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。     

Optical formation and manipulation of particle and cell patterns using a tapered optical fiber

A method for optical formation and controllable manipulation of particle and cell patterns using a tapered optical fiber is demonstrated. With a laser beam at 980‐nm wavelength launched into the fiber, different sized silica particles were formed into particle patterns (both one‐dimensional chains and two‐dimensional arrays) with different particle numbers by optical binding. The formed particle patterns can be controllably manipulated in three dimensions. Using yeast cells as an example, it was demonstrated that the method is applicable for the formation of biological cell patterns, without damage to the yeast cell viability. This method provides a new facile way for biophotonic and biological researches with particles and cells in a highly organized manner.     

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。     

Third-order nonlinear optical response of Au:SiO 2 thin films: Influence of gold nanoparticle concentration and morphologic parameters

We report a study on the third-order nonlinear optical properties of nanocomposite thin films composed of gold particles embedded in a silica host matrix. Samples of various metal volume fractions, ranging from 8 to 35%, are synthesized by the sputtering technique. Some of them are annealed. Nonlinear optical measurements, which are performed by using the z-scan technique, reveal both a very large nonlinear absorption and a weak nonlinear refraction close to the surface plasmon resonance frequency of the particles. We especially study the effect of the metal concentration and the influence of thermal treatment on the real and imaginary components of the third-order nonlinear susceptibility. Our results reveal that, as the metal concentration reaches a few percent, the mutual electromagnetic interactions between particles greatly enlarge the nonlinear optical response of the material and can not be neglected in the theoretical analysis. Moreover, the thermal treatment leads, for a given concentration, to a significant increase of the nonlinear response, which is ascribed to a modification of the material morphology. We finally point out that the material nonlinear properties are very sensitive to the incident wavelength through the local field enhancement phenomenon. Received 12 December 2001     

A facile high‐performance SERS substrate based on broadband near‐perfect optical absorption

Plasmonic systems based on metal nanoparticles on a metal film with high optical absorption have generated great interests for surface‐enhanced Raman scattering (SERS). In this study, we prepare a broadband‐visible light absorber consisting Au nanotriangles on the surface of a continuous optically opaque gold film separated with a dielectric SiO₂ layer, which is a typical metal‐insulator‐metal (MIM) system, and demonstrate it as an efficient SERS substrate. The MIM nanostructure, prepared using nanosphere lithography with a very large area, shows a broadband with absorption exceeding 90% in the wavelength regime of 630–920 nm. We observe an average SERS enhancement factor (EF) as large as 4.9 × 10⁶ with a 22‐fold increase compared to a single layer of Au nanotriangles directly on a quartz substrate. A maximum SERS EF can be achieved by optimizing the thicknesses of the dielectric layer to control the optical absorption. Owing to the simple, productive, and inexpensive fabrication technique, our MIM nanostructure could be a potential candidate for SERS applications. Copyright © 2015 John Wiley & Sons, Ltd.     

Plasmonic sensors based on thick metal film perforated with rectangular nanohole arrays

The dependence of optical properties on the ambient medium, the period of nanohole arrays and the metal film thickness in a thick silver film perforated with rectangular nanohole arrays is investigated using the finite‐difference time‐domain technique. As a result of the coupling between top and down surface plasmon polaritons, mediated by localized surface plasmon resonances supported by the metallic rectangular nano‐ holes, interesting light phenomena are observed for varying thickness of the metal film and period of the rectangular nanohole arrays. Based on the dependence of the optical properties on the ambient medium, the possibility of exploiting thick metal rectangular nanohole arrays as plasmonic sensors is further discussed, the potential application as plasmonic sensors is revealed. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Uniform plasmonic near-field nanopatterning by backward irradiation of femtosecond laser

We present localized optical field distribution properties in the vicinity of gold particles on a silicon substrate by backward and forward irradiation. It is technically difficult to fabricate nanostructures on the surface by a conventional forward laser incident to the substrate because gold nanoparticles easily aggregate to form double-layered particle arrays. We calculated enhanced optical field properties in order to pattern the substrate surface only with a template of the bottom-layered particle arrays in the case that the backward irradiation of a femtosecond laser is used in the system of aggregated double-layered gold nanoparticle arrays. With the backward irradiation, the optical field intensity in the substrate for the double-layered hexagonal arrays is found to be only 30% lower than the mono-layered system. Moreover, a near field cannot be generated with the forward irradiation. As a result, only the backward irradiation scheme is found to be effective for uniform surface nanopatterning at enhanced plasmonic near-field zones.     

