金和银纳米粒子二维周期阵列的光学性质

本文利用离散点偶极子近似方法(DDA)研究了金和银纳米粒子二维周期阵列的光学性质。研究结果表明二维周期阵列的消光性质及其表面等离子共振(SPR)波长受到阵列内粒子组成材料、粒子形状尺寸、阵列周期和阵列排布方式等因素的影响。对于二维正方阵列,当周期较小时(一般小于300 nm),阵列的共振波长主要取决于粒子组成材料和形状尺寸;当周期与阵列单体的共振波长附近时,阵列的消光谱中会出现极窄且锐的SPR共振峰,峰位只与阵列的周期值相关。改变阵列在平行和垂直于入射光偏振方向的周期,可以方便地调节二维长方阵列的共振峰的峰位和峰宽。     

三层材料纳米颗粒形状对消光特性的影响

通过高分辨率电子束光刻方法制备了不同形状的三层复合材料纳米颗粒,研究了这种纳米颗粒的形状变化对消光特性的影响。测试结果表明,当入射波偏振方向平行于短轴时,随着长宽比的增大,共振峰位置发生蓝移;当光源偏振方向平行于长轴时,随着长宽比的增大,共振峰位置发生红移。还用时域有限差分算法以及表面等离波子的Lorentz模型对纳米颗粒的消光特性进行数值计算,所得的消光频谱曲线、共振峰位置变化趋势与实验基本一致。此外,还研究了主体材料层厚度对消光特性的影响,发现其厚度在20～90nm变化时,共振峰发生3～115nm的蓝移。     

Study on optical properties of aggregated ultra-small metal nanoparticles

We study the optical properties of dimer and septamer aggregates (in forms of being separated or merged) of ultra-small silver nanoparticles (a few nanometers in diameter) by calculating their extinction spectra and optical field distributions using the discrete dipole approximation method. Characteristics of their extinction spectra are identified due to different resonance modes dependent on the incidence states of light. Specifically, as polarization of the incidence light is perpendicular to the center-to-center lines of the nanoparticles, interaction of neighboring nanoparticles is in the “repulsive coupling mode”, which results in blue-shift of the resonance peak with decrease of the nanoparticle interspacing. While, whenever there is a projection of the polarization of incident light on the center-to-center lines of the nanoparticles, the “attractive coupling mode” between the nanoparticles dominates in their resonant interaction, which results in red-shift of the resonance peak with decrease of the nanoparticle interspacing. It is also shown that optical interaction of the ultra-small nanoparticles is only effective when their interspacings are approximately less than 15 nm, and particularly prominent when Coulomb interactions of the electronic charges of plasmons are active within a few nanometers.     

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     

倾斜光纤光栅谱特性

基于倾斜光纤光栅耦合模理论,采用数值分析法研究了前后向导模耦合时倾斜角度和调制深度对倾斜光纤光栅反射谱的影响,以及导模和辐射模耦合时针对不同的入射光偏振态在倾斜角度、调制深度、光栅长度等不同时倾斜光纤光栅透射谱(或反射谱)的特性.研究结果表明,在前后向导模耦合时,不同偏振态入射光的光谱几乎相同;而对于辐射模耦合,由于反射谱的包络受消光系数的调制,而不同偏振态入射光的消光系数不同,并且倾斜角度越大不同偏振态的入射光的消光系数差别越大,故在研究辐射模耦合时需要将偏振态予以考虑.     

倾斜光纤光栅谱特性

基于倾斜光纤光栅耦合模理论,采用数值分析法研究了前后向导模耦合时倾斜角度和调制深度对倾斜光纤光栅反射谱的影响,以及导模和辐射模耦合时针对不同的入射光偏振态在倾斜角度、调制深度、光栅长度等不同时倾斜光纤光栅透射谱(或反射谱)的特性.研究结果表明,在前后向导模耦合时,不同偏振态入射光的光谱几乎相同;而对于辐射模耦合,由于反射谱的包络受消光系数的调制,而不同偏振态入射光的消光系数不同,并且倾斜角度越大不同偏振态的入射光的消光系数差别越大,故在研究辐射模耦合时需要将偏振态予以考虑.     

