Localized Surface Plasmon Resonance of Cu@Cu2O core-shell nanoparticles: Absorption, Scattering and Luminescence

By co-deposition via RF-Sputtering and RF-PECVD methods and using Cu target and acetylene gas, we prepared Cu@Cu₂O core-shell nanoparticles on the a-C:H thin film at room temperature. Mie absorption of Cu cores, scattering from Cu₂O shell and luminescence that rises from carrier transfer in Cu@Cu₂O interface were employed to fit the whole range of visible extinction spectrum of these core-shells. From simulation it was found that scattering and luminescence have an important effect on the energy, width and shape of LSPR absorption peak. Shift of LSPR peak is more affected by the dielectric coefficient of shell than Cu core size particularly for Cu core diameter above 4 nm. Also, the LSPR absorption peak is damped by decreasing Cu core size and dielectric coefficient of shell. The energy of LSPR absorption peak is independent of shell thickness and host dielectric coefficient. The LSPR peak is damped by increasing shell thickness and host dielectric coefficient too. The scattering contribution in extinction spectra was affected more by shell size than dielectric coefficient. These points are important for detection techniques based on LSPR peak.     

Optimization of ultrathin carbon film coated silver nanoshell for biomedical applications in vivo

The extinction spectroscopy and near-field enhancement of dielectric-silver nanoshell coated by tetrahedral amorphous carbon [ta-C] layer (DSC) have been calculated by using Mie theory. With decreasing the Ag layer thickness, the localized surface plasmon resonance (LSPR) of DSC nanoshell moves from the visible region into the near-infrared region and the corresponding local field factor (LFF) increases first and then decreases. In addition, the increase of ta-C shell thickness leads to red-shift of LSPR and the decrease of LFF in DSC nanoshell. We further find that the increase of the dielectric constant for the outer shell can induce a significant enhancement of near-field. Based on the simulation analysis, we show that the DSC nanoshell can provide strong near-field in near-infrared region and may be suitable for the biomedical applications in vivo.     

Optimization and design of pigments for heat-insulating coatings

This paper reports that heat insulating property of infrared reflective coatings is obtained through the use of pigments which diffuse near-infrared thermal radiation.Suitable structure and size distribution of pigments would attain maximum diffuse infrared radiation and reduce the pigment volume concentration required.The optimum structure and size range of pigments for reflective infrared coatings are studied by using Kubelka-Munk theory,Mie model and independent scattering approximation.Taking titania particle as the pigment embedded in an inorganic coating,the computational results show that core-shell particles present excellent scattering ability,more so than solid and hollow spherical particles.The optimum radius range of core-shell particles is around 0.3 ～ 1.6 μm.Furthermore,the influence of shell thickness on optical parameters of the coating is also obvious and the optimal thickness of shell is 100-300 nm.     

Ag/Si核壳结构纳米颗粒粒子系的吸收特性研究

当电子振动频率与入射光的频率相同时,部分金属纳米颗粒可以在其表面激发局部表面等离子共振效应(LSPR),该波长下颗粒的吸收增强。这种效应也被应用于增强拉曼光谱信号的强度。本文研究了以Ag为外壳材料、Si为内核的核壳结构纳米颗粒粒子系的吸收特性。采用时域有限差分方法求解了颗粒随机分布粒子系的吸收率,分析了颗粒体积分数、内核外壳尺寸、椭球化等因素对粒子系吸收特性的影响以及对吸收峰的调控作用。     

Theoretical studies on the near field properties of non-concentric core-shell nanoparticle dimers

The concentric core-shell nanoparticle dimers have “hot spots” with enhanced electric fields in their junctions, which can be used in the surface enhanced Raman spectra analysis. Here the non-concentric core-shell nanoparticle dimers are proposed by introducing a shift between the dielectric core and the metal shell. By using the three dimensional finite difference time domain method, the plasmon resonances and the near field properties of the core-shell nanoparticle dimers affected by the non-concentric shift, dimer separation, excitation wavelength and polarization are analyzed in detail. The results show that the local near fields of the non-concentric core-shell nanoparticle dimers can be much more enhanced than those of the concentric ones. Also the plasmon resonance wavelengths of the dimers can be effectively tuned by the non-concentric shifts between the core and shell. The proposed nanostructures can have great potential in various near field applications.     