Local plasmon sensor with gold colloid monolayers deposited upon glass substrates

A new optical sensor that uses local plasmon resonance is proposed. A peak that is due to the local plasmon resonance appears in the absorption spectrum of a gold colloid suspension in the visible region, and its height and wavelength depend on the refractive index of the suspension. These properties are used for optical sensors. We used gold colloid monolayers in which colloidal gold particles a few tens of nanometers in diameter were immobilized upon a glass slide by a functional organic coupling agent. We measured the absorption spectra of the the gold colloid monolayers, which were immersed in liquid samples or coated with thin films. We observed increases of both the resonance wavelength and the absorbance as the refractive indices of the sample liquids or the thickness of the coated films increased. The proportional constants of the resonance wavelength to the film thickness were 3.6 and 5.7 for a 13.9- and a 20.2-nm gold colloid monolayer, respectively.     

Pulsed-laser deposition and characterization of ZnO nanowires with regular lateral arrangement

We report on the high-pressure pulsed-laser deposition growth of periodic arrays of free-standing single zinc oxide nanowires with uniform hexagonal arrangement and cross-section with thickness of less than 100 nm. In order to achieve the wire alignment, we prepared an ordered array of catalytic gold seed particles by a nanosphere lithography mask transfer technique using monodisperse spherical polystyrol nanoparticles. These templates were investigated by scanning electron microscopy and atomic force microscopy prior to nanowire growth. X-ray diffraction revealed the epitaxial relationships between the nanostructures and the a-plane sapphire substrate and excellent crystal quality. The optical properties of the ZnO nanowire arrays were measured by cathodoluminescence. PACS 61.82.Rx; 81.05.-t; 81.05.Dz; 81.10.-h     

Third-order optical susceptibility of small metallic particles

Summary We present a tight-binding model for the linear and non-linear optical properties of small metal particles, which takes into account both size and matrix effects. We show that the surface states and the dielectric medium embedding the particles determine the properties of the microcrystals; in particular, we prove that the shallow-lyingd-band plays a crucial role in noble-metal particles. As an example, we calculate the third-order susceptibility and the phase-conjugated signalfor gold clusters made of several hundred atoms. A good agreement with experimental results is obtained.     

A Surface Study of Ultrathin Ceria Nanoparticles Decorated with Transition‐Metal Ions

A wide range of nanoparticle properties can be tuned by changing their surface characteristics, especially when dealing with ultrathin nanomaterials. Surface modification with transition‐metal ions may affect a variety of the nanoparticles' properties including the surface charge, the electronic structure, and the electrical and optical characteristics. In this work, a surface study of ceria nanoparticles modified by attachment of various transition‐metal ions to their surface is conducted. Characterization of the decorated particles as well as of the modifying transition‐metal ion is carried out using zeta potential in organic solution, UV–Vis absorption, and electron paramagnetic resonance measurements, together with isothermal titration calorimetry, X‐ray photoelectron spectroscopy, and energy dispersive X‐ray spectroscopy. All measurements confirm the attachment of the cation to the surface of ceria, both in solid state and in colloidal suspension. It is suggested that the modifying ion‐complex attaches to ceria both via chemical or strong physical interactions and weak physical interactions, demonstrated by a case‐study modification of ceria using a copper‐oleylamine complex. The metalization has a significant effect on the surface charge of the nanoparticles by shifting the zeta potential to more positive values and on the optical properties of the modifying transition‐metal ions by red‐shifting their absorption peak.     

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.     

Anomalies of light transmission in structurally ordered nanocomposites

We study the optical properties of spatially ordered nanocomposites consisting of spherical nanoparticles. Based on the integral equation method, we derive and investigate the expressions for the fields inside and outside the system. We show that two different states of the system possibly depend on the material and geometric parameters of the nanoaggregate. The states differ by the presence or absence of the forbidden band (an interference reflection peak) in the visible range for photons of definite energy. In the case of dielectric nanoparticles, we show that, if the nanoaggregate is not a photonic crystal in the visible wavelength range, scattering of light by the particles is suppressed in the nanostructure with definite parameters, and the ensemble under study becomes completely transparent. We propose a composite material, which possesses a 100% transmission at some wavelengths and is formed by densely packed dielectric nanospheres. We study the light transmission through an aggregate consisting of metal (gold) nanoclusters and find that, in spite of the fact that absorption is an intrinsic characteristic of metals, in a definite region of the near-IR range of the spectrum, this system is also characterized by an anomalously high transmission of radiation (close to 100%).     

A simple GUI for modeling the optical properties of single metal nanoparticles

We present a graphical user interface, based on the modified long-wavelength approximation, to compute the optical properties of single metal nanoparticles of ellipsoidal geometry (spheres, rods, and disks). The user-friendly interface allows one to readily gauge the accuracy of results obtained using the modified long-wavelength approximation. For spherical particles, up to 10-nm diameter, we confirm that our approach yields an exact correspondence with Mie theory, and gives an approximation error of less than 15% for gold (silver) particles with diameters approaching 40 nm (26 nm). Results are shown to be sensitive to the source data for the optical constants for a given material. The modular nature of the simulation platform provides a quick and intuitive guide for optical characterization experiments.     

