Controlling optical properties of periodic gold nanoparticle arrays by changing the substrate, topologic shapes of nanoparticles, and polarization direction of incident light

The effects of various parameters including thickness and dielectric constants of substrates,shapes of nanoparticles,and polarization direction of incident light,on the extinction spectra of periodic gold nanoparticle arrays are investigated by the full-vectorial three-dimensional (3D) finite difference time domain (FDTD) method.The calculated results show that the substrate affects the extinction spectra by coupling the fields co-excited by the substrate and gold nanoparticles.Extinction spectra are influenced by the shapes of the nanoparticles,but there are no obvious changes in extinction spectra for similar shapes.The polarization direction of incident light has a great influence on the extinction spectra.The implications of these results are discussed.     

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。     

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。     

内嵌圆饼空心方形银纳米结构的光学性质

采用离散偶极子近似方法计算了内嵌圆饼空心方形银纳米结构的消光光谱以及其近场的电场强度分布,并进一步与空心方形纳米结构的消光光谱和表面电场做比较.结果表明,在耦合作用下内嵌圆饼空心方形银纳米结构不仅产生了新的共振模式,而且新的共振模式在传统表面增强拉曼散射的激发波长范围内,进而可以弥补由于实验上运用纳米切片法所制备的空心方形纳米结构尺寸较大导致其共振吸收峰在远红外波长范围的不足.此外,可以通过改变内嵌圆饼空心方形银纳米结构的形貌参数调节其表面等离子体共振峰的共振波长,以满足在表面增强拉曼散射、生物分子或化学分子探测上的应用.     

Broadening of resonances in yttrium nanoparticle optical spectra

The dielectric function of yttrium in the range between 0.2 μm and 2 μm is composed of a harmonic oscillator contribution due to a discrete interband transition and the contribution of free electrons. Hence, it is possible to discuss surface plasmon polaritons as well as other electronic resonances in the optical extinction spectra of yttrium nanoparticles. For the latter, we discuss the broadening of the resonance caused by the aggregation of particles. When particles are lumped into aggregates, the color of the particle system also changes. Aggregation also affects the surface plasmon resonance in yttrium nanoparticles in a way comparable to silver or gold nanoparticle aggregates. Comparison is made with the first experimental results on yttriumnanoparticles, showing that aggregation is the dominant effect for the broad resonance in the measured extinction spectra. Received: 2 July 2001 / Revised version: 10 September 2001 / Published online: 15 October 2001     

Theoretical studies on the near field properties of non-concentric core-shell nanoparticle dimers

The concentric core-shell nanoparticle dimers have “hot spots” with enhanced electric fields in their junctions, which can be used in the surface enhanced Raman spectra analysis. Here the non-concentric core-shell nanoparticle dimers are proposed by introducing a shift between the dielectric core and the metal shell. By using the three dimensional finite difference time domain method, the plasmon resonances and the near field properties of the core-shell nanoparticle dimers affected by the non-concentric shift, dimer separation, excitation wavelength and polarization are analyzed in detail. The results show that the local near fields of the non-concentric core-shell nanoparticle dimers can be much more enhanced than those of the concentric ones. Also the plasmon resonance wavelengths of the dimers can be effectively tuned by the non-concentric shifts between the core and shell. The proposed nanostructures can have great potential in various near field applications.     

The color of finely dispersed nanoparticles

We discuss the dependence of the color of low-concentrated nanoparticle systems on particle size and mass concentration for Ag, Au and TiN nanoparticles, which exhibit a surface plasmon polariton resonance in extinction spectra. Comparison is made with color data obtained for Ag and Au colloidal suspensions. When particles lump into aggregates, the splitting of the surface plasmon resonance into new resonances affects the extinction of light and, hence, the color of the particle assembly. This is demonstrated for aggregated colloidal suspensions of Ag and Au nanoparticles. Finally, for highly concentrated assemblies such as pigment films, we discuss the dependence of the color in diffuse reflectance and transmittance according to Kubelka and Munk (P. Kubelka, F. Munk: Z. Techn. Phys. 12, 593 (1931)), and extend this model by using optical properties of aggregates of spheres. Received: 2 July 2001 / Published online: 10 October 2001     

菱形金属纳米粒子光学性质的研究

金属纳米粒子的光学性质与金属纳米粒子的组成、形状、尺寸及周围的介电常数有关。利用时域有限差分法研究菱形纳米粒子的尺寸与其消光特性关系, 发现粒子尺寸的大小对其消光谱共振峰有较大影响, 随着粒子尺寸的增大, 消光谱共振峰可分裂成两个或多个共振峰。而且在可见光范围内波长大于480 nm的区域, 表面等离子体共振峰是偶极子激发模式; 而在波长小于480 nm的区域, 共振模式则比较复杂, 有偶极子模式, 也有多极子模式。计算表明, 波长为480~ 600 nm区间与波长大于600 nm的区间, 菱形纳米粒子的尺寸对消光光谱的峰值和谱线宽度影响不同。在波长为480~600 nm之间, 短轴为140 nm时, 其消光效率最高。     

