Optical properties and ultrafast electron dynamics in gold–silver alloy and core–shell nanoparticles

Silver and gold are the two most popular metals used for many nanoparticle applications, such as surface enhanced Raman scattering or surface enhanced fluorescence, in which the local field enhancement associated with the excitation of the localized surface-plasmon–polariton resonance (SPR) is exploited. Therefore, tunability of the SPR over a wide energy range is required. For this purpose we have investigated core–shell nanoparticles composed of gold and silver with different shell thicknesses as well as the impact of alloying on these nanoparticles due to a tempering process. The nanoparticles were prepared by subsequent deposition of Au and Ag atoms or vice versa on quartz substrates followed by diffusion and nucleation. Their linear extinction spectra were measured as a function of shell thickness and annealing temperature. It turned out that different gold shell thicknesses on silver cores allow a tuning of the SPR position from 2.79 to 2.05 eV, but interestingly without a significant change on the extinction amplitude. Heating of core–shell nanoparticles up to only 540 K leads to the formation of alloy nanoparticles, accompanied by a back shift of the SPR to 2.60 eV. Calculations performed in quasi-static approximation describe the experimental results quite well and prove the structural assignments of the samples. In additional experiments, we applied the well-established persistent spectral hole burning technique to the alloy nanoparticles in order to determine the ultrafast dephasing time T ₂. We obtained a dephasing time of T ₂=(8.1±1.6) fs, in good agreement with the dephasing time of T _2,∞=8.9 fs, which is already included in the dielectric function of the bulk.     

Modelling of sensitivity of plasmon sensory elements based on silver nanoparticles obtained by laser evaporation and ablation

A comparison of the sensitivity of the spectral position of plasmon resonance calculated by numerical methods to a change in the refractive index of the environment for ellipsoidal and spherical silver nanoparticles with a dielectric shell synthesized by laser ablation has been performed. It has been shown that sensitivity is higher for nanoparticles with the shape of a prolate ellipsoid than for spherical nanoparticles. The modeling has shown that the optimal thickness of the dielectric shell should be 10–12 nm and its refractive index should be 1.6. With this, a sensitivity of the plasmon sensor of 32 nm/RIU (RIU is refractive index unit) may be provided.     

Surface plasmon optical sensor with enhanced sensitivity using top ZnO thin film

Surface plasmon resonance (SPR) is one of the most sensitive label-free detection methods and has been used in a wide range of chemical and biochemical sensing. Upon using a 200 nm top layer of dielectric film with a high value of the real part ε′ of the dielectric function, on top of an SPR sensor in the Kretschmann configuration, the sensitivity is improved. The refractive index effect of dielectric film on sensitivity is usually ignored. Dielectric films with different refractive indices were prepared by radio frequency magnetron (RF) sputtering and measured with spectroscopic ellipsometry (SE). The imaginary part ε′′ of the top nanolayer permittivity needs to be small enough in order to reduce the losses and get sharper dips. The stability of the sensor is also improved because the nanolayer is protecting the Ag film from interacting with the environment. The response curves of the Ag/ZnO chips were obtained by using SPR sensor. Theoretical analysis of the sensitivity of the SPR sensors with different ZnO film refractive indices is presented and studied. Both experimental and simulation results show that the Ag/ZnO films exhibit an enhanced SPR over the pure Ag film with a narrower full width at half maximum (FWHM). It shows that the top ZnO layer is effective in enhancing the surface plasmon resonance and thus its sensitivity.     

Surface plasmon resonance response of Au–WO3?x composite films

Surface plasmon resonance of metal–dielectric composite thin films formed by noble metal nanoparticles embedded in a dielectric matrix offers a high degree of flexibility and enables many applications such as surface enhanced spectroscopes, and biological and chemical sensing. In this article, Au–WO_3−x composite films of various Au contents and thicknesses were prepared by the pulsed laser deposition technique, and their SPR responses were measured in the Kreschmann geometry, using a polarized light beam at 640 nm wavelength. Theoretical calculation of SPR responses based on the Bruggeman or Maxwell–Garnett model with the MacLeod general characteristic matrix method is in obvious discrepancy with experimental measurements but it is able to predict the trend in term of the dependence of SPR responses on Au content and thickness of the Au–WO_3−x films. The SPR responses of the Au–WO_3−x films when exposed to NO gas molecules were measured and the preliminary results indicated that gas sensing using the SPR responses of metal–dielectric composite films is feasible.     

