有序金纳米颗粒阵列的制备及光吸收特性研究

采用纳米球刻蚀技术中漂移法在玻璃基片上制备较大 面积不同直径的聚苯乙烯小球掩模板, 采用磁控溅射技术在掩模板上沉积不同厚度的金薄膜, 去除聚苯乙烯小球后, 通过扫描电子显微镜观察到周期排列的三角状金纳米颗粒点阵. 通过紫外-可见分光光度计测试所制备样品的光吸收特性, 发现表面等离子体共振峰随粒径增大发生红移, 随金纳米颗粒高度增加发生蓝移. 基于Mie理论, 利用Matlab软件编程对不同粒径的金阵列光吸收特性进行理论模拟, 并与实验结果进行对比. 关键词： 纳米球刻蚀 金纳米颗粒阵列 表面等离子体共振     

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     

金属纳米颗粒LSPR光纤生物传感DDA方法研究

研究了金属纳米颗粒的局部表面等离子体共振(LSPR)行为,并讨论了其在光纤生物传感领域的应用.采用离散偶极近似(DDA)的方法,从理论上分析了金属纳米颗粒的尺寸、形状对其传感灵敏度的影响.计算结果显示,金属纳米颗粒的等离子共振吸收峰同时受到颗粒尺寸和形状的影响,但形状对其传感灵敏度的影响最为明显,计算结果与实验数据能较好地吻合.     

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。     

Spectral degeneracy breaking of the plasmon resonance of single metal nanoparticles by nanoscale near-field photopolymerization

We report on controlled nanoscale photopolymerization triggered by enhanced near fields of silver nanoparticles excited close to their dipolar plasmon resonance. By anisotropic polymerization, symmetry of the refractive index of the surrounding medium was broken: C infinity v symmetry turned to C2v symmetry. This allowed for spectral degeneracy breaking in particles plasmon resonance whose apparent peak became continuously tunable with the incident polarization. From the spectral peak, we deduced the refractive-index ellipsoid fabricated around the particles. In addition to this control of optical properties of metal nanoparticles, this method opens new routes for nanoscale photochemistry and provides a new way of quantification of the magnitude of near fields of localized surface plasmons.     

Lithography-free fabrication of large-area plasmonic nanostructures using colloidal gold nanoparticles

We report simple and efficient fabrication of large-area gold nanostructures using solution-processible gold nanoparticles, where lithography and vacuum evaporation techniques are not involved in the fabrication processes. These gold nanoisland structures exhibit strong particle plasmon resonance that is characterized by optical extinction spectroscopy in the visible spectral range. The tunability of the optical response is realized by controlling the annealing temperature and by changing the concentration of the colloidal solutions of gold nanoparticles. This enables a low-cost route for exploiting new photonic devices, biosensors, and optoelectronic devices with localized field-enhancement.     

Rapid tarnishing of silver nanoparticles in ambient laboratory air

Silver has useful surface-plasmon-resonance properties for many potential applications. However, chemical activity in silver nanoparticles exposed to laboratory air can make interpretation of optical scattering and extinction spectra problematic. We have measured the shift of the plasmon polariton wavelength of arrays of silver nanoparticles with increasing exposure to ambient laboratory air. The resonance peak wavelength shifts 65 nm in 36 h (1.8 nm/h). We show by scanning Auger spectroscopy that the shift is due to contamination from sulfur, most likely chemisorbed on the surface. The rate of corrosion product growth on the nanoparticles is estimated to be 3 nm per day, 7.5 times higher than that of bulk Ag under the same conditions.     

Optical Properties of Plasmon Resonances with Ag/SiO2/Ag Multi-Layer Composite Nanoparticles

Optical properties of plasmon resonance with Ag/SiO2/Ag multi-layer nanoparticles are studied by numerical simulation based on Green＇s function theory. The results show that compared with single-layer Ag nanoparticles, the multi-layer nanoparticles exhibit several distinctive optical properties, e.g. with increasing the numbers of the multi-layer nanoparticles, the scattering efficiency red shiRs, and the intensity of scattering enhances accordingly. It is interesting to find out that slicing an Ag-layer into multi-layers leads to stronger scattering intensity and more ＂hot spots＂ or regions of stronger field enhancement. This property of plasmon resonance of surface Raman scattering has greatly broadened the application scope of Raman spectroscopy. The study of metal surface plasmon resonance characteristics is critical to the further understanding of surface enhanced Raman scattering as well as its applications.     

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     

基于含时密度泛函理论的表面等离激元研究进展

纳米粒子的局域表面等离激元(LSP)由于其新颖的光学特性成为目前国内外研究的热点之一. 本文利用含时密度泛函理论(TDDFT)对金属团簇及石墨烯纳米结构中的等离激元激发及调制的物理本质进行了研究. 和宏观大小的材料相比, 由于纳米结构的尺寸和量子受限效应, 纳米结构的等离激元具有一些不同的特征. 在低能共振区, 光谱线发生展宽, 并且发生劈裂. 由于纳米单体间的电磁耦合作用, 使聚合的纳米结构表现出了与单体不同的光学性质. 这些结果为等离激元的调控提供了坚实的理论指导.     

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.     

