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。     

化合物/银核壳结构纳米复合颗粒的消光性能研究

利用离散偶极近似(Discrete Dipole Approximation,DDA)方法系统研究ITO/Ag、CdS/Ag、和ZnS/Ag纳米核壳结构的消光特性。研究结果表明,银纳米核壳的表面等离子体共振吸收峰位置随周围介质折射率和颗粒核壳比的增大逐渐红移;且当核壳比相同时,较大球径纳米核壳的消光峰位置处在长波长处。研究亦发现,银壳与化合物之间存在显著的电子迁移现象,相同球径的银表面电子密度降低程度由高到低为CdS/Ag、ZnS/Ag、ITO/Ag。     

Au@SiO2核-壳层单晶八面体纳米棒光吸收性质的研究

包覆材料改变了单一材料的力学、光学性质。利用离散偶极近似(Discrete Dipole Approximation,简称DDA)的方法,系统研究二氧化硅壳层、尺寸及形貌等因素对Au@SiO_2核-壳层单晶八面体纳米棒光学吸收谱峰值、峰位及其近场分布的影响。研究表明SiO_2壳层包覆的Au纳米棒的光学吸收谱同样表现为横向和纵向吸收峰。随着SiO_2壳层厚度增加,Au@SiO_2核-壳层单晶八面体纳米棒横向和纵向吸收缝的强度明显减弱,横向吸收峰的位置发生微小的蓝移,而纵向吸收峰位发生明显的红移。SiO_2壳层在提高纳米棒硬度的同时,改变光学吸收峰的峰值和峰位,削弱了Au核表面等离子体共振强度(Surface Plasma Resonance-SPR)。     

金纳米环结构的光学性质研究

采用离散偶极子近似方法(DDA)研究了两种不同形状的金纳米环结构的消光光谱及其近电场分布, 研究了等离子体消光峰的红移、蓝移现象及消光系数与结构参数之间的关系, 并与盘状的金纳米结构进行了比较. 在等离子体共振峰波长入射时, 金纳米环结构比金纳米盘结构产生更大的局域增强电场分布, 横截面为圆形的金纳米环结构比横截面为矩形的结构具有更大的局域增强电场分布, 更适合作为表面增强拉曼散射的衬底. 关键词： 离散偶极子近似 金纳米环 金纳米盘 光学性质     

基于局域表面等离子体共振效应的聚合物波导传感器特性研究

以SU-8光刻胶作为波导芯层材料,设计了基于金纳米粒子的局域表面等离子体共振(LSPR)波导传感器。根据Mie理论,建立了金纳米粒子的消光模型,理论分析了纳米粒子半径、待测物折射率等因素对局域表面等离子体共振曲线的影响。分析表明:当待测液体折射率增大时,LSPR共振峰的位置发生红移。随着金纳米粒子半径的逐渐增大,传感器灵敏度增加。共振吸收峰逐渐由单峰变为双峰,其中一个峰位于520 nm波长附近,主要由表面等离子体吸收造成;另一个峰随金纳米粒子半径的增大而逐渐红移,主要由表面等离子体散射造成。     

Ag-AAO纳米有序阵列复合结构等离子共振吸收特性研究

研究了Ag-AAO纳米有序阵列复合结构的等离子共振吸收特性。结果显示,Ag表面等离子共振吸收峰位于λ=352-377nm范围内,且可通过控制Ag纳米粒子的长径比使其吸收特性发生改变。若长径比增加,吸收峰位蓝移,强度增大,峰形变锐;反之,若长径比减少,吸收峰位红移,强度减弱,峰形逐渐宽化;运用麦克斯韦-加尼特（M-G）理论模拟的计算结果与实验规律基本相符,并较好地阐释了Ag表面等离子共振吸收峰的频移与其纳米粒子长径比之间的一些依赖关系。     

金纳米粒子光学性质中的尺寸和形状效应

纳米尺度的金属及半导体呈现出特殊的光学、电学及磁学性质,采用近年发展起来的离散偶极近似(DDA)的方法,我们分析了金纳米粒子的尺寸及形状对其光学性质的影响。粒子周围介质的影响在文中亦作了分析。计算结果显示,金纳米粒子的等离子体吸收带同时受到粒子尺寸和形状的影响,但来自形状的影响更为明显。与米氏理论及扩展的甘氏理论相比较,DDA方法在粒子尺寸不再远小于入射光波长的时候更准确,并能应用于任何形状的纳米粒子。理论计算与实验结果能较好的吻合。     

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。     

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。     

外围介质介电常数对金纳米棒光学性质影响的数值模拟

采用电化学方法制备出悬浮胶体金纳米棒。在室温下测得其紫外-可见吸收光谱和荧光发射光谱。结合准静电场理论与散射理论对金纳米棒的光学特性进行了数值模拟。计算结果表明,由于金纳米棒形状的各向异性,吸收截面与散射截面均出现两个共振峰,分别对应于横截方向与长轴方向的表面等离子共振。对于几何形状一定的金纳米棒,在外围介质介电常数从1.5增加到2.5的过程中,两个共振吸收峰均增强并非线性红移。然而对于散射光谱,短波方向的共振峰线性红移,强度变化微弱;长波方向的共振峰减弱并非线性红移。     

Effect of Aspect Ratio Distribution on Localized Surface Plasmon Resonance Extinction Spectrum of Gold Nanorods

Gold nanorods with different aspect ratios are prepared in micells using a seeded growth method. Their extinction spectra are observed with an UV-visible spectrophotometer and analysed theoretically. It is known that there are two plasmon resonance peaks for gold nanorod corresponding to transverse and longitudinal plasmon resonance respectively. Moreover, the longitudinal plasmon resonance peak shifts to long wavelength when we increase the aspect ratio determined from TEM. Especially, we model the extinction spectrum using Gans' theory and compare it with our experimental result. Considering the aspect radios distribution of gold nanorods, it is found that longitudinal plasmon resonance peak will be wider than the nanorods with single aspect ratio, which is consistent with our experimental result. In addition, the effect of dielectric constant of surrounding medium is considered.     

