the larger diameter tubes are more sensitive than small ones. The semiconducting metallic transition can be achieved through increasing the applied fields. The number and position of peaks in the JDOS spectrum are dependent on electric field strength. It is found that at a high electric field, the two lowest subbands are oscillatory with multiple nodes at the Fermi level.     

Thermal conductivity for single-walled carbon nanotubes from Einstein relation in molecular dynamics

Equilibrium molecular dynamics based Einstein relation with an appropriate definition for integrated heat current (i.e., with modified energy moment) are combined to quantify the thermal conductivity of individual single-walled carbon nanotubes, armchair, zigzag and chiral tubes. The thermal conductivity has been investigated as a function of three parameters, tube radius, length and chirality at and near room temperature with Brenner potential model. Thermal conductivity is found to have unusually high value and varies with radius, length and chirality of tubes. Also the thermal conductivity at temperature range from 50 to 100 K is found to have a maximum value. For 12.1 nm tube length, the thermal conductivity has converging trend which its value dependents on the tube radius and chirality. Tubes with large radius have lower values of thermal conductivity. Furthermore, the results show that armchair tubes have large values of the thermal conductivity comparing with zigzag and chiral tubes. It seems possible to uncover carbon nanotubes thermal properties based on measurements having heat dependence by adding another methods for calculations.     

Improvement in characteristics of natural rubber nanocomposite by surface modification of multi-walled carbon nanotubes

We aim to develop high-level applications of NR through the innovative use of multi-walled carbon nanotubes (MWCNTs) to improve reinforcing performance and thermal resistance. In this study, we examined the structures and characteristics of composite materials in which NR was the matrix and MWCNTs were the fillers. We studied the properties of composites containing surface-activated MWCNTs with three different diameters. The results show that the reinforcing performance improves as MWCNT diameter decreases, while thermal resistance improves as we decrease the heat-treatment temperature. The latter occurs because adherence between MWCNTs and NR becomes stronger at lower heat-treatment temperatures. We also found that for practical applications, we need to control active sites on MWCNTs to balance adhesion against thermal resistance.     

Nonvolatile unipolar resistive switching in ultrathin films of graphene and carbon nanotubes

We report unipolar resistive switching in ultrathin films of chemically produced graphene (reduced graphene oxide) and multiwalled carbon nanotubes. The two-terminal devices with yield >99% are made at room temperature by forming continuous films of graphene of thickness ∼20 nm on indium tin oxide coated glass electrode, followed by metal (Au or Al) deposition on the film. These memory devices are nonvolatile, rewritable with ON/OFF ratios up to ∼ 10⁵ and switching times up to 10 μs. The devices made of MWNT films are rewritable with ON/OFF ratios up to ∼400. The resistive switching mechanism is proposed to be nanogap formation and filamentary conduction paths.