Laser generated Ag and Ag–Au composite nanoparticles for refractive index sensor

Localized surface plasmon resonance (LSPR) wavelength of metal nanoparticles (NPs) is highly sensitive to size, shape and the surrounding medium. Metal targets were laser ablated in liquid for preparation of spherical Ag and Ag@Au core–shell NP colloidal solution for refractive index sensing. The LSPR peak wavelength and broadening of the NPs were monitored in different refractive index liquid. Quasi-static Mie theory simulation results show that refractive index sensitivity of Ag, Ag–Au alloy and Ag@Au core–shell NPs increases nearly linearly with size and shell thickness. However, the increased broadening of the LSPR peak with size, alloy concentration and Au shell thickness restricts the sensing resolution of these NPs. Figure-of-merit (FOM) was calculated to optimize the size of Ag NPs, concentration of Ag–Au alloy NPs and Au shell thickness of Ag@Au core–shell NPs. The refractive index sensitivity (RIS) and FOM were optimum in the size range 20–40 nm for Ag NPs. Laser generated Ag@Au NPs of Au shell thickness in the range of 1–2 nm showed optimum FOM, where thin layer of Au coating can improve the stability of Ag NPs.     

微小颗粒的光散射数值模拟

简单介绍了以经典Mie理论为基础的光散射测量技术在颗粒直径和颗粒浓度测量中广泛的应用。分别以Mie理论和离散偶极子近似理论(DDA)为基础, 用数值计算方法分析了球型颗粒的光散射特性，给出了微小颗粒对平行入射光散射的强度函数和散射偏振度的数值计算方法。得到了强度函数和偏振度随相关物理参量变化的三维图，为微小颗粒散射研究提供了一种三维视图。计算结果表明：当尺度参量x＜4时，2种方法所得结果差异不大；随尺度参量增大，2种方法所得结果出现较大差异。与经典Mie理论相比，由于离散偶极子近似理论可以解决各种形状的颗粒散射问题，其应用前景更广泛。     

Enhanced blue photoluminescence and new crystallinity of Ag/organic rubrene core-shell nanoparticles through hydrothermal treatment

Light-emitting organic semiconductors have attracted considerable attention for the nanoscale fabrication of organic-based displays and their potential application in optoelectronics, plasmonics, and photonics. In this study, core-shell hybrid nanostructures of organic rubrene coated on Ag nanoparticles (NPs) have been synthesized using a chemical reduction method. The thickness of the rubrene shell was 2.6–6.0 nm and the diameter of the Ag core was 30–70 nm. The optical and structural properties of the Ag/rubrene core-shell NPs were tuned by hydrothermal (HT) treatment at 190 °C. The Ag/rubrene core-shell NPs were characterized by high-resolution transmission electron microscopy and energy-dispersive X-ray (EDX) spectroscopy before and after the HT treatment, and their structural properties were confirmed through X-ray diffraction (XRD) analysis. XRD peaks related to an orthorhombic phase were observed along with the original triclinic crystal structure of the rubrene shell, and the triclinic crystal domain size increased from 28.2 nm to 30.8 nm owing to the HT treatment. Interestingly, the green light emission (λ_em = 550 nm) of the Ag/rubrene core-shell NPs changed to blue light emission (λ_em = 425 nm), increasing in intensity through the HT treatment. This is caused by the crystal change with H-type aggregation and enhanced energy transfer from a surface plasmon resonance.     

Fabrication of ZnO/Al2O3 core-shell nanostructures and crystalline Al2O3 nanotube

We have demonstrated the crystalline ZnO-Al₂O₃ core-shell nanowire structure by atomic layer deposition (ALD) at a temperature 100 °C. The core-shell structure could have potential applications in the fabrication of ZnO field effect transistor. After dissolving the ZnO core, shape defined, rigid and robust crystalline Al₂O₃ shelled nanostructures have been fabricated. Nanowire ZnO nanostructures have been replicated by alumina shell. This is one of the most effective techniques for producing core-shell or shell/hollowed nanostructures of any desired objects. The Al₂O₃ shelled nanostructures could have potential applications as space confined nanoreactors, drug delivery, nanofluidic channels and optical transmitting.     

Theoretical investigation on near-infrared and visible absorption spectra of nanometallic aluminium with oxide coating in nanoenergetic materials: size and shape effects

The effects of metal core dimension, oxide shell thickness and ellipsoid aspect ratio of Al-Al2O3 core-shell nanoparticles on the near-infrared and visible absorption spectra of nanocomposite Al-Al2O3/nitrocellulose（NC） film are investigated by numerical calculations. Both the size-dependent interband transitions and frequency-dependent free electron damping of the nanometallic aluminium are taken into account in the calculations. Oxidation effect of nanoaluminium is also analysed. It is shown that oxidation may enhance but may also reduce the optical absorption, depending on the excited light energy and initial dimension of nanoparticle. Metal core size and excited light energy dominate the absorption characteristic. The absorption ability of ellipsoidal nanoparticles is larger than that of spheroidal nanoparticles and increases by the square index as the aspect ratio increases. These calculations will provide some significant theoretical guidance for the preparation and laser ignition of nanoenergetic materials.     