金属纳米颗粒光学性质的离散偶极近似计算

采用离散偶极子近似(DDA)方法,研究了单体银纳米粒子和银纳米粒子阵列的光谱特性。研究结果发现,单体银纳米粒子的表面等离子体共振消光峰的位置随着周围介质折射率和粒子尺寸的增大逐渐红移,并且消光光谱的峰宽也越来越大。当银纳米粒子正方阵列的周期接近单体的共振波长时,阵列的消光光谱中会出现尖锐的共振峰,改变粒子尺寸的大小可以发现消光光谱中共振峰的峰值和位置有大幅度地改变,通过改变阵列在平行和垂直于入射光偏振方向上的周期,可以调节二维长方阵列共振峰的峰宽和峰位。该研究为纳米粒子在光学显微镜、生物传感元件、数据存储等领域中的应用提供有效地理论参考。     

Dependence of extinction cross-section on incident polarization state and particle orientation

This note reports on the effects of the polarization state of an incident quasi-monochromatic parallel beam of radiation and the orientation of a hexagonal ice particle with respect to the incident direction on the extinction process. When the incident beam is aligned with the six-fold rotational symmetry axis, the extinction is independent of the polarization state of the incident light. For other orientations, the extinction cross-section for linearly polarized light can be either larger or smaller than its counterpart for an unpolarized incident beam. Therefore, the attenuation of a quasi-monochromatic radiation beam by an ice cloud depends on the polarization state of the beam if ice crystals within the cloud are not randomly oriented. Furthermore, a case study of the extinction of light by a quartz particle is also presented to illustrate the dependence of the extinction cross-section on the polarization state of the incident light.     

Effect of shape and interstice on surface enhanced Raman scattering (SERS) of molecules adsorbed on gold nanoparticles in the near‐dipole and quadrupole regions

Surface enhanced Raman scattering (SERS) of adsorbed molecule on colloidal gold nanoparticles of different shapes, namely nanospheres (NSs), nanorods (NRs), and nanoprisms (NPs) as well as the three NPs arrays of different interstice prepared by NS lithography, are studied with incident wavenumbers in the near‐dipole and near‐quadrpole regions of the nanoparticles. In the colloidal gold nanoparticles, the SERS enhancement is the largest for the sharp tip followed by the truncated tip NPs, then the NRs and least enhancement for the NSs. This decreasing order of enhancement occurs although the incident wavenumber was near the dipole resonance of NSs and the quadrupole resonance for the NPs. These varied enhancements are explained in part as due to the binding energies of the nanocrystal facets, but the larger contribution results from the plasmon electromagnetic fields. A parallel finite difference time domain (FDTD) calculations were carried out, which corporate the experimental results and show agreement with ratios of the SERS enhancement for the different shapes. The normalized SERS intensity for NPs of different interstice distances show a sharp rise with the decrease of the interstice distances because of interparticle dipolar and quadrupolar coupling as evidenced also by FDTD calculations. Furthermore, these calculations show that the enhancement is polarization independent for an incident wavelength near quadrupole resonance but polarization dependent for an incident wavelength near the plasmon dipole transition. In the last case, the enhancement is larger by an order of magnitude for a polarization parallel to the NPs bisector than for polarization normal to the bisector with no hot spots for the relatively large interstice dimensions used. Copyright © 2012 John Wiley & Sons, Ltd.     

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     

Particle Shape Effects in the Extinction Spectra of Gold and Silver Nanoparticles

Particle shape effects in the absorption and scattering spectra of gold and silver nanoparticles are studied for optical-range radiation. Numerical calculations of extinction cross section are performed using the FDTD approach for particles of three shapes: disks, triangular prisms, and triradial-base prisms. It is established that the spectra of nanoparticles of different shapes differ qualitatively even if they are of the same characteristic dimensions. The obtained results can be used to develop a spectroscopic procedure for determining the shape of metallic nanoparticles and producing quantitative estimates of their characteristic dimensions.     

