具有双共振吸收峰的Au纳米粒子制备及其拉曼表征

表面增强拉曼散射(SERS)很大程度的弥补了拉曼散射强度弱的缺点,迅速成为科研工作者们的研究热点,在食品安全、环境污染、毒品以及爆炸物检测等领域应用广泛。纳米技术的发展使得目前对于SERS的研究主要集中于金属纳米颗粒基底的制备,金属纳米粒子的种类、尺寸及形貌对SERS增强和吸收峰峰位均有影响,要获得好的增强效果,需要对金属纳米结构进行工艺优化。特别是,需要结合金属纳米粒子的结构和激励光波长,以期获得更好的增强效果。为了研究SERS增强和吸收峰之间的关系,开展了具有双共振吸收峰的金属纳米粒子的研究。首先利用FDTD Solutions仿真建模,主要针对金纳米颗粒直径、金纳米棒长径比及分布状态对共振吸收峰进行仿真,得到金纳米球理论直径在50 nm左右,金纳米棒理论长径比在3.5~4.5左右时,吸收峰分别分布在532及785 nm附近,符合多波段激励光拉曼增强条件;对于激励光偏振方向,其沿金纳米棒长轴方向偏振时吸收峰位于785 nm附近,沿金纳米球短轴方向偏振时吸收峰位于532 nm附近。然后采用种子生长法,制备了可用于多种波长激励光的双吸收峰表面增强拉曼散射基底。通过改变硝酸银用量(5,10,20,30和40 μL)、盐酸用量(0.1和0.2 mL)以及其生长时间(15,17,21和23 h)等多种工艺参数来控制金纳米棒含量,得到了同时含有金纳米球及金纳米棒的双吸收共振峰金纳米粒子。最后用该样品作为基底,罗丹明6G(R6G)作为探针分子,分别测试其在532,633和785 nm激励光入射时的SERS表征,对分析物R6G最低检测浓度均达到了10-7 mol·L-1,增强因子达到了~105,满足了多波段SERS检测的需要。     

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。     

不同形貌金纳米粒子的制备及其表面增强拉曼散射效应的研究

不同形状的金纳米粒子在表面增强拉曼散射(surface enhanced Raman scattering,SERS)中有不同的增强效果,多面体金纳米粒子具有多角结构,显示出比金纳米板更为明显的增强效果,近年来对其合成和性质的研究备受关注。该研究探究了十二面体,二十面体,三角板,球形四种形状的金纳米粒子在SERS中不同的增强效果。分别采用硼氢化钠还原法和以N,N-二甲基甲酰胺(DMF)为还原剂制备金三角纳米片和二十面体金纳米粒子,又以二十面体金纳米粒子为种子制备出十二面体金纳米粒子,并分别以以上三种不同形貌的金纳米粒子及球形金溶胶为基底,4-巯基吡啶,对巯基苯甲酸为探针分子检测了其在不同激发波长下的增强效果。透射电子显微镜结果表明金三角纳米板的平均边长为130nm,二十面体和十二面体金纳米粒子的粒径分别为100和120nm。三者的紫外可见吸收峰分别在589,598和544nm处。表面增强拉曼散射结果表明金多面体比金三角纳米板表现出更好的增强效果。     

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。     

Size characteristics of surface plasmons and their manifestation in scattering properties of metal particles

The change of the scattering properties of sodium, gold and silver spherical particles with size is discussed in the context of surface multipolar plasmon resonances. The presented surface plasmon size characteristics are abstracted from the quantity which is observed and deliver multipolar plasmon resonance frequencies and plasmon damping rates in the form of a continuous function of particle radius. The performed analysis of the plasmon dispersion relation is analogous to the problem of surface plasmon localized at a semi-infinite, flat metal/dielectric interface.Correlation between the multipolar plasmon resonance parameters, and the spectroscopic optical properties of conductive nanoparticles appearing as peaks in the measurable light intensities is analyzed. We discuss the fact, that such peaks arise from interference of all the electromagnetic fields contributing to the measured intensity, and not solely to the fields due to surface plasmon multipolar modes.We describe the results of light scattering experiment in orthogonal polarization geometries with use of spontaneously growing sodium droplets. The polarization geometry of the experiment allows for distinct separation of resonant contribution of dipole and quadrupole plasmon TM mode contributions to the measured intensities as a function of size.Predictions concerning size characteristics for dipole and quadrupole plasmons are compared with the results of light scattering experiments using spherical sodium droplets (our results) and gold and silver particles in suspension [other authors: Sönnichsen C, Franzl T, Wilk T, von Plessen G, Feldmann J. Plasmon resonances in large noble-metal clusters. New J Phys 2002; 4:93.1–8; Haiss W, Thanh NTK, Aveyard J, Fernig DG. Determination of size and concentration of gold nanoparticles from UV–vis spectra. Anal Chem 2007; 79:4215–21; Njoki PN, Lim I-IS, Mott D, Park H-Y, Khan B, Mishra S, et al. Size correlation of optical and spectroscopic properties for gold nanoparticles. J Phys Chem C 2007; 111:14664–9; Mock JJ, Barbic M, Smith DR, Schultz DA, Schultz S. Shape effects in plasmon resonance of individual colloidal silver nanoparticles. J Chem Phys 2002; 116:6755–9].     