Tuning the number of plasmon band in silver ellipsoidal nanoshell: refractive index sensing based on plasmon blending and splitting

Because of the geometric features of both rod and shell, dielectric-silver core–shell ellipsoidal nanostructure with 12–40 nm semi-major axis may bring forth four surface plasmon resonance (SPR) absorption peaks at most. Theoretical calculations based on quasi-static approximation show that there is surrounding refractive index-dependent plasmon blending and splitting in the absorption spectra, which makes the number of plasmon band of the silver ellipsoidal nanoshell is tunable. The sensitivity of the plasmon blending and splitting to the surrounding refractive index may be improved by increasing the shell thickness, aspect ratio or core refractive index. This local refractive index dependent-plasmon blending and splitting presents a new sensing picture based on tuning the number of SPR absorption peaks.     

Optical properties of composite thin films containing silver nanoparticles

Absorption and reflection of electromagnetic radiation by a composite thin film consisting of a transparent dielectric matrix with inclusions of metal nanoparticles of radius much less than the wavelength were theoretically investigated based on the Maxwell–Garnett model. The absorption, reflection, and transmission of optical radiation in such a dielectric composite film were analyzed using effective optical parameters for the refractive index and absorption coefficient that depended on the nanoparticle size.     

Selective suppression of extinction within the plasmon resonance of gold nanoparticles

We present extinction measurements on rectangular two-dimensional arrays of gold nanoparticles on a dielectric waveguide. The spectra exhibit spectrally narrow bands of suppressed extinction within the particle–plasmon resonance, resulting from destructive interference between the incident light field and the excited waveguide modes. The dependence of the spectral position of these high-transmission bands on different waveguide modes is investigated in detail. Received: 3 July 2001 / Published online: 10 October 2001     

Metal nanoparticle-doped coloured films on glass and polycarbonate substrates

In a program on the development of metal (e.g. Au, Ag, Cu and their alloy) nanoparticles in sol-gel derived films, attempts were made to synthesize different coloured coatings on glasses and plastics. The absorption position of surface plasmon resonance (SPR) band arising from the embedded metal nanoparticles was tailored by controlling the refractive index of the matrix for the development of different colours. Thus different coloured (pink to blue) coatings on ordinary sheet glasses were prepared by generating Au nanoparticles in mixed SiO₂-TiO₂ matrices having refractive index values ranging from about 1.41 to 1.93. In another development,in situ generation of Ag nanoparticles in the inorganic-organic hybrid host leads to the formation of different abrasion resistant coloured coatings (yellow to pink) on polycarbonate substrates after curing. As expected, the SPR peak of Ag or Au is gradually red-shifted due to the increase of refractive index of the coating matrices causing a systematic change of colour     

Determination of the refractive index of spherical erythrocytes of human blood in the range 0.3–1.2 µm

A proposed procedure for determining the spectral values of the refractive index of spherical erythrocytes of human blood is based on angular light scattering and the use (for one-time scattering) of a multiple regression equation. A theoretical study of the stability of the relationship between the light scattering indicatrix and the refractive index of erythrocytes toward possible variations of their microstructure parameters is performed in order to select the optimal angles. The precision of the proposed method and its sensitivity to indicatrix measurement uncertainties are estimated. __________ Translated from Zhurnal Prikladnoi Spektroskopii Vol. 74, No. 3, pp. 382–386, May–June, 2007.     

Polarization mapping of nanoparticle plasmonic coupling

We propose the use of polarization mapping as a tool to better separate the effects of plasmonic coupling from the local refractive index for molecular imaging and biosensing using gold nanoparticles. Polarization mapping allows identification of the orthogonal excitation mode when the particle dimer orientation is unknown, as may be the case when using plasmonic nanoparticles for cell labeling. This information can be used to sense relative changes in the dielectric environment, or for absolute dielectric sensing with additional a priori interparticle distance information. First, the theoretical scattering by nanoparticle pairs is modeled under parallel and orthogonal polarization orientations and increasing interparticle separation. Second, polarization mapping of substrate bound nanoparticles using dark-field microspectroscopy is investigated as a method to isolate the individual plasmonic coupling modes associated with a pair of nanoparticles without reorientation of the sample. The results of this study provide useful insight toward potential avenues for monitoring distances using plasmonic nanoparticles and sensing the local refractive index using nanoparticle pairs when the pair orientation is not known, as may be the case when using nanoparticles for cell receptor labeling.     