Physical mechanisms behind the SERS enhancement of pyramidal pit substrates

In this paper we theoretically consider the physical mechanisms behind the surface‐enhanced Raman scattering (SERS) enhancement produced by commercially available Klarite substrates, which consist of rectangular arrays of micrometre‐sized pyramidal pits in silicon with a thin gold coating. Full three‐dimensional numerical simulations of the pits are conducted for both a real gold metal coating and a perfect electrical conductor (PEC) to determine whether the SERS enhancement is due to diffraction or plasmon effects. The pit apex angle and metal coating thickness are also varied to determine whether it is possible to further enhance the SERS signal by optimising the structural parameters of these substrates. By decreasing the film thickness and adjusting the apex angle, it is possible to achieve an enhancement almost double that of a standard Klarite substrate. Copyright © 2010 John Wiley & Sons, Ltd.     

Metal Nanoparticle Photocatalysts: Synthesis,Characterization, and Application

Metal nanoparticles (NPs) have emerged as a kind of new photocatalyst to drive various chemical reactions by visible‐light irradiation. A distinct advantage of metal NP photocatalysts is that their light absorption is not limited to a certain wavelength but instead they are able to utilize a broad range of wavelengths, constituting a large fraction of the solar spectrum. Metal NPs like gold, silver, and copper NPs can strongly absorb visible light due to the localized surface plasmon resonance (LSPR) effect. Recent developments have shown that the light absorption properties strongly depend on the shape, size, and particle–particle interactions of NPs, which directly influence their photocatalytic activities. In this review, an overview of the preparation of metal NPs photocatalysts with various morphologies is given along with a brief discussion of the relationship between the morphology/composition and optical properties. The latest photocatalytic applications of these morphologies are also presented, and some of the challenges for the development of metal NPs photocatalysts are provided.     

Ultrabroadband strong light absorption based on thin multilayered metamaterials

Light absorbers have drawn intensive attention as crucial components for solar‐energy harvesting, thermal emission tailoring, modulators, etc. However, achievement of light absorbers with wide bandwidth remains a challenge thus far. Here, a thin, unprecedentedly ultrabroadband strong light absorber is proposed and experimentally demonstrated, which consists of periodic taper arrays constructed by an alumina–chrome multilayered metamaterial (MM) on a gold substrate. This MM can change from a hyperbolic material to an anisotropic dielectric material at different frequency ranges and the special material features are the fundamental origins of the ultrabroadband absorption. The absorber is quite insensitive to the incident angle, and can be insensitive to the polarization. One two‐dimensional periodic array of 400‐nm height MM tapers is fabricated. The measured absorption is over 90% over almost the entire solar spectrum, reaching an average level of 96%, and remains high (above 85%) even in the longer‐wavelength range till 4 μm. The proposed absorbers open up a new avenue to realize broadband thin light‐harvesting structures.     

Absorption and Scattering of Light by Hybrid Metal/J-Aggregate Nanoparticles: Plasmon–Exciton Coupling and Size Effects

We report the results of our theoretical studies of the optical properties of hybrid nanoparticles consisting of the metal core covered with molecular J-aggregates. We evaluate the cross sections of absorption and scattering of light by such particles on the basis of the extended Mie theory for two concentric spheres with material dielectric functions that take into account the size effect associated with scattering of free electrons from the core/shell interface. We carry out our calculations in a wide range of light wavelengths and geometrical parameters of the composite system for silver and gold core and for a J-aggregate shell composed of different cyanine dyes. The results obtained demonstrate the quite different behavior of the extinction spectra of such particles caused by the different strengths of interaction between the Frenkel exciton and the dipolar or multipolar plasmons. We pay particular attention to the investigation of spectral peak positions associated with the eigenfrequencies of hybrid modes in the system and peak intensities as functions of reduced oscillator strength in the molecular J-band for various relationships between the core radius and shell thickness. This provides an efficient means for the explanation of the main features in the optical properties of metal/J-aggregate nanoparticles and can be used for an effective control of the plasmon–exciton coupling strength in such hybrid complexes.     

X‐ray absorption spectroscopic study on gold particles formed on titania and alumina

X‐ray absorption near‐edge structure (XANES) measurements near the Au L₃ edge were made on Au(III) complex ions adsorbed on titania and alumina without a specific reducing agent. Compared with the XANES spectrum of a pure gold foil, the gold adsorbed on titania and alumina was found to be reduced to Au(0). The XANES method could obtain spectra of gold particles less than 1 nm in diameter, although a UV–visible absorption spectrum was difficult to observe with such samples. Copyright © 2003 John Wiley & Sons, Ltd.