Revisiting the physical processes of vapodeposited thin gold films on chemically modified glass by atomic force and surface plasmon microscopies

The preparation of very thin (at the scale of a few tens of nanometers) gold films by thermal evaporation and deposition on a solid substrate (glass) remains a key step for the elaboration of transparent and sensitive optical biosensors. We study the influence of the glass surface treatment and its thermal conductivity on the structure and composition of evaporated gold films. Using a combination of atomic force microscopy (AFM), high resolution surface plasmon resonance (SPR) imaging, and X-ray photoelectron spectroscopy (XPS), we demonstrate that the grafting of a layer of long chain mercaptant, using 11-mercaptoundecyltrimethoxysilane (S_ξSi), prior to gold deposition produces a drastic modification of gold inner and surface textures. A thorough investigation of AFM image topography by 2D wavelet-based segmentation method reveals the flat conical shape of the gold surface grains and their shape invariance with the glass surface chemical treatment. However, this treatment leads to a drastic decrease of the mean size and polydispersity of these grains by a factor of 2, thereby lowering the gold surface roughness. The rationale is that the combination of surface forces and thermal transfer drives the formation of homogeneous and flatter gold films.     

氧化钛薄膜调控金属铜的表面等离子体共振特性研究

提出了一种利用氧化钛薄膜对金属铜薄膜表面等离子体共振特性调制的想法。实验中首先使用电子束蒸发制备一批同等厚度的氧化钛薄膜,再利用磁控溅射方法在氧化钛薄膜上沉积厚度为5～80 nm不等的金属铜薄膜。测试结果表明,氧化钛膜层对不同厚度的金属铜薄膜表面等离子体共振增强具有不同调制效果,金属铜薄膜厚度小于20 nm时,底层的氧化钛薄膜对Cu薄膜表面等离子体共振增强效果显著,且随着金属Cu膜层厚度增加表面等离子体共振峰发生蓝移,而当金属铜膜层的厚度超过20 nm时,共振增强效果因金属Cu薄膜消光能力的上升而开始减弱。     

Functional and optical properties of Au:TiO2 nanocomposite films: The influence of thermal annealing

A set of nanocomposite thin films consisting of Au nanoclusters dispersed in a TiO₂ dielectric matrix was deposited by reactive magnetron sputtering, and subjected to thermal annealing in vacuum, at temperatures ranging from 200 to 800 °C. The obtained results show that the structure and the size of Au clusters, together with the matrix crystallinity, changed as a result of the annealing, and were shown to be able to change the optical properties of the films and keeping good mechanical properties, opening thus a wide number of possible applications. The crystallization of the gold nanoclusters induced by the annealing was followed by a systematic change in the overall coating behaviour, namely the appearance of surface plasmon resonance (SPR) behaviour. This effect enables to tailor the thin films reflectivity, absorbance and colour coordinates, contributing to the importance of this thin film system. The different attained optical characteristics (reflectance values ranging from interference to metallic-like behaviours and colour varying for interference rainbow-like to several tones of red-brownish), associated with a reasonable mechanical resistance of the coatings (good adhesion to different substrates and hardness values ranging from 5 to 7.5 GPa), induce the possibility to use this film system in a wide range of decorative applications.     

Investigation of the surface properties of gold nanowire arrays

Gold nanowire arrays with diameters ranging from 45 to 200 nm were obtained via electrochemical deposition within the ion-track templates. The morphology of gold nanowires was imaged by scanning electron microscopy (SEM). The surface properties were investigated by surface plasmon resonance (SPR) and X-ray photoelectron spectroscopy (XPS). The SPR peaks were observed as the gold nanowire arrays embedded in the templates and their intensity decreased after the sample exposed to the air for a certain time due to the formation of chemisorbed oxygen on nanowire surface. The positive binding energy shifts in Au core level was found when the gold nanowire arrays embodied in template and the initial- and finial-state effects were introduced to explain this phenomenon.     

