金复合纳米微粒的消光特性

基于Mie光散射理论,研究了金壳介质芯的金复合纳米球壳微粒在光散射与吸收中的消光特性.对微粒增大时的多极子特性以及内半径变动时共振峰的移动作了计算和分析,证实了共振峰位置随内外半径比增大而增大的规律.还对纯金纳米微粒的多极子特性作了计算,并讨论了总消光效率中散射和吸收各自的贡献.     

球型和棒状金纳米粒子的光谱性质比较

柠檬酸钠还原和诱导晶种生长法合成了球型和棒状金纳米粒子。金纳米粒子的吸收光谱表明,表面等离子体共振(SPR)强烈依赖于金属粒子的形状,球型粒子表现为单-SPR谱峰,而棒状粒子则具有横向和纵向SPR谱峰,且纵向SPR峰位和强度取决于棒状粒子的径横比。棒状金纳米粒子对吸附的对巯基苯甲酸分子的拉曼散射比球型金纳米粒子具有更强的表面增强性能,归因于棒状粒子高能晶面上的吸附可能导致的更强的化学增强效应。     

基于Ag纳米棒阵列的表面等离激元微型偏振器

采用静电近似理论计算了Ag纳米棒阵列在不同偏振光入射下的消光光谱。当入射光偏振方向平行于纳米棒长轴时会激发表面等离激元纵向振动模式,而当入射光偏振方向垂直于纳米棒长轴时会激发表面等离激元横向振动模式。基于两种模式共振波长的不同,采用Ag纳米棒阵列可以用来设计高性能的表面等离激元微型偏振器。Ag纳米棒阵列的偏振性能在纵向共振波长明显优于在横向共振波长,通过调节纳米棒的纵横比可以对纵向模式的共振峰位进行大范围调控。结果表明这种微型偏振器所适用的波长能够通过纳米棒的纵横比在可见到近红外波段范围内调控,而消光比和插入损耗能够通过纳米棒的直径和长度实现调控。     

Ag-Au二元纳米微粒吸收谱的计算

纳米微粒的光学性能与其表面等离子体共振关系密切.本文利用推广的Mie理论计算研究了Au-Ag体系单质、合金以及核壳结构纳米颗粒的消光、吸收和散射的性能(包括壳核结构Ag-Au微粒在紫外-可见光的吸收性能),计算结果与实验值相符合得很好.研究表明,随着粒径的增加,微粒表面等离子体共振偶极吸收峰出现红移,波峰位置与纳米微粒的尺寸具有线性关系.壳核结构中,粒径与核壳比决定了整个微粒的吸收性能.进一步研究表明,当Au壳层较薄时,可以获得具有可调光学性能的壳核纳米结构;而当Au壳层较厚时,其光学性能与同尺寸单质Au微粒一致.通过计算分析,本文还将Mie理论推广到具有空腔结构并且壳层厚度达到一定值的纳米微粒.另外,研究发现合金结构纳米微粒的吸收峰位置与合金成分有着线性关系.本研究表明,人们可以通过控制纳米微粒的尺寸、形貌和结构,调节其表面等离子体共振峰位,这大大拓展了纳米微粒的应用范围.     

利用表面等离子体共振效应确定金纳米棒的尺寸

金属纳米粒子的尺寸和形状对其物理和化学性质有很大影响,通常利用昂贵的透射电子显微镜和扫描电子显微镜进行其尺寸测量。为了节约测量成本,利用时域有限差分法研究了金纳米棒的尺寸与吸收峰的对应关系得到间接的测量方法。即当金纳米棒的纵横比增大时,横向等离子峰几乎没有变化,纵向等离子峰出现明显的红移,且红移速度随着金纳米棒半径的增大而增大。实际制备了两种不同尺寸的金纳米棒样品,通过理论模拟确定的金纳米棒的尺寸与利用透射电子显微镜测量的金纳米棒的尺寸符合的很好。     

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.     

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。     

用扫描近场光学显微镜技术研究金膜表面等离体子共振

表面等离体子波(SPW)可与入射光横磁波极化能量耦合并被共振激发,这种现象被称为表面等离体子共振现象(SPR)。主要利用扫描近场光学显微镜(SNOM)技术和表面等离体子共振现象技术相结合,来研究金膜表面等离体子共振。设计并建立了结构独特的新型Kretschmann型表面等离体子共振现象耦合装置,同时又设计了具有厚度梯度的表面等离体子的制备方法。在此基础上,测量了改变入射角条件下的表面等离体子共振曲线,测得该装置的等离体子共振角灵敏度为1°。并且对金膜表面进行表面等离体子共振条件下的扫描近场光学显微成像。实验结果表明,在共振时金膜表面的扫描成像比不共振时清晰,而且增加了很多细节。应用表面等离体子共振现象技术将可以明显提高扫描近场光学显微镜的信噪比、分辨力等性能。     

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.     