Comparisons of the discrete-dipole approximation and modified double interaction model methods to predict light scattering from small features on surfaces

Two numerical methods to model light scattering from illuminated features on surfaces are presented. The discrete-dipole approximation (DDA) method is considered, as well as the modified double interaction method (MDIM). The DDA method models electromagnetic scattering of continuous features using discrete dipoles placed on a lattice structure. Sommerfeld integral terms are used to model dipole/surface interaction in the near-field. The MDIM method first computes scattering from the features based in free space using other methods such as Mie theory or other standard light scattering codes (including DDA). The surface interaction is modeled as a first approximation by means of a geometrical shadowing effect and the Fresnel coefficients. Comparisons of the methods will be shown for light scattering from spherical features. The material properties of dielectric and metallic materials will be considered and the feature sizes will be varied. The prediction accuracy and computational requirements of each method will be investigated. For most cases, the studies will show that the DDA method is more accurate than the MDIM method for dielectric materials since the modeling of the feature and surface electromagnetic interaction is more accurate; however, the modified double interaction method may be advantageous over the discrete-dipole approximation method for metallic features because of lesser computational times and memory requirements.     

Broadband tunability of surface plasmon resonance in graphene-coating silica nanoparticles

Graphene decorated nanomaterials and nanostructures can potentially be used in military and medical science applications. In this article, we study the optical properties of a graphene wrapping silica core–shell spherical nanoparticle under illumination of external light by using the Mie theory. We find that the nanoparticle can exhibit surface plasmon resonance(SPR) that can be broadly tuned from mid infrared to near infrared via simply changing the geometric parameters. A simplified equivalent dielectric permittivity model is developed to better understand the physics of SPR, and the calculation results agree well qualitatively with the rigorous Mie theory. Both calculations suggest that a small radius of graphene wrapping nanoparticle with high Fermi level could move the SPR wavelength of graphene into the near infrared regime.     

Structural and thermal stabilities of Au@Ag core-shell nanoparticles and their arrays:A molecular dynamics simulation

Thermal stability of core-shell nanoparticles(CSNPs)is crucial to their fabrication processes,chemical and physical properties,and applications.Here we systematically investigate the structural and thermal stabilities of single Au@Ag CSNPs with different sizes and their arrays by means of all-atom molecular dynamics simulations.The formation energies of all Au@Ag CSNPs we reported are all negative,indicating that Au@Ag CSNPs are energetically favorable to be formed.For Au@Ag CSNPs with the same core size,their melting points increase with increasing shell thickness.If we keep the shell thickness unchanged,the melting points increase as the core sizes increase except for the CSNP with the smallest core size and a bilayer Ag shell.The melting points of Au@Ag CSNPs show a feature of non-monotonicity with increasing core size at a fixed NP size.Further simulations on the Au@Ag CSNP arrays with 923 atoms reveal that their melting points decrease dramatically compared with single Au@Ag CSNPs.We find that the premelting processes start from the surface region for both the single NPs and their arrays.     

Numerical simulations on longitudinal surface plasmons of coupled gold nanorods

We analyze numerically the localized surface plasmon resonance (LSPR) frequencies of coupled metal nanorods using discrete dipole approximation (DDA) and finite element method (FEM). The two configurations of identical nanorods are considered: end-to-end and side-by-side. Dependence of LSPR frequencies on the interparticle distance is determined by DDA. The latter for the case of large separations agrees with the result of approximate analytical method developed earlier for single metal nanorods. Distributions of electric near-fields of nanorods as well as enhancement factors at hot spots for both configurations are calculated by FEM.     

芯帽纳米颗粒的光热性质

贵金属纳米结构中的光热效应在肿瘤光热治疗、光热成像、纳米药物等领域具有重要的应用价值.各向异性的芯帽纳米结构以其丰富的可调结构参数和对激发光偏振态敏感的特性,可灵活地在近红外波段获得理想的光学吸收性质,从而可以实现温度的高效调节.本文基于有限元方法研究了颗粒物纳米结构参数对其光热效果的作用规律,数值结果表明:通过对结构参数的微量改变(包括金壳厚度、芯壳比、芯径、金属表面覆盖率等)可实现温度的显著调整;在偏振态的旋转范围(30?—70?)内可快速地产生大温变光热的准线性调整.其不弱于纳米芯壳和纳米棒结构的光热性能可为纳米光热生医研究提供一种新的选择.     