Extinction of polarized light in ferrofluids with different magnetic particle concentrations

The magnetic field intensity and nanoparticle concentration dependence of the polarized light extinction in a ferrofluid made of magnetite particles stabilized with technical grade oleic acid dispersed in transformer oil was experimentally investigated. The magnetically induced optical anisotropy, i.e. the dichroism divided by concentration, was found to decrease with increasing sample concentration from 2% to 8%. The magnetically induced change in the optical extinction of light polarized at 54.74° with respect to the magnetic field direction was found to be positive for the less concentrated sample (2%) and negative for the samples with 4% and 8% magnetic nanoparticle concentrations, the more negative the higher the concentration and field intensity. Based on the theoretically proven fact [11] that the particle orientation mechanism has no effect on the extinction of light polarized at 54.74° with respect to the field direction, we analyzed the experimental findings in the frames of the agglomeration and long-range pair correlations theories for the magnetically induced optical anisotropy in ferrofluids. We developed a theoretical model in the approximation of single scattering for the optical extinction coefficient of a ferrofluid with magnetically induced particle agglomeration. The model predicts the existence of a polarization independent component of the optical extinction coefficient that is experimentally measurable at 54.74° polarization angle. The change in the optical extinction of light polarized at 54.74° is positive if only the formation of straight n-particle chains is considered and may become negative in the hypothesis that the longer chains degenerate to more isotropic structures (polymer-like coils, globules or bundles of chains). The model for the influence on the light absorption of the long-range pair correlations, published elsewhere, predicts that the change in the optical extinction of light polarized at 54.74° is always negative, the more negative the higher the magnetic field intensity and particle concentration.     

Spectroscopy of Plasmon-Excitons in Semiconductor-Metal Nanostructures

The results of the theory considering mixed plasmon-excitonic modes and their spectroscopy are presented. The plasmon-excitons are formed owing to strong Coulomb coupling between quasi-two-dimensional excitons of a quantum well and dipole plasmons of nanoparticles. The effective polarizability associated with a nanoparticle is calculated in a self-consistent approximation taking into account the local field determined by in-layer dipole plasmons and their image charges due to the excitonic polarization of a near quantum well. The spectra of elastic scattering and specular reflection of light are investigated in cases of a single silver nanoparticle and a monolayer of such particles situated in close proximity to a quantum well GaAs/AlGaAs. The optical spectra show a two-peak structure with a deep and narrow dip in the resonant range of plasmon-excitons. Propagation of plasmon-excitonic polaritons is discussed for periodic superlattices whose unit cell consists of a quantum well and a layer of metal nanoparticles. The superradiance regime originating in the Bragg diffraction of plasmon-excitonic polaritons by the superlattice is investigated. It is shown that the broad spectrum of plasmonic reflection depending on the number of unit cells in a superlattice also has a narrow dip at the exciton frequency.

     

Synthesis and photo physical properties of Au @ Ag (core @ shell) nanoparticles disperse in poly vinyl alcohol matrix

Synthesis of core @ shell (Au @ Ag) nanoparticle with varying silver composition has been carried out in aqueous poly vinyl alcohol (PVA) matrix. Core gold nanoparticle (~15 nm) has been synthesized through seed-mediated growth process. Synthesis of silver shell with increasing thickness (~1–5 nm) has been done by reducing Ag⁺ over the gold sol in the presence of mild reducing ascorbic acid. Characterization of Au @ Ag nanoparticles has been done by UV–Vis, High resolution transmission electron microscope (HRTEM) and energy dispersive X-ray (EDX) spectroscopic study. The blue shift of surface plasmon resonance (SPR) band with increasing mole fraction of silver has been interpreted due to dampening of core, i.e. Au SPR by Ag. The dependence of nonlinear optical response of spherical core @ shell nanoparticles has been investigated as a function of relative composition of each metal. Simulation of SPR extinction spectra based on quasi-static theory is done. A comparison of our experimental and the simulated extinction spectra using quasi-static theory of nanoshell suggests that our synthesized bimetallic particles have core @ shell structure rather than bimetallic alloy particles.     