银纳米三棱柱二聚体的光学性质研究

本文利用离散偶极子近似方法研究了银纳米三棱柱二聚体的光学性质, 考察了粒子相对位置、粒子间隔和入射光偏振方向对消光谱和电场的影响。入射光偏振对二聚体的消光谱和表面电场均有较大的影响。纳米粒子间隔较小时, 粒子间存在较强的耦合; 粒子间隔较大时, 二聚体的消光谱更接近两个相互独立的粒子情形。另外二聚体的表面电场分布和平均电场强度还受到粒子相对位置和间隔的影响, 随着粒子间隔的增大, 表面平均电场值振荡上升达到最大值后减小。     

具有双共振吸收峰的Au纳米粒子制备及其拉曼表征

表面增强拉曼散射(SERS)很大程度的弥补了拉曼散射强度弱的缺点,迅速成为科研工作者们的研究热点,在食品安全、环境污染、毒品以及爆炸物检测等领域应用广泛。纳米技术的发展使得目前对于SERS的研究主要集中于金属纳米颗粒基底的制备,金属纳米粒子的种类、尺寸及形貌对SERS增强和吸收峰峰位均有影响,要获得好的增强效果,需要对金属纳米结构进行工艺优化。特别是,需要结合金属纳米粒子的结构和激励光波长,以期获得更好的增强效果。为了研究SERS增强和吸收峰之间的关系,开展了具有双共振吸收峰的金属纳米粒子的研究。首先利用FDTD Solutions仿真建模,主要针对金纳米颗粒直径、金纳米棒长径比及分布状态对共振吸收峰进行仿真,得到金纳米球理论直径在50 nm左右,金纳米棒理论长径比在3.5~4.5左右时,吸收峰分别分布在532及785 nm附近,符合多波段激励光拉曼增强条件;对于激励光偏振方向,其沿金纳米棒长轴方向偏振时吸收峰位于785 nm附近,沿金纳米球短轴方向偏振时吸收峰位于532 nm附近。然后采用种子生长法,制备了可用于多种波长激励光的双吸收峰表面增强拉曼散射基底。通过改变硝酸银用量(5,10,20,30和40 μL)、盐酸用量(0.1和0.2 mL)以及其生长时间(15,17,21和23 h)等多种工艺参数来控制金纳米棒含量,得到了同时含有金纳米球及金纳米棒的双吸收共振峰金纳米粒子。最后用该样品作为基底,罗丹明6G(R6G)作为探针分子,分别测试其在532,633和785 nm激励光入射时的SERS表征,对分析物R6G最低检测浓度均达到了10-7 mol·L-1,增强因子达到了~105,满足了多波段SERS检测的需要。     

偏振方向及结构间耦合作用对空心方形银纳米结构表面等离子体共振的影响

空心方形纳米结构能够激发更大面积的增强电场,故其可以作为衬底用于表面增强拉曼散射.应用离散偶极子近似算法研究了空心方形银纳米结构的消光光谱及其近场电场分布与入射光偏振方向之间的关系.研究表明,空心方形银纳米结构的表面等离子体共振峰不随入射光偏振方向的改变而移动,但是其表面增强电场分布却强烈地依赖于入射光的偏振方向.另外,还讨论了空心方形银纳米结构间的耦合作用对其表面等离子体共振模式的影响.结果发现,可以通过调节结构间的距离来改变结构间的耦合作用,同时改变了表面等离子体共振峰的位置.这些结果将为理解闭合纳米 关键词： 空心方形银纳米结构 表面等离子体 偏振 电场耦合     

Factors affecting the spectrum of an electromagnetic light wave on scattering from a semisoft boundary medium

The spectrum of an electromagnetic light wave on scattering from a semisoft boundary medium is discussed within the accuracy of the first-order Born approximation. It is shown that spectral shifts and spectral switches are affected both by the polarization of the incident light wave and by the characters of the scat-tering medium. Moreover, numerical results show that the direction at which the spectral switch occurs is governed by the characters of the scattering medium, whereas the magnitude of the spectral switch is affected by the polarization of the incident light wave.     

