Reversible adsorption of Au nanoparticles on SiO2/Si: An in situ ATR-IR study

Adsorption and desorption of Au nanoparticles (AuNP) on the (aminopropyl)triethoxysilane (APTES) treated SiO₂/Si surface was monitored by in situ attenuated total reflection (ATR) infrared spectroscopy in combination with a liquid flow cell. With increasing the AuNP coverage at the surface, the absorption by water vibration was increased due to surface enhanced infrared absorption (SEIRA). Repulsive electrostatic forces between the incoming AuNP and the already adsorbed AuNP layer lead to saturation at submonolayer coverage of the surface. We clarified that the adsorption process can be described very well by a diffusion limited first-order Langmuir-kinetics model. Furthermore, we show that the AuNPs desorb from the surface when they are exposed to the solution of aminoethanethiol (AET).     

Charge-transfer enhancement in infrared absorption of thiocyanate ions adsorbed on a gold electrode in the Kretschmann ATR configuration

The intensity of an enhanced infrared absorption of SCN⁻ ions adsorbed on an Au film electrode reaches a maximum at a negative electrode potential, where the number of adsorbed ions should be smaller than at higher potentials. In addition, the enhancement of infrared absorption is restricted to species adsorbed directly on the electrode surface. These observations suggest that a charge-transfer enhancement is working on the infrared absorption of the SCN⁻/Au electrode system. A probable precursor of the thiocyanato complex of Au was detected in the same system.     

Portable smart films for ultrasensitive detection and chemical analysis using SERS and SERRS

Metallic nanostructures, much smaller than the wavelength of visible light, which support localized surface plasmon resonances, are central to the giant signal enhancement achieved in surface‐enhanced Raman scattering (SERS) and surface‐enhanced resonance Raman scattering (SERRS). Plasmonic driven SERS and SERRS is a powerful analytical tool for ultrasensitive detection down to single molecule detection. For all practical SERS applications a key issue is the development of reproducible and portable SERS‐active substrates, where the most widely used metals for nanostructure fabrication are silver and gold. Here, we report the fabrication of a ‘smart film’, containing gold nanoparticles (AuNPs), produced by in situ reduction of gold chloride III (Au⁺³) in natural rubber (NR) membranes for SERS and SERRS applications. The composite films (NR/AuNP membranes) show characteristic plasmon absorption of Au nanostructures, which notably do not influence the mechanical properties of the NR membranes. The term ‘smart film’ has to do with the fact that the SERS substrate (smart film) is flexible and standalone, which allows one to take it anywhere and to dip it into solutions containing the analyte to be characterized by SERS or SERRS technique. Besides, the synthesis of the AuNPs at the surface of NR films is much simpler than making an Au colloid and cast it onto a substrate surface or preparing an Au evaporated film. Copyright © 2012 John Wiley & Sons, Ltd.     

Deposition of Au/TiO2 film by pulsed laser

Au nanoparticles, which were photoreduced by a Nd:YAG laser in HAuCl₄ solution containing TiO₂ colloid and accompanied by the TiO₂ particles, were deposited on the substrate surface. The film consisting of Au/TiO₂ particles was characterized by the absorption spectra, scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis. The adhesion between the film and substrate was evaluated by using adhesive tape test. It was found that the presence of TiO₂ dramatically enhanced the adhesion strength between the film and the substrate, as well as the deposition rate of film. The mechanism for the deposition of Au/TiO₂ film was also discussed.     

Infrared and Raman spectroscopies of InP/II–VI core-shell nanoparticles

We use infrared (IR) and Raman spectroscopies to investigate the optically active phonon modes in InP nanoparticles and InP/II–VI core-shell nanoparticles fabricated by similar colloidal chemistry methods. The IR transmission spectra of several InP nanoparticle samples exhibit a common absorption feature, which we assign to the Fröhlich mode. The Raman results for the same samples show transverse and longitudinal optical phonon peaks, and scattering strength in between due to surface optical (SO) modes. Infrared spectra of the InP/ZnSe core-shell nanoparticles () exhibit three absorption features, one due to the InP core, and the others associated with the ZnSe shell layer. Raman measurements (12–292 K) also show three phonon-related peaks, whose intensities vary sharply with temperature. The frequencies of the IR and Raman lines are in approximate accord with dielectric continuum theory.     

Structure and Orientation of 1-Hydroxyl-5-Hexadecyloxy-Naphthalene LB Films Studied By UV-VIS and FTIR Spectroscopy

Ultraviolet-visible (UV-Vis), infrared transmission, and reflection absorption(RA) spectra have been measured for one-and multi-monolayer Langmuir-Blodgett(LB) films of C₁₆H₃₃30Naph(1,5)OH at various temperature to investigate dependencies of the aggregation and phase transitions on the number of monolayers. The UV-vis spectra of the LB films have revealed that the C₁₆H₃₃ONaph(1,5)OH forms aggregates in the LB film. From the temperature dependence of UV-vis absorption spectra, it is clear that the aggregate is gradual converted to monomer upto 80 °C. A comparison of the infrared transmission and RA spectra reveals that the hydrocarbon chains are tilted considerably in the LB film. As for the naphthalene ring part, the result suggest that the ring plane is oriented approximately perpendicular to the substrate surface. The Temperature dependence of infrared transmission spectra have been measured for 1-, 3-, and 11-monolayer LB films to investigate dependence of phase transitions on the number of monolayers. These observations show that the one-monolayer LB films does not have a clear order-disorder transition, while the three-and eleven-monolayer films have a phase transition near 60 °C. Therefore, it seems that the title angles of both the alkyl chain and chromophore part change largely concomitantly with the conversion from the aggregate to the monolayer.     