纳米金表面修饰与表面等离子体共振传感器的相互作用研究

为了分析纳米金表面修饰对表面等离子体共振(SPR)的放大作用,以及其对传感器本身的影响,首先,基于色散介质的吸收理论,通过建立波长型SPR生物传感器四层膜结构的数学模型,理论分析了传感器表面所吸附纳米金对传感器的影响:纳米金的表面修饰,改变了表面等离子体传感器中棱镜表面各介质层内电磁场的能量分布,削弱了金属膜在共振吸收中的作用,从而使SPR曲线的半波宽度增加,最小反射系数增大,金膜的最优膜厚度也随之改变.其次,通过不同厚度的金膜外吸附纳米金的对比试验,验证了此理论.金膜厚45nm、表面修饰10nm纳米金颗 关键词： 表面等离子体共振 生物传感器 纳米金 金属膜     

Spectral modulation of ultra-broadband femtosecond laser pulses based on surface plasmon resonance

The surface plasmon resonance (SPR) for spectral modulation of the femtosecond laser pulses with 110 nm ultra-broad bandwidth is demonstrated on the basis of the development of ultrashort pulse laser sources which supports good spatial resolution and high peak intensity. Employing the femtosecond surface plasmon polariton pulses launched by a Kretschmann configuration, whose reflectivity curve has the characteristic of the ultra-broad bandwidth, we observe a frequency-dependent loss with greater attenuation at the peak of the spectrum profile than in the wings, which is very useful for adequate spectral modulation. The SPR for the spectral modulation is investigated in theoretical and experimental aspects. The arbitrary spectral modulation of the femtosecond laser pulses can be fulfilled by controlling and optimizing the SPR of the gold film. The experimental result agrees well with the calculation.     

Surface plasmon resonance sensor based on diffraction grating with high sensitivity and high resolution

A surface plasmon resonance (SPR) sensor based on diffraction grating with high sensitivity and high resolution is proposed. The sensitivity of grating coupled SPR sensor based on angular interrogation is enhanced by replacing +1st diffraction order of metallic grating with −1st diffraction order to excite the surface plasmon. To improve the resolution of grating-based SPR sensor, aluminum is used as an SPR-active metal. The reflectivity dip of the Al-based sensor is sharper than an Au-based one, which is the mostly widely used as SPR-active metal. And 3-nm-thick gold film is deposited on the grating surface in order to protect the Al layer from getting oxidized. Numerical simulations show that the sensor not only has high sensitivity and high resolution, but also exhibits good linearity.     

Optical method to differentiate tequilas based on angular modulation surface plasmon resonance

We report the use of the prism-based surface plasmon resonance (SPR) technique to differentiate between three types of tequilas white or silver, aged, and extra-aged. We used the angular interrogation method in which the structure is based on prism fabricated with BK7 glass coated with a gold layer as the SPR active layer. Our study was centered in the analysis of the resonant angle of the SPR generated by the three types of tequilas produced by the three major tequila-producing firms. We observed that each tequila sample produced a well-differentiated SPR curve. We found that resonant angle of the SPR curve produced by silver tequilas is larger than that produced by the aged and extra-aged tequilas of the same producer firm. We found that the position of the SPR curve is not exclusively determined by the alcohol contents; we believe that there are other parameters derived from the aging process that should be considered. The refractive index of the tequilas used in this study was estimated using the measured resonant angle.     

Surface plasmon tunneling through a touching gold nanocylinder array on a thin gold film

The optical property of a structure composed of a touching gold nanocylinder array on a thin gold film is investigated using finite-difference time-domain (FDTD) method. It is discovered that the transmission behavior can be tuned by tuning the geometry of the structure. As the film thickness increases, the transmission mode associated with the localized surface plasmon resonance blue shifts accompanied with a decrease of magnitude and full width at half maximum, and a second transmission appear due to the interaction of the plasmons on the cylinder with their images induced on the film. The localized waveguide resonance diminishes but the second resonance peak is intensified and broadened noticeably with the separation of the cylinder array and film increase. The cylinder radius size influences the localized surface plasmon resonance mode obviously. These results may be helpful for the design of a novel optical device.     

Fiber optic sensor based on surface plasmon resonance with nanoparticle films

This paper reports on a novel design of a fiber optic surface plasmon resonance (SPR) sensor based on nanoparticle metal film. The performance of the proposed sensor in terms of its signal-to-noise ratio (SNR) and sensitivity under different conditions related to the film with spherical gold nanoparticles embedded in a host material is theoretically analyzed. In particular, the effect of the parameters such as gold particle size, film thickness, and refractive index of host material is studied and the possible explanation, whenever required, is given. The numerical results presented in this paper leads to fulfill the requirement of significant optimization of the important design parameters to achieve a high SNR and sensitivity of a fiber optic SPR sensor with nanoparticle films.     