非对称银纳米双环表面等离激元光谱特性

贵金属纳米材料在入射光激发下能够产生表面等离激元,即金属表面自由电子产生集体振荡。当其振荡频率与入射光频率相同时,发生表面等离激元共振,形成一种特殊的电磁场模式和光谱特性。利用该电磁场模式和光谱特性, 能够调节金属纳米材料的光谱学行为,例如通过改变金属纳米结构的大小、形状以及周围介质介电常数等参数, 在微纳尺度上实现光谱学信号的有效调控。目前,除了具有一定对称性的贵金属纳米材料被大量研究和应用外,非对称纳米结构的表面等离激元光谱特性也受到广泛关注。研究表明,在可见-近红外波段光谱范围内设计表面等离激元光电传感器件的关键问题在于,如何有效地调节其消光谱的共振波长、半峰宽以及峰值强度等主要特征参数。提出一种基于银纳米双环组成的非对称结构,利用时域有限差分方法,在可见-近红外波段内,通过分别改变银纳米双环的尺寸、间距及入射光偏振方向等参数,计算了该纳米结构在不同条件下的消光谱。结果表明,在0.4～3 μm的消光谱内,入射光能够激发产生两个独立的表面等离激元共振峰。通过研究峰值波长处的电场分布图发现,上述共振峰分别对应两种不同的电磁场模式。结果还表明,消光谱内两个独立的共振峰可以通过改变该双环结构的不同参数,被分别地进行调节。其中,可以通过改变该双环结构的半径来有效调节短波长峰的共振波长和半峰宽,同时保持长波长峰的共振波长和半峰宽基本不变。此外,通过改变两环间距或入射光偏振方向,可以分别以不同趋势来调节两个共振峰的峰值强度。在提出的非对称银纳米双环的消光谱中,获得了能够被分别调节的两个表面等离激元共振峰,研究结果能够为可见-近红外波段内基于银纳米材料光电传感器件的开发设计提供理论基础。     

Design and fabrication of a three-dimensional polymer optical waveguide polarization splitter

We present a design and fabrication of a three-dimensional polymer optical waveguide polarization splitter by taking into consideration of the induced birefringence effect of the polymer. We show that it is not possible to couple TM light from one waveguide to the other but evanescent coupling for TE light is possible. Hence the polarization splitter can be designed by considering TE mode coupling alone. This has an advantage of short interaction length of the device. Based on this consideration, we fabricated a polarization splitter with a TE extinction ratio of 15 dB and TM extinction ratio of 21 dB.     

Controlling the interaction between light and gold nanoparticles: selective suppression of extinction

The interaction of visible light with the particle-plasmon resonance of metallic nanoparticles can be controlled by geometrical arrangement of nanoparticle arrays. These arrays are placed on a substrate that supports guided modes in the wavelength range of the particle plasmon. Coupling of this particle-plasmon resonance to the directly incident light and to the waveguide modes results in almost complete suppression of light extinction within narrow spectral bands due to destructive interference. Variation of the structure parameters allows continuous tuning of these high-transmission bands across the particle-plasmon resonance.     

金属粒子阵列共振的偏振特性

当金属纳米粒子形成规则分布且阵列周期与单粒子的共振波长近似匹配时, 会形成一种特殊的阵列共振, 这种共振比单粒子的局域表面等离子体共振具有更窄的共振线宽和更高的共振强度. 基于修正的长波近似方法, 讨论了矩形阵列的消光截面与阵列因子和单粒子的极化率之间的关系; 并详细研究了在不同偏振的入射光照射下, 阵列因子随着电偶极子方向的改变而产生的变化, 以及这一效应对阵列共振和消光截面所产生的影响. 结果表明, 大型的方阵是偏振无关的; 在矩形阵列中, 沿着阵列两个轴向的相邻粒子之间的耦合形成了阵列因子的两个极值, 并且分别对应了散射截面的最小值.     

二氧化钒纳米点阵红外光学特性研究

针对二氧化钒纳米点阵从半导体到金属的可逆相变,考虑到点阵中各个点之间散射光的交互作用,基于VO2在不同温度和波长下的折射率和消光系数,以及小颗粒的吸收和散射特性,建立了VO2纳米颗粒的数学模型,研究了VO2纳米颗粒的相变光学特性.结果表明,随着波长变化,吸收截面相对散射截面占主导,金属相在980 nm附近出现吸收峰值|随着温度变化,可见光区域的消光系数变化较小,而红外区域较大,其中在近红外区域的消光系数变化最大.在纳米点阵中,消光截面随着颗粒间距变化,当颗粒间距增大时,消光峰值出现红移,且峰值大小也会随之增大|当间距超过一定数值后,峰值反而会逐渐减小.采用多孔氧化铝掩模的方法,通过磁控反应溅射制备VO2纳米点阵,测试结果表明其透过率比薄膜的透过率高.     

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.     

Influence of surface properties on the structure of granular silver films and excitation of localized plasmons

Granular silver films deposited on a thin insulating film of amorphous hydrogenated carbon (a-C:H) and transparent conducting electrode (polycrystalline indium tin oxide (ITO) layer) have been investigated by spectroscopy and microscopy methods. The extinction spectra of silver films on the surface of these materials are found to be significantly different. An annealing of silver films causes a blue shift of the peak of plasmon resonance band in the spectrum of silver nanoparticles: by 16 nm on the a-C:H surface and by 94 nm on the ITO surface. Silver films on the surface of a-C:H films are characterized by a narrower band in the extinction spectrum, which is peaked at 446 nm. The changes observed in the optical density of Ag films are related to the change in size and area of nanoparticles. The results of spectral studies of Ag films are in agreement with the data on the nanostructure obtained by scanning electron microscopy and statistical image processing. The spectra of granular silver films are shown to correlate well with the nanoparticle distribution function over the film area.     

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.     

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。