Large enhancement of Faraday rotation by localized surface plasmon resonance in Au nanoparticles embedded in Bi:YIG film

A large enhancement of the Faraday rotation, which is associated with localized surface plasmon resonance (LSPR), was obtained in a sample with Au nanoparticles embedded in a Bi-substituted yttrium iron garnet (Bi:YIG) film. On a quartz substrate, Au nanoparticles were formed by heating an Au thin film, and a Bi:YIG film was then deposited on them. A sample containing the Au nanoparticles produced by 1000 °C heating showed a resonant attenuation with narrower bandwidth in the transmission spectrum than nanoparticles of other samples formed by low-temperature heating. The sharp resonant Faraday rotation angle was 4.4 times larger than the estimated intrinsic Bi:YIG film at the LSPR wavelength; the angular difference was 0.14°. A discrepancy in the bandwidth between the transmission attenuation and the resonant Faraday rotation is discussed.     

膜结构对金纳米线阵列表面增强拉曼散射的影响

金纳米线阵列作为表面增强拉曼散射的基底能够产生有效的增强效应,金纳米线阵列通过金线之间的电场耦合产生增强的拉曼信号。在实验中,制备出金纳米线阵列与金纳米刷,两种样品结构不同,金纳米刷的一面带有金膜。用巯基吡啶作为探针分子,金纳米刷的SERS实验显示出很好的增强效应,增强因子为106,不同位点的SERS谱具有区域不均一的特征。而相同实验条件下的金纳米线阵列的增强因子只有102。光学吸收谱表明这两种结构均发生了共振吸收增强电场,对其结构的分析表明,这两种结构具有不同的电场局域化分布,同时金纳米刷中金线上端强烈的电场耦合,这是其具有更好的增强效用的原因。同时,4-MP的表面增强拉曼谱的变化特征体现了化学增强效应的影响。     

Rapid microwave-assisted synthesis and electrochemical characterization of gold/carbon nanotube composites

Hybrid nanostructures composed of gold nanoparticles (NPs) and carbon nanotubes (CNTs) have been prepared by a microwave-assisted method in the mixed solvents of oleylamine and oleic. The morphology, structure and composition of as-obtained Au/CNT composites are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD). The composites show characteristic plasmon absorption of Au NPs in the Ultraviolet–visual spectrum. Fourier transform infrared spectrum shows the successful introduction of functional groups on the surface of CNTs, which are crucial factors to assist the nucleation in situ of Au NPs on the surface of CNTs. Electrochemical measurements show the enhancement electrochemical response for the gold electrode modified with Au/CNT composites.     

苯硫酚吸附在新型Ag-Au合金纳米粒子上的表面增强拉曼光谱研究

以柠檬酸钠同时还原制备的Ag-Au合金纳米粒子为种子,用盐酸羟胺进一步使其生长得到粒径为40～60 nm的新型Ag-Au合金纳米粒子,采用UV-Vis光谱和TEM对纳米种子和再生长后的纳米粒子分别进行表征。两种粒子的UV-Vis光谱均只观察到一个等离子体共振峰,其频率随金的摩尔分数(x_Au)增加而红移,且TEM图像表明这两种粒子的颜色均一,因此判断这两种粒子均为合金结构。以苯硫酚为探针分子,研究了该新型合金纳米粒子的表面增强拉曼光谱(SERS),结果表明吸附了苯硫酚的合金纳米粒子的紫外最大吸收峰红移,并在近红外区出现聚集体的吸收峰。在632.8 nm波长激发下,由于表面等离子体共振效应Au上的SERS信号最强,而合金纳米粒子上的SERS信号随x_Au增大而增强。     

Preparation and property of polyvinyl alcohol-based film embedded with gold nanoparticles

Gold nanoparticles were prepared by a simple heat-treated method using polyvinyl alcohol (PVA) as reducing and stabilizing agent in this article. UV/Vis spectroscopy was used to monitor the preparation. The formation of a sharp band at ~530 nm in the UV/Vis spectra and morphological characters revealed by transmission electron microscopy indicated the generation of Au nanoparticles. The PVA film embedded with Au nanoparticles was prepared by flow casting method and characterized by thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectra, and X-ray photoelectron spectroscopy. The results showed that Au nanoparticles embedded in PVA film can improve the thermal stability of the film under investigation, leading to interesting technological applications.     

