Plasmon hybridization in nanorod dimers

Using the plasmon hybridization method we investigate the plasmon modes of nanorod dimers in axial and parallel orientations. We show that the plasmon modes of the system can be viewed as bonding and anti-bonding modes resulting from the hybridization of the plasmon modes of the individual nanorods. The dimer plasmon modes are found to depend sensitively on separation between the nanorods and on their relative spatial orientation. The calculated optical properties agree quantitatively with results from the numerical finite-difference time-domain method. The electric field enhancements are found to depend strongly on aspect ratio defined as the ratio of the major and minor radii, and on the relative orientation of the nanorods. For a nanorod dimer of fixed overall length, the maximum field enhancements are lower than those induced in a solid sphere dimer.     

Fano resonances in dipole-quadrupole plasmon coupling nanorod dimers

We theoretically investigate the plasmon coupling in metallic nanorod dimers. A pronounced dip is found in the extinction spectrum due to plasmonic Fano resonance, which is induced by destructive interference between the bright dipole plasmon of a short nanorod and the dark quadrupole plasmon of a long nanorod. This Fano interference can also be explained as the coupling between the bright and dark modes both supported by the whole dimer. The Fano resonance can be tuned by adjusting the spatial or spectral separation between two nanorods in the dimer.     

金纳米棒三聚体中的等离激元诱导透明

基于金纳米棒构成的三聚体微元结构模型,详细地研究了等离激元诱导透明(plasmon induced transparency,PIT)现象产生的物理过程.研究发现,三聚体的吸收谱线随着其耦合距离以及尺寸的变化,竖直金纳米棒所对应的偶极明模在平行双长条金纳米棒对应的暗模作用下会产生分裂.依据这一结果提出了一个新的物理解释,PIT现象的产生主要来自于竖直金纳米棒中偶极振荡的模式分裂后的相干叠加.同时,考虑到两个振子之间的耦合会伴随着一定的相位关联性,进而引入了耦合相位因子修正了洛伦兹振子耦合模型,解析地研究了耦合相位因子对吸收谱的调控作用和分裂明模之间的相干叠加效应对PIT效应的影响.这为在纳米尺寸范围设计人造原子、光开关、慢光效应等方面的应用提供了理论参考.     

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.     

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 .     

Deviating from the nanorod shape: Shape-dependent plasmonic properties of silver nanorice and nanocarrot structures

Noble metallic nanostructures exhibit special optical properties resulting from excitation of surface plasmons. Among the various metallic nanostructures, nanorods have attracted particular attention because of their unique and intriguing shape-dependent plasmonic properties. Nanorods can support transverse and longitudinal plasmon modes, the latter ones depending strongly on the aspect ratio of the nanorod. These modes can be routinely tuned from the visible to the near-infrared spectral regions. Although nanorods have been investigated extensively, there are few studies devoted to nanostructures deviating from the nanorod shape. This review provides an overview of recent progress in the development of two kinds of novel quasi-one-dimensional silver nanostructures, nanorice and nanocarrot, including their syntheses, crystalline characterizations, plasmonic property analyses, and performance in plasmonic sensing applications.     

二维方形量子点体系等离激元的量子化

量子点体系等离激元的研究是光电子学领域的热点.为进一步加深和完善对等离激元的量子效应的认识,本文利用紧束缚近似和线性响应理论研究了二维方形量子点体系对外场的集体响应.结果表明,当外场频率等于等离激元的频率时,量子点体系会有强烈的电荷振荡,并伴随着能量的极大吸收和近场的增强.在量子点中,等离子体存在分立的元激发.等离子体元激发的个数将随着量子点尺寸和电子个数的增加而增加.随量子点尺寸的增加,分立的等离激元将逐步呈现准连续的特性,即过渡为经典连续的等离激元,其频谱曲线演化为经典的色散曲线.结果还表明:随量子点尺寸的增加,等离激元的频率会红移,等离激元的激发强度会增大;随量子点中电子数的增加,等离激元的频率会蓝移,等离激元的激发强度会增大.     

Site‐specific deposition of Ag nanoparticles on ZnO nanorod arrays via galvanic reduction and their SERS applications

A controllable heterostructure consisting of ZnO nanorod arrays with attached Ag nanoparticles at only one end has been synthesized via a facile and convenient galvanic reduction method. Scanning electron microscopic images of these nanostructures showed good selectivity of Ag deposition on the tip of ZnO nanorod arrays. The formation of these regular Ag ZnO heterogeneous nanorod arrays can be explained by a localization of the electrons at the ends of the ZnO nanorods after the electron transfer step. By tuning the reaction time and the concentration of silver nitrate, the density of Ag nanoparticles on the tip of ZnO nanorods can be well controlled. Owing to the introduction of Ag nanoparticles with different densities, the resulting Ag ZnO heterogeneous nanorod arrays have been proved to be a versatile substrate for surface‐enhanced Raman scattering not only for common organic molecules but also for label‐free protein detection. Copyright © 2009 John Wiley & Sons, Ltd.     