单一金纳米棒的光学及折射率传感特性研究

基于贵金属纳米粒子在折射率传感及探测中的应用,本文运用离散偶极近似,模拟计算了单一金纳米棒的远场消光光谱,研究了其偶极局域表面等离子体共振波长的可调性及折射率的传感特性。研究表明,通过调控金纳米棒的长径比,纳米棒的局域表面等离子体共振波长在可见至近红外波长范围内广泛可调;在可见与近红外波长范围内,该共振波长及对应的折射率灵敏度对纳米棒长径比的响应皆分别呈现出二次与线性的分段特征。此外,利用金介电函数虚部随入射光波长的变化关系,揭示了金纳米棒表面等离子体所对应的半高宽随该共振波长的变化规律;并利用长径比对金纳米棒的品质因子进行了优化,得到了优化的长径比。本文的研究结果对未来设计和制造性能优异的基于局域表面等离子体共振的传感/探测基底和元器件具有重要的理论指导意义。     

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 .     

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.     

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.     

Seedless synthesis of gold nanorods by using hydrogen peroxide as a weak reducing agent

Abstract

A new seedless wet chemistry synthesis of gold nanorods by using hydrogen peroxide as the weak reducing agent is reported. A reduced concentration of hexadecyltrimethylammonium bromide is used in our experiment, and the synthesized gold nanorods exhibit tunable longitudinal surface plasmon resonance peaks ranging from 725 to 945?nm. The influence on gold nanorods growth by adjusting the amounts of sodium hydroxide, silver nitrate, sodium borohydride, and hexadecyltrimethylammonium bromide were investigated by the visible-near infrared spectroscopy. Under the proper experimental parameters, the longitudinal surface plasmon resonance peaks can be tuned by varying the hydrogen peroxide amounts. Furthermore, it can be seen that the redshift of the longitudinal absorption peak of the prepared gold nanorods with increasing hydrogen peroxide amount is consistent with the increase tendency of the length-to-width aspect ratio obtained from the transmission electron microscopy images. The method provides a facile pathway to prepare gold nanorods with tunable longitudinal surface plasmon resonance peaks, which have potential applications in biomedicine and nanophotonics.     

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.     

Shape dependent full width at half maximum of the absorption band in gold nanorods

The dependence of full width at half maximum (FWHM) of the absorption peak in gold nanorods was investigated as a function of aspect ratio. Numerical calculations based on Drude model and quasi-static theory indicated that, the FWHM of longitudinal absorption peak is wider than that of transverse mode. Further more, with the increasing aspect ratio, the FWHM of longer wavelength absorption peak increasing in a nonlinear way, which is in agreement with the experimental results.     

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.     

Calculated Optical Properties of Dielectric Shell Coated Gold Nanorods

Optical absorption spectra of dielectric shell coated gold nanorods are simulated using the discrete dipole ap- proximation method. The influence of the aspect ratio, shell thickness, dielectric constant of the shell, and surrounding medium on the longitudinal resonance mode is investigated. It is found that the coated dielectric shell does not affect the trend in the dependence of resonance position on the aspect ratio, while it broadens the resonant line width and reduces the sensitivity of plasmon resonance in response to changes of the surrounding medium. F~arthermore, the difference of dielectric constants between the shell and surrounding medium plays an important role in determining the resonance position. The screening effect of the dielectric shell tends to be less apparent for a thicker shell thickness.Optical absorption spectra of dielectric shell coated gold nanorods are simulated using the discrete dipole ap- proximation method. The influence of the aspect ratio, shell thickness, dielectric constant of the shell, and surrounding medium on the longitudinal resonance mode is investigated. It is found that the coated dielectric shell does not affect the trend in the dependence of resonance position on the aspect ratio, while it broadens the resonant line width and reduces the sensitivity of plasmon resonance in response to changes of the surrounding medium. F~urthermore, the difference of dielectric constants between the shell and surrounding medium plays an important role in determining the resonance position. The screening effect of the dielectric shell tends to be less apparent for a thicker shell thickness.     

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.