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.     

Shape and size dependence of the surface plasmon resonance of gold nanoparticles studied by Photoacoustic technique

We report on the optical absorption properties of as prepared gold naoparticles of different shapes and sizes measured by photoacoustic (PA) method. The gold nanoparticles of two different shapes (dots, rods) have been prepared using the seed mediated growth method. The shape and the size of these different nanoparticles were determined by STM measurements. PA spectra show the splitting of the surface plasmon resonance (SPR) into two modes (transverse and longitudinal) in case of gold nanorods. The increase in the aspect ratio of the nanorods leads to clear redshifts of the longitudinal SPR. These shifts were used to determine the dielectric constant of the surrounding medium and its variation with the aspect ratios.     

Preparation of monodisperse bimetallic nanorods with gold nanorod core and silver shell and their plasmonic property and SERS efficiency

In this study, monodisperse bimetallic nanorods with gold (Au) nanorod core and silver (Ag) shell (Au@AgNRs) were synthesized through seed‐mediated growth process by reduction of AgNO₃ using Au nanorods with narrow size and shape distribution as seeds. With increasing the used amount of AgNO₃, the Ag shell thickness of their lateral facets is raised faster than that of their two tips, leading to a decrease of their aspect ratios. Four plasmon bands are observable on the extinction spectra of Au@AgNRs, which are attributed to the longitudinal dipolar plasmon mode, transverse dipolar plasmon mode, and octupolar plasmon mode of the core‐shell structured bimetallic nanorods, respectively. As their Ag shell thickness increases, their longitudinal plasmon band blue‐shifts notably with the transverse plasmon band blue‐shifting and the two octupolar plasmon bands red‐shifting slightly, due to the decrease of their aspect ratios and enhancement of Ag plasmon resonance contribution. When used as surface‐enhanced Raman scattering (SERS) substrate for probing minute amounts of 4‐mercaptobenzoic acid in aqueous solution, Au@AgNRs have much stronger SERS activity than Au nanorods, and the obtained Raman signals are highly reproducible arising from their excellent monodispersity. Their SERS activity is remarkably increased with their Ag shell thickness thanks to the enhancing surface electric field and the chemical enhancement associated with electronic ligand effect. Copyright © 2014 John Wiley & Sons, Ltd.     

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     

Seedless synthesis of gold nanorods with longitudinal surface plasmon resonance wavelength of 1200 nm

Gold nanorods with the longitudinal plasmonic resonance peak position up to 1200?nm are prepared using an improved seedless synthetic technique. In this method, dopamine is employed as the weak reducer, whereas cetyltrimethylammonium bromide and sodium oleate are used as the binary surfactant mixture. Gold nanorods produced at various amounts of silver nitrate and hydrochloric acid were characterized by visible-near-infrared spectroscopy and scanning electron microscopy. Results show that the sizes, length-to-width aspect ratios, and the corresponding longitudinal surface plasmon resonance peaks of the synthesized gold nanorods can be tuned by altering the silver nitrate and hydrochloric acid amounts. The present method provides a new procedure for fabrication of gold nanorods with a broad range of plasmonic resonance peaks, which has a great potential for applications such as photothermal therapy and sensing.     

金纳米棒状微粒的胶囊模型及吸收光谱

提出了金纳米棒状微粒的胶囊模型,用Waterman发展的T矩阵方法计算了金纳米棒状微粒的吸收光谱.计算谱和实验谱基本符合,520 nm左右处的吸收峰对应于金纳米棒的横向表面等离体子共振（横模）,长波长处的吸收峰对应于金纳米棒的纵向表面等离体子共振（纵模）.随着金纳米棒纵横比的增加,纵模吸收峰表现出显著的红移,横模吸收峰则微弱地蓝移.此外,计算结果表明,金纳米棒状微粒外部介质的介电常数必须随着金纳米棒纵横比的增大非线性地减小.     

Synthesis and Optical Properties of Anisotropic Metal Nanoparticles

In this paper we overview our recent studies of anisotropic noble metal (e.g. gold and silver) nanoparticles, in which a combination of theory and experiment has been used to elucidate the extinction spectra of the particles, as well as information related to their surface enhanced Raman spectroscopy. We used wet-chemical methods to generate several structurally well-defined nanostructures other than solid spheres, including silver nanodisks and triangular nanoprisms, and gold nanoshells and multipods. When solid spheres are transformed into one of these shapes, the surface plasmon resonances in these particles are strongly affected, typically red-shifting and even splitting into distinctive dipole and quadrupole plasmon modes. In parallel, we have developed computational electrodynamics methods based on the discrete dipole approximation (DDA) method to determine the origins of these intriguing optical features. This has resulted in considerable insight concerning the variation of plasmon wavelength with nanoparticle size, shape and dielectric environment, as well as the use of these particles for optical sensing applications.