Enhanced surface plasmon resonance detection using porous ITO–gold hybrid substrates

We demonstrated enhanced surface plasmon resonance (SPR) detection by incorporating an indium tin oxide (ITO) layer on a thin gold film. Porous ITO layers were fabricated by e-beam evaporation and slanted deposition at room temperature and the ITO structure was optimized in terms of the surface roughness and the SPR curve characteristics. In sensing experiments, the results obtained by ethanol–water mixture test showed that SPR substrates with a porous ITO layer provided a notable sensitivity improvement compared to a conventional bare gold film, which is attributed to the nonlinear dispersion characteristic of surface plasmons. Our approach is intended to show the feasibility and extend the applicability of the porous ITO-mediated SPR biosensor to diverse biomolecular binding events.     

功能光学纳米Ag薄膜的制备及其光学特性研究

对以热蒸发法制备的超薄Ag薄膜,扫描电子显微镜结果显示其呈纳米尺度的颗粒状,由透射谱测量发现其具有表面等离子体激元特征.检测到不同条件制备纳米Ag薄膜的表面等离子体共振吸收峰的位移规律,且纳米Ag材料具有选择性的透过、反射特性.通过不同的制备条件,得到了在长波范围内透过率超过90％、在表面等离子体共振峰值位置处反射率接近50％且峰位可调的光学薄膜材料.这种薄膜材料有望成为应用在薄膜太阳电池中间层中具有潜在性光管理功能的光学薄膜材料. 关键词： 热蒸发 纳米Ag薄膜 表面等离子体激元 光管理     

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。     

Optical fiber SPR biosensor with sandwich assay for the detection of prostate specific antigen

We present a new, sensitive, few mode fiber (FMF) surface plasmon resonance (SPR) biosensor with a sandwich assay for the detection of PSA. The side-polished FMF biosensor does not need a polarizer and a thin high-index overlayer. The optical sensitivity of the SPR sensor was determined as 2.5 × 10⁻⁶ RIU. In the SPR PSA sensor, the SPR signals were amplified by a factor of 6 in average over no secondary antibody, using the sandwich assay. The proposed FMF SPR biosensor has great potential for real-time analysis of immune reaction between biomolecules and the advantages of high-sensitivity and label-free detection.     

Interfacial kinetic enhancement of metal ion adsorption on binary mixed self-assembled monolayers

The adsorption of metal ions, a type of surface reaction on binary mixed self-assembled monolayers (SAMs) on a gold surface composed of 1,6-hexanedithiol (HDT) with 11-mercaptoundecanoic acid (MUA), was monitored by in situ surface plasmon resonance (SPR) measurements. The differential SPR reflectance (ΔR) enables the kinetics of adsorption of Pt²⁺ on the mixed SAMs to be investigated. Unlike single HDT SAM, kinetic analyses of the mixed SAMs showed that the rate of adsorption of Pt²⁺ was enhanced and that it was highly dependent on the fraction of MUA present. These SPR measurements suggest that the adsorption rate of metal ions can be readily manipulated simply by using mixed SAMs.     

Effects of post-thermal annealing temperature on the optical and structural properties of gold particles on silicon suboxide films

In this work, silicon suboxide (SiO_x) thin films were deposited using a RF magnetron sputtering system. A thin layer of gold (Au) with a thickness of about 10 nm was sputtered onto the surface of the deposited SiO_x films prior to the thermal annealing process at 400 °C, 600 °C, 800 °C and 1000 °C. The optical and structural properties of the samples were studied using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and optical transmission and reflection spectroscopy. SEM analyses demonstrated that the samples annealed at different temperatures produced different Au particle sizes and shapes. SiO_x nanowires were found in the sample annealed at 1000 °C. Au particles induce the crystallinity of SiO_x thin films in the post-thermal annealing process at different temperatures. These annealed samples produced silicon nanocrystallites with sizes of less than 4 nm, and the Au nanocrystallite sizes were in the range of 7-23 nm. With increased annealing temperature, the bond angle of the Si-O bond increased and the optical energy gap of the thin films decreased. The appearance of broad surface plasmon resonance absorption peaks in the region of 590-740 nm was observed due to the inclusion of Au particles in the samples. The results show that the position and intensity of the surface plasmon resonance peaks can be greatly influenced by the size, shape and distribution of Au particles.     