Amplification of raman scattering by localized plasmons in silver nanoparticles on the surface of zinc oxide nanorods

The magnetron sputtering of Ag nanoparticles onto ZnO nanorod arrays is studied. The lateral faces of the nanorods are coated with nanoparticles at a much lower density as compared to the flat faces at comparable sputtering times. The silver density is high on the edges of the lateral faces of the nanorods. The plasmon absorption in the synthesized arrays of nanorods coated with individual Ag nanoparticles is maximal at 450?C500 nm. The appearance of local plasmon excitations increases the intensity of the multiphonon processes with the participation of ZnO polar modes in Raman spectra. The cross section of resonance Raman scattering for A ₁(LO) phonon overtones increases with the equivalent Ag film thickness.     

Energy loss and plasmon excitation during electron emission in the proximity of a solid surface

We study the interaction with bulk and surface modes of electrons emitted in the proximity of a solid surface. We analyze the modifications in the energy loss, and in bulk and surface plasmon excitations, taking into account the effects due to the sudden creation of the electron and residual atomic hole, and the finite distance to the surface. The process is described using the dielectric function formulation and the specular reflection model. We derive expressions for the electrostatic potential in the medium and in vacuum, which include all the terms due to bulk and surface modes. The effect of each term in the energy loss rate and in the average number of plasmon excitations is discussed. The results illustrate in detail the different spatial dependences of the electron and ion interactions with the bulk and surface perturbations, through the relevant range of distances for studies of electron emission in the proximity of solid surfaces.     

Silver nanorods used to promote SERS as a quantitative analytical tool

We have fabricated silver nanorod arrays by electrodepositing the nanorods evenly in the shallow pores of porous anodic aluminum oxide (AAO) templates. The diameter and length were 28 and 44 nm, respectively. The maxima of the transverse and longitudinal modes of the surface plasmon were near 417 and 511 nm, respectively. A good surface‐enhanced Raman scattering (SERS) spectrum was observed by excitation with the 514.5‐nm laser line. The SERS intensity increased almost linearly upon malachite green isothiocyanate adsorption on the tips of the silver nanorods as the concentration of the mother solutions increased. Our results show that silver nanorods fabricated on AAO templates could be used as an SERS substrate for quantitative analyses. Copyright © 2009 John Wiley & Sons, Ltd.     

金纳米棒复合体的消光特性

金属纳米颗粒局域表面等离激元共振时能够产生消光和近场增强效应已经成为国内外研究的热点. 应用时域有限差分法对L形纳米棒与普通纳米棒构成的金纳米棒复合体的消光光谱及其近场增强和电流矢量密度分布进行了研究. 计算结果表明, 普通纳米棒和L形纳米棒二聚体的光谱响应与纳米棒间的间距有关, 而金纳米棒复合体的消光光谱可通过调整L形纳米棒与普通纳米棒间的间距、L形纳米棒的臂长度以及普通纳米棒的长度进行调谐. 此外金纳米棒复合体可以分解成L形纳米棒二聚体和普通纳米棒二聚体两个部分, 通过分别改变L形纳米棒的臂长和普通纳米棒的长度, 对比L形纳米棒二聚体和普通纳米棒二聚体间的共振峰位置变化, 可以更直观地了解金纳米棒复合体消光光谱线型的变化. 这些结果可用于指导金纳米棒复合体纳米光子器件的设计, 以满足其在表面增强拉曼散射和生物传感等方面应用.     

Resonance and composition effects on the Raman scattering from silver-gold alloy clusters

Low-frequency Raman scattering experiments have been performed on thin films consisting of pure gold or gold-silver alloy clusters embedded in alumina matrix. It is clearly shown that the quadrupolar vibrational modes are observed by Raman scattering because of the effect of resonance with the excitation of the electronic surface dipolar plasmon. This is due to the strong coupling between the collective electronic dipolar excitation and the quadrupolar vibrational modes. This effect of resonance does not exist with the core electron excitations. The mixing of the conduction electron dipolar excitation (surface plasmon) with the core electrons leads to the quenching of the resonant Raman scattering. Received 16 November 2000     

Experimental investigation of plasma excitations in asymmetric stripes of two-dimensional electrons

The plasmon microwave response of symmetric and asymmetric stripes of two-dimensional electrons with different boundary conditions has been studied. The symmetric case corresponds to stripes either without ohmic contacts or with ohmic contacts on both sides, while the contact in asymmetric stripes is present only on one side. It has been shown that there is a frequency shift of the observed plasma modes in asymmetric stripes. The lowest-frequency mode becomes a previously unobserved mode for which the quarter wavelength of the plasmon coincides with the length of the stripe. The behavior of the lowest mode and its multiple frequencies in asymmetric stripes has been studied under variation of the magnetic field, electron density, and temperature and size of the stripes. The results indicate that all plasma modes in symmetric and asymmetric stripes have the same physical nature.     