Gold aggregates on silica templates and decorated silica arrays for SERS applications

In this work, we report the fabrication and characterization of size controllable gold nanoparticles (NPs) aggregates for their application in surface enhanced Raman scattering (SERS). Aggregates were prepared using two methodologies: (i) by using silica particles arrays as a template to agglomerate gold NPs between the inter-particle interstices, and (ii) by functionalizing silica particles to be used as support to graft gold nanoparticles and thus to form decorated silica particle arrays. These substrates were used in the detection of Rhodamine 6G producing an enhancement factor (EF) from 10⁴ to 10⁶ that is associated to the increment of hot spot (HS) sites, and the fact that plasmon resonance from aggregates and absorption wavelength of test molecules are closely in resonance with excitation wavelength. The EF was also reduced when the plasmon resonance was red-shifted as a result of the increment of aggregate size. In spite of this, the EF is high enough to make these SERS substrates excellent candidates for sensing applications.     

不同类型银纳米粒子的吸收和拉曼增强特性的关系研究

一直以来,将纳米结构材料用于其表面增强拉曼散射(SERS)时会先测试其吸收光谱,因为一般研究认为,纳米结构材料产生SERS的原因是纳米结构材料对于入射光的吸收产生了局域表面等离子体共振(LSPR),因此我们常把SERS的增强因子随波长变化的曲线等同于吸收光谱曲线。近年来,有学者认为两者之间的联系可能是非常间接的,并且在许多情况下会产生误导。为了能够阐明两个之间的具体关系,考虑到银纳米粒子(AgNPs)以其局域表面等离子体共振而显著提高拉曼散射的能力而闻名, 是制备SERS基底的理想纳米材料,我们从实验和理论两个角度研究了三种不同状态的AgNPs中表面增强拉曼散射的增强因子(EF)、吸收光谱以及空间的电场分布。实验上,利用化学还原法制备了银溶胶(Ag-sol),并对Ag-sol做了透射电子显微镜(TEM)、紫外可见分光光度计(UV-Vis)以及拉曼的表征实验,统计和计算了银溶胶的EF和吸收光谱。理论上,利用仿真软件COMSOL Multiphysics建立了不同聚合类型AgNPs的仿真模型,模拟计算了与实验相对应的EF随波长变化的曲线以及吸收光谱。结果表明：表面等离子体共振的空间分布对吸收和最大EF值起着重要的作用;具有固定位置的共振吸收峰(第一个峰位)主要受“单颗粒类型”效应的影响,而最大EF处的吸收峰(第二个峰位)由“耦合间隙类型”效应引起的蓝移谐振峰主导,且最大EF值及第二个吸收峰的峰位会随着粒子的间隙、偏振角度等因素而变化。研究表明,AgNps样品的吸收光谱和最大EF曲线之间是部分相关的。     

The optical properties between an incident wave and the active layer of a bubble-pit AgO<Subscript>x</Subscript>-type super-resolution near-field structure

The deformation and plasmon effects of collective localized surface plasmons between incident light and bubble-pit AgO_x-type super-RENS structure have been studied using finite-difference time-domain (FDTD) method. We find that the polarization, wavelength of incident light, and particle sizes of Ag nanoparticles are sensitive to the plasma resonance. The Ag nanoparticles inside the bubble-pit AgO_x-type super-RENS structure give the additional outer boundaries to the motion of the Ag nanoparticles, and excite more evanescent field which located in the far edge of the bubble from the optical axis of the incident beam. The optical properties between active layer and incident light with polarization direction, different wavelengths, and varied particle sizes of Ag nanoparticles exhibits nonlinear optical behavior in the near field. The far-field signals of different wavelength of incident light confirm the relation between highly localized near-field distributions and enhanced resolution of far-field signals. The subwavelength recording marks smaller than the diffraction limit were distinguishable since the Ag nanoparticles with high localized fields transferred evanescent waves to detectable signals in the far field. PACS 42.79.Vb; 71.15.Rn; 72.15.Rn; 73.22.-f; 73.22.Lp; 78.67.Bf; 73.20.Mf     

Resonant Effects of FPL and SPP for Light Transmitting through Subwavelength Metallic Gratings

A new model is proposed to explain the physical mechanism of the extraordinary transmission enhancement in subwavelength metallic grating. The extraordinary transmission enhancement is described by the co-operation of Fabry-Perot-like (FPL) resonance and the surface plasmon polariton (SPP) resonance. The rigorous coupled-wave analysis (RCWA) and the finite difference time domain (FDTD) method are employed to illustrate the model by calculating the transmission and the field distributions in the subwavelength metallic grating, respectively. And the numerical calculations show that transmission enhancement is achieved when the coupling resonance of the incident light, the surface plasmon polariton mode and the Fabry-Perot-Like mode is happened, which are in good agreement with the proposed model.     