Effect of metallic nanoparticle sizes on the local field near their surface

We have used numerical calculations based on Mie theory to analyze the near field distribution patterns for 4–150 nm spherical silver nanoparticles (nanospheres). We have shown that as the nanoparticle sizes increase, the region where “hot spots” are concentrated is shifted to the forward hemisphere. We have observed a nonmonotonic dependence of the maximum attainable local field enhancement factor on the size of the silver nanospheres. We have determined a correlation between the optimal nanosphere size for the maximum attainable local field enhancement factor and the optical absorption efficiency factor. We have established a nonmonotonic dependence of the optimal size of the nanoparticles and the maximum attainable local field enhancement factor on the refractive index of the surrounding medium. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 831–837, November–December, 2008.     

胶体金纳米颗粒的表面等离子体发射特性

利用电化学方法制备出粒径为20-80 nm的胶体金纳米颗粒。研究其荧光发射光谱特性,在485nm处观察到表面自由电子集体激发导致的表面等离子体共振发射峰,其位置不随激励光波长的变化而移动。当激励光波长为485 nm时,观察到最强的发射峰。在240和640 nm处,还观察到倍频发射峰和3/4分频发射峰。增加金纳米颗粒粒径,观察到发射谱的峰值增大而发射峰的位置只有很小的红移。     

Evaluation of nonlinear optical parameters of TiN/PVA nanocomposite – A comparison between semi empirical relation and Z-Scan results

We report on the third order non linearity of TiN/PVA nanocomposites. Linear and nonlinear optical properties were studied from theoretical and experimental method. Theoretical method involved Tichy and Ticha relation pooled with generalised Miller's rule. During the study dispersion of refractive index is analysed using the Wemple–Di Domenico single oscillator model. Z-Scan was used as the experimental tool. The results derived from theoretical method deviated greatly from the experimental. We believe that such incongruity is due to the SPR property of the TiN nanoparticle whose SPR peak almost coincides with the irradiated laser wavelength.     

Design and Fabrication of GaInAsP/InP VCSEL with Two a-Si/a-SiN x Bragg Reflectors

We report on the design and fabrication of a 1.55 μm wavelength Vertical Cavity Surface Emitting Lasers (VCSELs) which consists of two dielectric Bragg mirrors and a InGaAsP-based active region. The dielectric materials are amorphous silicon and amorphous silicon nitride. Layers of such materials have been deposited by magnetron sputtering and analyzed in order to determine their optical properties. A large refractive index difference of 1.9 is found between these materials. Distributed Bragg Reflectors (DBRs) based on these dielectric materials quarter wave layers have been studied by optical measurements and confronted to theoretical calculations based on the transfer matrix method. A maximum reflectivity of 99.5% at 1.55 μm and a large spectral bandwidth of 800 nm are reached with only four and a half periods of a-Si/a-SiN_x. The VCSEL was fabricated by metallic bonding process. This method allows to bond an InP-based active region as the gain medium on a Si substrate thanks to the formation of a Au–In alloy. This process is performed at a low temperature of 240°C without damaging the optical properties of the microcavity. This VCSEL has been characterized by an optical pumping experiment with a low and a high-density optical power and a laser emission has been obtained at room-temperature.     

Concentration variations in the optical pseudogap and refractive index of crystals of Cu6PS5I1–xClx solid solutions

The effect of anionic substitution of halogen atoms on the spectral position and shape of the optical absorption edge and the dispersion of the refractive index of crystals of Cu₆PS₅I_1–xCl_x solid solutions are studied. The concentration dependences of the width of the optical pseudogap, refractive index, and lattice parameters are shown to be interrelated in these solid solution crystals.     