Electromagnetic coupling between a metal nanoparticle grating and a metallic surface

The electromagnetic coupling between a two-dimensional grating of resonant gold nanoparticles and a gold metallic film is investigated. We report on the observation of multipeaks in the extinction spectra attributed to resonant modes of the hybrid system, resulting from the coupling between the localized plasmon of the nanoparticles with the underlying surface plasmon mode. Simulations based on the Fourier modal method give good agreement with the experimental measurements and allow for the identification of the respective contributions.     

Light transmission properties of double-overlapped annular apertures

We investigate the light transmission properties of double-overlapped annular apertures in a silver film with the three-dimensional finite-difference time-domain method. It has been found that the transmission peaks are attributed to the localized surface plasmon resonance (LSPR) of nanocavities and the surface plasmon polaritons (SPPs) of the nanoparticles. The peaks of the LSPR are blueshifted when the overlapping distance is increased. Moreover, a Fano-type resonance appears in the transmitted spectral response with an appropriate overlapping distance, which is elucidated as the hybridization results of the SPPs of the nanoparticles. The number and position of the Fano resonance can be tuned through varying the overlapping distance and other geometric parameters.     

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.     

Diagnostics of aqueous colloids of noble metals by extinction modeling based on mie theory

Two-factor dependences of the maximum and half-width of a surface plasmon resonance band on both the average diameter of nanoparticles and the scatter in their particle-size distributions were defined for colloidal silver and gold aqueous solutions based on modeling the extinction effectiveness factor by Mie theory. The obtained three-dimensional surfaces determined the shape of calibration curves used to define the average particle diameters and the scatter in their particle-size distributions from measurements of the maximum and half-width of the surface plasmon resonance band in spectra of the silver and gold colloidal solutions. The calibration curves were correlated with experimental samples of aqueous ultradispersed media containing silver and gold nanoparticles.     

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     

金纳米颗粒的有序制备及其光学特性

采用纳米球蚀刻技术在石英衬底上制备了不同高度的金纳米颗粒阵列.通过扫描电子显微镜对其表面形貌进行了观测,表明金纳米颗粒为有序分布的三棱柱结构.通过红外—紫外吸收光谱仪在190—900nm波长范围内对其光吸收特性进行了测量, 并成功观测到了金纳米颗粒表面等离子体振荡效应引起的光吸收峰,结果表明随着金纳米颗粒高度的增加,其吸收峰的位置向短波方向移动(蓝移).同时对金纳米颗粒的光吸收特性进行了基于离散偶极子近似的理论计算,并与实验结果进行了比较. 关键词： 纳米球蚀刻技术 金纳米颗粒 离散偶极子近似     

Plasmonic nanoparticles and their analytical applications: A review

Plasmonic nanoparticles (NPs) have been reviewed herein for their fascinating optical properties in a wide spectral range and for their various applications. The surface plasmon resonance (SPR) bands of metal NPs can be tuned from visible to near infrared region by varying the shape of the metal NPs. As a result, the tuning of the SPR band over a spectral range is possible by making plasmonic NPs of different shapes. This review emphasizes fundamental studies of plasmonic NPs and nanocomposites with well-defined and controlled shapes that have several analytical applications such as molecular detection and determination in different fields. This review describes how oxidative etching and kinetic control can be utilized to manipulate the shape and optical properties of NPs. This review also describes the specific examples of the sensing applications of the localized surface plasmon resonance studies in which the researchers use both wavelength shift and surface-enhanced Raman scattering sensing to detect the molecules of chemical and biological relevance. The review ends with a perspective of the field, identifying the main challenges to be overcome and suggesting areas where the most promising developments are likely to happen in future.     

银纳米棒光学性质的离散偶极近似计算

利用离散偶极近似 (Discretedipoleapproximation ,简称DDA)的方法 ,从理论上对粒子的形状、尺寸及周围介质等因素对银纳米粒子 ,特别是银纳米棒的光学性质的影响进行了较系统的研究 .计算表明 ,置于空气中的棒状银纳米粒子的光学性质与其形状密切相关 ,纵向表面等离子体共振吸收峰的位置随纳米棒长径比的增加呈现线性红移关系 .给出了空气中银纳米棒纵向表面等离子体共振吸收峰的位置随长径比变化的DDA拟合公式 .如果将金属纳米粒子置于折射率更高的介电环境中 ,其纵向等离子体共振吸收峰的位置进一步呈现线性红移关系 .合成的银纳米粒子的TEM图像及相关的UV VIS消光光谱显示DDA计算结果与实验值相当一致 .DDA算法与Mie′s理论在计算球状银纳米粒子的消光系数时给出很接近的结果 ,这表明用DDA的方法来分析银的光学性质是准确可靠的 ;而DDA算法对银纳米棒消光特性的成功拟合则表明 ,该算法相对Gans′理论而言 ,在研究纳米粒子的光学性质时具有更广的适用性及更高的准确性 .     

Surface plasmon characteristics of tunable photoluminescence in single gold nanorods

Light emission resulting from two-photon excited gold nanoparticles has been proposed to originate from the radiative decay of surface plasmon resonances. In this vein, we investigated luminescence from individual gold nanorods and found that their emission characteristics closely resemble surface plasmon behavior. In particular, we observed spectral similarities between the scattering spectra of individual nanorods and their photoluminescence emission. We also measured a blueshift of the photoluminescence peak wavelength with decreasing aspect ratio of the nanorods as well as an optically tunable shape-dependent spectrum of the photoluminescence. The emission yield of single nanorods strongly depends on the orientation of the incident polarization consistent with the properties of surface plasmons.