Near‐field optical enhancement by lead‐sulfide quantum dots and metallic nanoparticles for SERS

There is a growing interest in using quantum dots (QDs) and metallic nanoparticles (NPs), both for luminescence enhancement and surface‐enhanced Raman scattering (SERS). Here, we study the electromagnetic‐field enhancement that can be generated by lead‐sulfide (PbS) QDs using three‐dimensional finite‐element simulations. We investigate the field enhancement associated with combinations of PbS QDs with metallic NPs and substrates. The results show that high field enhancement can be achieved by combining PbS QDs with metallic NPs of larger sizes. The ideal size for Ag NPs is 25 nm, providing a SERS enhancement factor of ~5*10⁸ for light polarization parallel to the NP dimer axis and a gap of 0.6 nm. For Au NPs, the bigger the size, the higher is the field for the studied diameters, up to 50 nm. The near‐field values for PbS QDs above metallic substrates were found to be lower compared to the case of PbS QD‐metal NP dimers. This study provides the understanding for the design and application of QDs for the enhancement of near‐field phenomena. Copyright © 2013 John Wiley & Sons, Ltd.     

SERS activity of carbon nanotubes modified by silver nanoparticles with different particle sizes

A two-dimensional (2D) surface-enhanced Raman scattering (SERS) substrate is fabricated by decorating carbon nanotube (CNT) films with Ag nanoparticles (AgNPs) in different sizes, via simple and low-cost chemical reduction method and self-assembling method. The change of Raman and SERS activity of carbon nanotubes/Ag nanoparticles (CNTs/AgNPs) composites with varying size of AgNPs are investigated by using rhodamine 6G (R6G) as a probe molecule. Meanwhile, the scattering cross section of AgNPs and the distribution of electric field of CNTs/AgNPs composite are simulated through finite difference time domain (FDTD) method. Surface plasmon resonance (SPR) wavelength is redshifted as the size of AgNPs increases, and the intensity of SERS and electric field increase with AgNPs size increasing. The experiment and simulation results show a Raman scattering enhancement factor (EF) of 10⁸ for the hybrid substrate.     

Tunable local surface plasmon resonance in liquid-crystal-coated Ag nanoparticles

The far-field and near-field properties of a spherical nematic liquid crystal (NLC) coated metal nanoparticle (NPs) have been investigated in an external field, basing on the quasistatic theory. The resonant wavelength is tunable by varying metallic material of core, anisotropy extent and thickness of liquid crystals (LCs). The field enhancement is along the incident polarization near the outer surface of the shell. The direction of field is reverse in the inner surface comparing with the one if outer shell. In contrast to isotropy shell, the surface plasmon resonance (SPR) shows an obvious red shift and field enhancement near outer surface of the shell always is stronger.     

Surface‐enhanced Raman scattering study of Ag@PPy nanoparticles

Surface‐enhanced Raman scattering (SERS) spectra of Ag@polypyrrole (PPy) nanoparticles with both 488 and 1064 nm excitation were investigated. Experimental results as well as theoretical analysis demonstrated that electromagnetic (EM) enhancement and charge transfer (CT) both rebounded to the SERS effect of Ag@PPy nanoparticles. When near‐IR excitation (1064 nm) was used for the SERS measurements, the contribution from CT was amplified relative to that from EM because the energy of the near‐IR excitation is far from the surface plasmon resonance of the nanosized Ag particles. The increased doping level of PPy, leading to optimal energy matching between the Fermi levels of the Ag nanoparticles and the energy levels in PPy molecules, could obviouslyenhance the SERS signal. These results suggested that the SERStechnique wasan effective tool for investigating the doping effect and interface interaction in metal‐conductingpolymer composite nanoparticles. In particular, the SERS technique with near‐IR excitation could give more information regarding the contribution of the charge‐transfer mechanism to the spectral enhancement of this kind of system. Copyright © 2010 John Wiley & Sons, Ltd.     