后退火处理对铟锡氧化物表面等离激元共振特性的影响

近年来,表面等离激元光子学发展迅速,并取得了众多新成果.重掺杂半导体材料的表面等离激元共振性质的研究,也得到了人们越来越多的关注.本文通过纳米球刻印技术制备准三维二氧化硅纳米球阵列,在阵列上沉积铟锡氧化物薄膜,通过不同条件下的后退火处理改变铟锡氧化物薄膜的载流子浓度和载流子迁移率,并研究随着材料性质的改变其相应表面等离激元共振特性的变化规律.结果表明：退火处理均使铟锡氧化物薄膜的晶粒长大,光学透过率增加;在空气中退火会导致铟锡氧化物薄膜的载流子浓度减少,其表面等离激元共振峰红移;而真空退火则使铟锡氧化物薄膜的载流子浓度增加,共振峰蓝移.这些研究结果可为后续铟锡氧化物表面等离激元材料及器件的研究提供科学依据和实际指导.     

Quantitative model for the change of optical resonance in neural activity detection systems based on surface plasmon resonance

The mechanism of neural activity detection using the surface plasmon resonance (SPR) phenomenon was theoretically explored in this paper. Investigating the mechanism of SPR neural recordings has been difficult due to the complex relationship between different physiological and physical processes such as excitation of a nerve fiber and coherent charge fluctuations on the metal surface. This paper examines how these different processes may be connected by introducing a set of compartmental theoretical models that deal with the molecular scale phenomena; Poisson-Boltzmann (PB) equation, which was used to describe the ion concentration change under the time varying electrostatic potential, Drude-Lorentz electron model, which was used to describe electron dynamics under the time varying external forces, and a Fresnel's three-layered model, which expresses the reflectivity of the SPR system in terms of the dielectric constants. Each physical theoretical model was numerically analyzed using the finite element method (FEM) formulated for the PB equation and the Green's method formulated for the Drude-Lorentz electron equation. The model predicts that the ionic thermal force originating from the opening of the K⁺ ion channel is fundamental for modifying the dipole moment of the gold's free electron; thus, the reflectivity is changed in the SPR system. The discussion was done also on important attributes of the SPR signal such as biphasic fluctuation and the electrical noise-free characteristics.     

The film thickness dependent thermal stability of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>:Ag thin films as high-temperature solar selective absorbers

The monolayer Al₂O₃:Ag thin films were prepared by magnetron sputtering. The microstructure and optical properties of thin film after annealing at 700 °C in air were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and spectrophotometer. It revealed that the particle shape, size, and distribution across the film were greatly changed before and after annealing. The surface plasmon resonance absorption and thermal stability of the film were found to be strongly dependent on the film thickness, which was believed to be associated with the evolution process of particle diffusion, agglomeration, and evaporation during annealing at high temperature. When the film thickness was smaller than 90 nm, the film SPR absorption can be attenuated until extinct with increasing annealing time due to the evaporation of Ag particles. While the film thickness was larger than 120 nm, the absorption can keep constant even after annealing for 64 h due to the agglomeration of Ag particles. On the base of film thickness results, the multilayer Al₂O₃:Ag solar selective thin films were prepared and the thermal stability test illustrated that the solar selectivity of multilayer films with absorbing layer thickness larger than 120 nm did not degrade after annealing at 500 °C for 70 h in air. It can be concluded that film thickness is an important factor to control the thermal stability of Al₂O₃:Ag thin films as high-temperature solar selective absorbers.     

基于表面等离子体共振传感器的金胶体表征

设计了表面等离子体共振(SPR)传感器实验装置,制备了金膜和金纳米胶体溶液,测量了不同厚度金膜和不同浓度金胶体溶液的SPR角谱,得到了不同浓度金胶体溶液的折射率.