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.     

Polarization properties of single metallic nano-spheroid using 3-D boundary element method

The polarization properties of an individual metallic nano-spheroid illuminated by the linearly polarized light are studied based on 3-D boundary element method. The scattering cross sections and the local field enhancements are investigated in detail when the incident lights are with different polarization directions and wavelengths. The numerical results show that the polarization direction of the incident light can strongly influence the scattering spectrum and the enhanced field distribution of the metallic nano-spheroid. The incident light with polarization direction parallel or perpendicular to the major axis can inspire longitudinal or transversal local surface plasmons resonance modes, respectively. The electric field enhancement and distribution around the nano-spheroid can be conveniently tuned by carefully selecting the polarization direction and wavelength of the incident light.     

偏振光在非球形气溶胶中传输特性的Monte Carlo仿真

非球形气溶胶是影响辐射传输的重要因素. 系统给出了矢量辐射传输Monte Carlo模型, 并验证了其准确度; 考虑入射光偏振态, 讨论了不同方向漫射光Stokes矢量对气溶胶形状的敏感性; 分析了气溶胶形状、入射光偏振状态对光波退偏振度、透过率及反射率的影响. 模拟仿真结果表明, 对于不同偏振态的入射光, 不同方向的Stokes矢量对气溶胶形状变化的灵敏程度并不一致, 而在天顶角0°方向区域,Q, U及V分量对形状的灵敏程度普遍不高; 气溶胶形状对反射漫射光退偏程度的影响强于透射漫射光, 入射光偏振态不同, 漫射光退偏程度也存在较大差异. 气溶胶形状对光波整体透过率与反射率影响显著, 且该影响随传播距离增大而增大; 入射光偏振态对透过率与反射率影响相对较小, 与自然光相比, 水平偏振光透过率略偏小, 反射率略偏大, 垂直偏振光反之, 圆偏振光与自然光的模拟结果相当.     

Attenuation,scattering, and depolarization of light by gold nanorods with silver shells

Gold nanoparticles with silver nanoshells are obtained by synthesizing gold nanorods in a growing solution containing cetyltrimethylammonium bromide, subsequent separation in a concentration gradient of glycerol, and reduction of silver nitrate by ascorbic acid under alkaline conditions in the presence of polyvinylpyrrolidone. The formation of silver nanoshells was monitored by the shift of plasmon resonances of extinction and differential light scattering, by the appearance of characteristics peaks of silver in the energy dispersive X-ray (EDX) spectra of samples, by the data of transmission electron microscopy, and by visual changes in the color of colloids. The spectrum of the intensity ratio of the co- and cross-polarized compo- nents of light scattered by gold-silver nanorods is measured for the first time, and it is observed that the maximum is shifted by 80–100 nm compared to previously published spectra of gold nanorods (Khlebtsov et al., J. Phys. Chem. C 112, 12760 (2008)). The extinction and light scattering spectra are calculated by the method of separation of variables using the model of a confocal two-layer spheroid and these calculations are found to agree with spectral measurements. A method for determining the thickness of a silver nanolayer by the spectral shift of an extinction longitudinal resonance is described. The obtained data of optical spectroscopy and transmission electron microscopy and estimations of the mass of the deposited metal show that the aver-age thickness of the silver layer varies from 0.12 to 4 nm as the Ag/Au ratio changes from 2/80 to 90/80 μg/μg.     

Observation of light propagation across a 90 degrees corner in chains of microspheres on a patterned substrate

To demonstrate light-path manipulation in arbitrary shapes we fabricated coupled-resonator optical waveguides (CROWs) having a 90 degrees-corner structure on a lithographically patterned substrate. The spectra of propagation light within the CROWs were directly measured by guide-collection-mode near-field scanning optical microscopy. The spectra revealed that the propagation light through the CROWs has a larger transverse-magnetic polarization mode than a transverse-electric (TE) one. The most plausible cause of the lower intensity in the TE mode is that light leaks out to the Si substrate.