Plasmon resonances in a two-dimensional lattice of metal particles in a dielectric layer: Structural and polarization properties

The results of experimental and theoretical investigation of planar two-dimensional (2D) samples of plasmon structures are presented. The samples represent a 2D lattice of gold nanoparticles embedded in a thin dielectric layer and are studied by atomic force microscopy (AFM) and optical methods. Absorption bands associated with the excitation of various surface plasmon resonances (SPR) are interpreted. It is found that the choice of the mutual orientation of the polarization plane and the edge of the unit cell of the 2D lattice determines the spectral position of the lattice surface plasmon resonance (LSPR) related to the lattice period. It is shown that the interaction of p- and s-polarized light with a 2D lattice of nanoparticles is described by the dipole–dipole interaction between nanoparticles embedded in a medium with effective permittivity. Analysis of the spectra of ellipsometric parameters allows one to determine the amplitude and phase anisotropy of transmission, which is a consequence of the imperfection of the 2D lattice of samples.     

Spectral measurements of dielectric characteristics of petroleum and petroleum oils in the millimeter wave range

We obtain experimental data on the complex refractive index N = n+ik of petroleum, five petroleum oils, and water-petroleum emulsion in the frequency range f = 75–120 GHz. Measurements were performed in a quasioptical equipment with a backward-wave oscillator generating the radiation and an OAP-7 optical-acoustic receivers for a temperature of 27°C of studied liquids. The refractive indices n of petroleum and oil have a weak negative dispersion (dn/df < 0) and close values. At a frequency of 100 GHz, they lie in the range n = 1.477–1.495. The absorption indices k have different frequency dependences such that k increases for four oils, while it decreases for petroleum and SM-4.5 oil with increasing f. At the frequency f = 100 GHz, the values of k vary in a wide range from 2.4 · 10⁻⁴ to 1.7 · 10⁻³. The measurement results for petroleum and oils are compared with experimental results obtained by other authors. The frequency dependences of n and k of water-petroleum emulsion for water concentrations 0.11% and 0.58% are compared with the data calculated using various analytical models of dielectric mixtures. The dependences n(f) and k(f) calculated by the Kubo-Nakamura formula are the closest to the experimental data. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 50, No. 6, pp. 485–495, June 2007.     

Novel model for the optical function of GaN

In this work we propose an analytical expression for the complex dielectric function which includes both discrete and continuum exciton effects. We have introduced Lorentzian broadening into Elliott’s formula. The introduction of broadening leads to equations for the dielectric function containing only elementary functions. We have applied the proposed model to the dielectric function of wurtzite GaN in the spectral region 1–10 eV. Excellent agreement with the experimental data has been obtained. We show that the Lorentzian-broadened dielectric function decays more slowly than the experimental data for hexagonal GaN at the low-energy side. This indicates that the broadening of the absorption edge in GaN is not purely Lorentzian. The agreement with the experimental data can be improved using adjustable broadening modification. Received: 29 January 2001 / Accepted: 30 May 2001 / Published online: 25 July 2001     

Construction of the refractive index profiles for few-mode planar optical waveguides

We present a nondestructive technique to predict the refractive index profiles of isotropic planar waveguides, on which a thin gold film is deposited to as the cladding. The negative dielectric constant of the metal results in significant differences of effective indices between TE and TM modes. The two polarized modes and a surface plasmon resonance (SPR) with abundant information of the surface index can be used to construct the refractive index profiles of single-mode and two-mode waveguides at a fixed wavelength.     

侧边抛磨的U型金溅射塑料光纤等离子体共振传感器

为了测量溶液折射率变化，对塑料光纤纤芯表面的纤芯-金层-液体的3层膜结构进行研究，制作了一种使用U型结构并结合侧边抛磨方法的表面等离子体共振传感器。将截取的一段塑料光纤弯曲成为U型，并在烘箱中通过较高温度使这段光纤的曲率固定，对弯曲部分的外表面进行抛光，暴露该位置塑料光纤芯层并在其上溅射金纳米薄膜层，将制备好的传感器浸入不同折射率的液体中，使用光谱分析仪观察光谱的移动。实验结果表明:当塑料光纤SPR传感器测量折射率变化范围在1.333~1.406的液体时，可以通过光谱观察到随着液体折射率的增大，等离子体共振吸收峰位置也不断地向波长增大的方向移动，并且二者之间存在线性关系，其灵敏度为7.5×10-4 RIU/nm。该传感器探头具有灵敏度高、小型化、易制备、低成本的特点。