Influence of amount of CTAB and ascorbic acid concentration on localized surface plasmon resonance property of gold nanorod

Gold nanorods (AuNRs) are prepared through seeded growth approach. Synthesis parameters of the amount of cetyltrimethylammonium bromide (CTAB), and concentration of ascorbic acid (AA) were studied. We were aiming for an aspect ratio of 3 which could be achieved by a nanorod feature in the range of 45 nm length and 15 nm width. The absorption spectra are observed with an UV–visible NIR spectrophotometer and analysed theoretically. It is known that there are two plasmon resonance peaks for gold nanorod corresponding to transverse surface plasmon resonance (TSPR) and longitudinal surface plasmon resonance (LSPR), respectively. It is found that as the concentration of CTAB increases, the yield of NRs increases. As the concentration of AA increased from 0.05 to 0.2 M, LSP shifts to longer wavelength but upon further increasing the concentration, LSP shifts back to shorter wavelength. A linear relationship between LSPR wavelength and surrounding medium dielectric constant is obtained, which is in good agreement with the theoretical results.     

硝酸铟诱导的电沉积氧化锌纳米柱光学性质裁剪

为在新型太阳能电池等光电器件中应用ZnO纳米结构,需要对ZnO纳米结构阵列的几何形貌及光电物理性质进行裁剪与操控。采用电化学沉积路线制备ZnO纳米柱阵列,In(NO3)3与NH4NO3两种盐类被溶入在传统Zn(NO3)2主电解液中。对ZnO纳米柱阵列进行扫描电子显微镜、透射反射光谱、光致发光光谱测试,分析其形貌与光电物理性质。随着引入的In(NO3)3浓度的增加,ZnO纳米柱阵列的平均直径随之由57 nm减小至30 nm。同时ZnO纳米柱的阵列密度也可降低,进而增大纳米柱间距至41 nm。由于新的盐类的引入,ZnO纳米柱的光学带隙由3.46 eV蓝移至3.55 eV。随着电解液中In(NO3)3的增加,ZnO纳米柱的斯托克斯位移由198 meV减小至154 meV,ZnO纳米柱中的非辐射复合可以得到一定程度的抑制。通过在主电解液中引入In(NO3)3与NH4NO3两种盐类,可对ZnO纳米柱的直径、密度、间距、透射反射率、光学带隙、近带边发射与非辐射复合进行操控与裁剪。     

A study of the orientation dependence of the electron energy loss spectra for single crystal films of copper and silver

Apart from two peaks caused by bulk and surface plasmons, four or five peaks (depending on the crystal type) of electron energy losses due to inter- and intraband electron transitions are observed in the investigation of the electron energy loss spectra for metals (Cu, Ag). A comparative analysis of the spectra for Cu or Ag films reveals a shift of bulk plasmon loss peaks to higher values for polycrystals, as in the case of transition metals and semiconductors. In a study concerning the orientation dependence of the energy loss spectra (ELS) for electrons scattered from the copper and silver surface, the anisotropy of the bulk plasmon peak is found when the incident beam’s polar angle or the sample’s azimuthal angle are altered. The anisotropy of the primary electron energy loss for plasmon excitation is also observed, depending on the sample orientation relative to the direction incident electrons. The energy losses are found to increase with an increasing atomic packing density of planes and crystal transparency relative to the incident beam.     

Surface electron accumulation in indium nitride layers grown by high pressure chemical vapor deposition

Surface termination and electronic properties of InN layers grown by high pressure chemical vapor deposition have been studied by high resolution electron energy loss spectroscopy (HREELS). HREEL spectra from InN after atomic hydrogen cleaning show N-H termination with no indium overlayer or droplets and indicate that the layer is N-polar. Broad conduction band plasmon excitations are observed centered at 3400 cm⁻¹ in HREEL spectra with 7 eV incident electron energy which shift to 3100 cm⁻¹ when the incident electron energies are 25 eV or greater. The shift of the plasmon excitations to lower energy when electrons with larger penetration depths are used is due to a higher charge density on the surface compared with the bulk, that is, a surface electron accumulation. These results indicate that surface electron accumulation on InN does not require excess indium or In-In bonds.     

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.     

Surface-enhanced Raman scattering properties of highly ordered self-assemblies of gold nanorods with different aspect ratios

Gold nanorods with aspect ratios of from 1 (particles) to 31.6 were synthesized by the seed-mediated method and packed in a highly ordered structure on a large scale on silicon substrates through capillary force induced self-assembly behaviour during solvent evaporation.The gold nanorod surface exhibits a strong enhancing effect on Raman scattering spectroscopy.The enhancement of Raman scattering for two model molecules (2-naphthalenethiol and rhodamine 6G) is about 5-6 orders of magnitude.By changing the aspect ratio of the Au nanorods,we found that the enhancement factors decreased with the increase of aspect ratios.The observed Raman scattering enhancement is strong and should be ascribed to the surface plasmon coupling between closely packed nanorods,which may result in huge local electromagnetic field enhancements in those confined junctions.