银镜法制备具有表面增强红外活性Ag纳米粒子的探讨

利用银镜法在玻璃基底上沉积金属银制得表面增强红外材料,扫描电镜显示,沉积在基片上的银为球状颗粒,且平均直径在100nm左右,银纳米粒子形成一个个不相连的金属岛。以邻硝基苯胺为探针分子,用衰减全反射法(ATR)考察了邻硝基苯胺在银镜基底上的表面增强红外光谱。结果表明:邻硝基苯胺的最小检出质量约为40ng,增强因子约为70。制备银膜的最佳条件为:A gNO3质量分数为1%,反应温度为60℃,且加入表面活性剂可使银纳米粒子分散均匀。     

Microstructure and optical absorption of Au-MgF2 nanoparticle cermet films

The microstructure and optical absorption of Au-MgF2 nanoparticle cermet films with different Au contents are studied. The microstructural analysis shows that the films are mainly composed of the amorphous MgF2 matrix with embedded fcc Au nanoparticles with a mean size of 9.8-21.4nm. Spectral analysis suggests that the surface plasma resonance （SPR） absorption peak of Au particles appears at λ=492-537nm. With increasing Au content, absorption peak intensity increases, profile narrows and location redshifts. Theoretical absorption spectra are calculated based on Maxwell-Garnett theory and compared with experimental spectra.     

界面自组装的金/氧化石墨烯复合材料的表面增强拉曼散射行为研究

采用Frens法制备金纳米粒子溶胶,通过界面自组装技术在掺磷的非晶碳衬底表面构筑三维的金/氧化石墨烯/金复合结构.以罗丹明B为探针分子,考察金/氧化石墨烯/金复合材料的表面增强拉曼散射活性.结果表明,由于氧化石墨烯的化学增强和金纳米粒子的电磁场增强的协同作用,在该三维复合材料上获得了很强的罗丹明B拉曼信号.所设计的三维金/氧化石墨烯/金复合材料在生物分析、环境监测、疾病防控、食品安全等领域具有潜在的应用价值.     

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.     

Synthesis and structural properties of polypyrrole/nano-Y2O3 conducting composite

In this work, polypyrrole/nano-Y₂O₃ conducting composite was synthesized by chemical oxidative polymerization. The composite was characterized using transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectra, UV-vis absorption spectra, X-ray photoelectron spectroscopy and electrical conductivity measurements. The results indicate that Y₂O₃ nanoparticles are almost enwrapped by polypyrrole. The addition of Y₂O₃ nanoparticles results in changes in the surface structure and conductivity of the composite. Thermogravimetric analysis shows that composite has better thermal stability than that of pure polypyrrole.     

Synthesis of bismuth nanocap arrays on quartz substrates and their surface plasmon resonance properties

Bismuth nanocap arrays have been prepared by vacuum depositing Bi films onto the surfaces of self-assembled monolayer arrays of SiO₂ nanoparticles. The surface morphologies, structures, and optical properties of the obtained samples have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscope (AFM), X-ray diffraction (XRD), and ultraviolet–visible–near infrared (UV–vis–NIR) spectrophotometer. TEM and AFM images indicated that the SiO₂/Bi composite nanoparticles were incompletely encapsulated and their surfaces were relatively rough. UV–vis–NIR absorption spectra showed that Bi nanocap arrays had strong and tunable surface plasmon resonance peaks in the visible and near infrared regions, which were dependent dramatically on the relative ratio of the SiO₂ core diameter to the Bi cap thickness.     

Silver,gold and the corresponding core shell nanoparticles: synthesis and characterization

Simple strategies for producing silver and gold nanoparticles (AgNP and AuNP) along with the corresponding core shell nanoparticles (Au–Ag and Ag–Au) by reduction of the metal salts AgBF₄ and HAuCl₄ by NaBH₄ in water will be presented. The morphologies of the obtained nanoparticles are determined by the order of addition of reactants. The obtained NPs, with sizes in the range 3–40 nm, are characterized by transmission electronic microscopy (TEM) and UV–Vis absorption spectroscopy, so as to evaluate their qualities. Moreover, a direct electrochemical detection protocol based on a cyclic voltammetry in water solution that involves the use of glassy carbon electrode is also applied to characterize the prepared NPs. The developed NPs and the related electroanalytical method seem to be with interest for future sensing and biosensing applications including DNA sensors and immunosensors.     

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。     

Au/SiO2纳米复合薄膜的微结构及光吸收特性研究

用多靶磁控溅射技术制备了Au/SiO₂纳米多层薄膜.利用透射电子显微镜以及吸 收光谱对Au/SiO₂复合薄膜的微观结构、表面形貌及光学性能进行了表征和测试 .研究结果表明：单层Au/SiO₂薄膜中Au沉积时间小于10s时，分散在SiO_{2< /sub>中的Au颗粒随Au的沉积时间的延长而增大；当沉积时间超过10s后，Au颗粒的尺寸几乎 不随沉积时间变化，但Au颗粒的形状由网络状结构变为薄膜状结构.［Au(t1关键词： 尺寸效应 纳米复合薄膜 吸收光谱 有效媒质理论}