金银三层纳米管局域表面等离激元共振特性研究

相对于单一金属纳米材料,二金属复合纳米材料具有更大的潜在应用价值.基于时域有限差分方法,研究了SiO₂-Ag-Au和SiO₂-Au-Ag二金属三层纳米管的消光光谱,并对其局域表面等离激元共振(Localized Surface Plasmon Resonance,LSPR)特性进行了分析.研究发现,内核尺寸变大将导致上述两种金属纳米管LSPR峰红移;内层金属及外层金属壳层厚度增大均会导致其LSPR峰蓝移.银壳厚度变化对纳米管LSPR的调制作用大于金壳厚度变化造成的影响.上述现象可以利用等离激元杂化理论及自由电子和振荡电子变化的竞争机制进行分析.     

Optical equivalence of isotropic ensembles of ellipsoidal particles in the Rayleigh-Gans-Debye and anomalous diffraction approximations and its consequences

Light scattering by isotropic ensembles of ellipsoidal particles is considered in the Rayleigh-Gans-Debye approximation. It is proved that randomly oriented ellipsoidal particles are optically equivalent to polydisperse randomly oriented spheroidal particles and polydisperse spherical particles. Density functions of the shape and size distributions for equivalent ensembles of spheroidal and spherical particles are presented. In the anomalous diffraction approximation, equivalent ensembles of particles are shown to also have equal extinction, scattering, and absorption coefficients. Consequences of optical equivalence are considered. The results are illustrated by numerical calculations of the angular dependence of the scattering phase function using the T-matrix method and the Mie theory.     

Continuum modelling of spherical and spheroidal carbon onions

Carbon nanostructures are of considerable interest owing to their unique mechanical and electronic properties. Experimentally, a wide variety of different shapes are obtained, including both spherical and spheroidal carbon onions. A spheroid is an ellipsoid with two major axes equal and the term onion refers to a multi-layered composite structure. Assuming structures of either concentric spherical or ellipsoidal fullerenes comprising n layers, this paper examines the interaction energy between adjacent shells for both spherical and spheroidal carbon onions. The Lennard-Jones potential together with the continuum approximation is employed to determine the equilibrium spacing between two adjacent shells. We also determine analytical formulae for the potential energy which may be expressed either in terms of hypergeometric or Legendre functions. We find that the equilibrium spacing between shells decreases for shells further out from the inner core owing to the decreasing curvature of the outer shells of a concentric structure.     

Anomalous diffraction approximation method for retrieval of spherical and spheroidal particle size distributions in total light scattering

Using total light scattering technique to measure the particle size distribution has advantages of simplicity in measurement principle and convenience in the optical arrangement. However, the calculation of extinction efficiency based on Mie theory for a spherical particle is expensive in both time and resources. Thus, a simple but accurate approximation formula for the exact extinction efficiency may be very desirable. The accuracy and limitations of using the anomalous diffraction approximation (ADA) method for calculating the extinction efficiency of a spherical particle are investigated. Meanwhile, the monomodal and bimodal particle size distributions of spherical particles are retrieved using the genetic algorithm in the dependent model. Furthermore, the spheroidal model in the retrieval of non-spherical particle size distribution is also discussed, which verifies the non-sphericity has a significant effect on the retrieval of particle size distribution compared with the assumed homogeneous isotropic sphere. Both numerical computer simulations and experimental results illustrate that the ADA can be successfully applied to retrieve the particle size distributions for spherical and spheroidal particles with high stability even in the presence of random noise. The method has advantages of simplicity, rapidity, and suitability for in-line particle size measurement.     

Light scattering by a spheroidal bubble with geometrical optics approximation

This paper proposes the spheroidal model for analyzing the light scattering characteristics of an air bubble. The angular distributions of light scattered by a large spheroidal bubble with end-on incidence are calculated using geometrical optics approximation. The divergence factor, diffraction, and phase shift are considered in the computation. The MATLAB code was developed and verified using the Mie result for a spherical bubble, and the scattering patterns of the two methods agreed well. The effects on the scattering properties are analyzed in terms of the size and shape parameter of the bubble and the incident beam width. The relations between the deviation angle and incident angle, emergent light intensity, and scattering angle are analyzed and used to explain the scattering patterns of a spheroidal bubble.