Anomalous light scattering by small particles

Light scattering by a small spherical particle with a low dissipation rate is discussed based upon the Mie theory. It is shown that if close to the plasmon (polariton) resonance frequencies the radiative damping prevails over dissipative losses, sharp giant resonances with very unusual properties may be observed. In particular, the resonance extinction cross section increases with an increase in the order of the resonance (dipole, quadrupole, etc.); the characteristic values of electric and magnetic near fields for the scattered light are singular in the particle size, while energy circulation in the near field is rather complicated, so that the Poynting vector field includes singular points whose number, types, and positions are very sensitive to fine changes in the incident light frequency. The results may provide new opportunities for a giant, controlled, highly frequency-sensitive enhancement and variation of electromagnetic field at nanoscales.     

P-thiocresol 吸附在银纳米粒子表面系统的表面增强拉曼散射和表面增强共振拉曼散射的增强研究

文中从实验和计算两方面报道了在514.5 nm激发光下P-Thiocresol吸附在银胶表面系统的表面增强拉曼散射(SERS).文中分析了它的增强机制,发现增强主要来自于电磁场增强.如果考虑距离为2nm的两个银纳米粒子的耦舍效应,两粒子之间的SERS的电磁场增强为7.16 × 107.静态化学增强亦起到部分增强作用,它的增强倍数为6.所以,总的SERS增强,包括静态化学增强和电磁场增强,是Gtotal=Gsc ×GEM=4.4×108.我们也理论地研究了此系统的表面增强共振拉曼散射(SERRS).当激发光与P-Thiocresol-Ag3系统的激发态共振时,电荷转移机制(化学增强)也将起到重要作用,最强的增强可迭106.我们使用电荷密度将激发光下p-Thlocresol和Ag团簇问的电荷转移结果可视化,这是电荷转移的直接理论证据.对于SERRS增强,包括电荷转移和电磁场增强机制,能达到1013.     

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.     

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.     

A facile method for the synthesis of large‐size Ag nanoparticles as efficient SERS substrates

Silver nanoparticles (Ag NPs) enjoy a reputation as an ultrasensitive substrate for surface‐enhanced Raman spectroscopy (SERS). However, large‐scale synthesis of Ag NPs in a controlled manner is a challenging task for a long period of time. Here, we reported a simple seed‐mediated method to synthesize Ag NPs with controllable sizes from 50 to 300 nm, which were characterized by scanning electron microscopy (SEM) and UV–Vis spectroscopy. SERS spectra of Rhodamine 6G (R6G) from the as‐prepared Ag NPs substrates indicate that the enhancement capability of Ag NPs varies with different excitation wavelengths. The Ag NPs with average sizes of ~150, ~175, and ~225 nm show the highest SERS activities for 532, 633, and 785‐nm excitation, respectively. Significantly, 150‐nm Ag NPs exhibit an enhancement factor exceeding 10⁸ for pyridine (Py) molecules in electrochemical SERS (EC‐SERS) measurements. Furthermore, finite‐difference time‐domain (FDTD) calculation is employed to explain the size‐dependent SERS activity. Finally, the potential of the as‐prepared SERS substrates is demonstrated with the detection of malachite green. Copyright © 2016 John Wiley & Sons, Ltd.     

不同形状的金纳米粒子的表面增强拉曼光谱

使用514 5nm激光激发,第一次得到了不同形状金纳米粒子的表面增强拉曼光谱(SERS)。一般情况下,较短波长(<600nm)激发所获得的增强要小于使用较长波长(>600nm)的激发。然而,对特殊形状的自组装金纳米粒子,由于避雷针效应,即使使用绿光激发也可获得很高增强的SERS。     

Multiscale electromagnetic SERS enhancement on self‐assembled micropatterned gold nanoparticle films

In this work, we demonstrate a cascaded, multiplicative electromagnetic enhancement effect in surface‐enhanced Raman scattering (SERS) on periodically micropatterned films made of colloidal gold nanoparticles, prepared by a self‐assembly approach, without implying lithography procedures. The multiplicative enhancement effect is obtained by combining surface plasmon near‐field enhancement due to nanoscale features with far‐field photonic coupling by periodic microscale features. The effect is observed for both internal Raman reporters (molecules attached to the Au colloids before their assembly) and external Raman probes (molecules adsorbed on the samples after film assembly). The ability of the patterned films for far‐field light coupling is supported by reflectivity spectra, which present minima/maxima in the visible spectral range. Finite‐difference time‐domain computer simulations of the electric field distribution also support this interpretation. The fabricated dual‐scale SERS substrates exhibit a good spot‐to‐spot reproducibility and time stability, as proved by the SERS response over a time scale longer than 1 month. The experimental demonstration of this cascaded electromagnetic enhancement effect contributes to a better understanding of SERS and can affect future design of SERS substrates. Moreover, such dual‐scale colloidal films prepared by convective self‐assembly can be of general interest for the broader field of nanoparticle‐based devices. Copyright © 2014 John Wiley & Sons, Ltd.