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.     

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}     

Transport and abatement of fluorescent silica nanoparticle (SiO<Subscript>2</Subscript> NP) in granular filtration: effect of porous media and ionic strength

The extensive production and application of engineered silica nanoparticles (SiO₂ NPs) will inevitably lead to their release into the environment. Granular media filtration, a widely used process in water and wastewater treatment plants, has the potential for NP abatement. In this work, laboratory-scale column experiments were performed to study the transport and retention of SiO₂ NPs on three widely used porous materials, i.e., sand, anthracite, and granular activated carbon (GAC). Synthetic fluorescent core-shell SiO₂ NPs (83 nm) were used to facilitate NP detection. Sand showed very low capacity for SiO₂ filtration as this material had a surface with limited surface area and a high concentration of negative charge. Also, we found that the stability and transport of SiO₂ NP were strongly dependent on the ionic strength of the solution. Increasing ionic strength led to NP agglomeration and facilitated SiO₂ NP retention, while low ionic strength resulted in release of captured NPs from the sand bed. Compared to sand, anthracite and GAC showed higher affinity for SiO₂ NP capture. The superior capacity of GAC was primarily due to its porous structure and high surface area. A process model was developed to simulate NP capture in the packed bed columns and determine fundamental filtration parameters. This model provided an excellent fit to the experimental data. Taken together, the results obtained indicate that GAC is an interesting material for SiO₂ NP filtration.     

Dewetting process of Au films on SiO2 nanowires: Activation energy evaluation

SiO₂ nanowires gain scientific and technological interest in application fields ranging from nano-electronics, optics and photonics to bio-sensing. Furthermore, the SiO₂ nanowires chemical and physical properties, and so their performances in devices, can be enhanced if decorated by metal nanoparticles (such Au) due to local plasmonic effects.In the present paper, we propose a simple, low-cost and high-throughput three-steps methodology for the mass-production of Au nanoparticles coated SiO₂ nanowires. It is based on (1) production of the SiO₂ nanowires on Si surface by solid state reaction of an Au film with the Si substrate at high temperature; (2) sputtering deposition of Au on the SiO₂ nanowires to obtain the nanowires coated by an Au film; and (3) furnace annealing processes to induce the Au film dewetting on the SiO₂ nanowires surface. Using scanning electron microscopy analyses, we followed the change of the Au nanoparticles mean versus the annealing time extracting values for the characteristic activation energy of the dewetting process of the Au film on the SiO₂ nanowires surface. Such a study can allow the tuning of the nanowires/nanoparticles sizes for desired technological applications.     

Fabrication and characterization of Au/SiO2 nanocomposite films grown by radio-frequency cosputtering

Au/SiO₂ nanocomposite films were prepared on Si wafers by cosputtering of SiO₂ and gold wires. Au/Si atomic ratios in Au/SiO₂ nanocomposite films were varied from 0.53 to 0.92 by controlling the length of gold wire to study the evolution of the crystallization of gold, the size of Au/SiO₂ nanocomposite particles, and the optical properties of as-deposited Au/SiO₂ nanocomposite films. An X-ray photoelectron spectroscopy reveals that Au exists as a metallic phase in the bulk of SiO₂ matrix. Dome-shaped Au/SiO₂ nanocomposite particles and both Au (1 1 1) and (2 0 0) planes were observed in a field-emission scanning electron microscopy and X-ray diffraction studies respectively. With an ultraviolet-visible, absorption peaks of Au/SiO₂ nanocomposite films were observed at 525 nm.     

Light scattering calculations from Au and Au/SiO2 core/shell nanoparticles

Given the importance of the optical properties of Au and Au/SiO₂ core/shell nanoparticles, in this article we focus our attention on the light scattering properties of such systems and on a relative comparison. In particular, we report theoretical results of angle-dependent light scattering intensity and scattering efficiency for Au and Au/SiO₂ core/shell nanoparticles increasing the Au particle radius from 30 to 130 nm, and for Au/SiO₂ core/shell particles changing the core-to-shell sizes ratio. Finally, a comparison between the scattering efficiency of the Au and Au/SiO₂ core/shell nanoparticles is drawn. The results of this work can be used in the design of tunable efficiency light scattering devices (biological and molecular sensors, solar cells).     

Study of resonant tunneling in Au nanoclusters on the surface of SiO2/Si thin films using the combined scanning tunneling microscopy and atomic-force microscopy technique

The morphology and electronic properties of Au nanoclusters on the surface of SiO₂ thin films on n ⁺-Si substrates are studied using the combined scanning tunneling microscopy (STM) and atomic-force microscopy (AFM) technique. The peaks associated with the resonant tunneling of electrons from the states of the valence band of the probe material to the states of the conduction band of the substrate material through Au nanoclusters are observed on the current-voltage characteristics for the contact of a p ⁺-Si AFM probe with Au nanoclusters. Experimental results are interpreted by calculating the tunnel transparency of the SiO₂/Au/SiO₂ double barrier structure in a strong electric field.     

Synthesis of Silver Nanoparticles by the Ion Implantation Method and Investigation of their Optical Properties

We have investigated the process of metal nanoparticle (NP) synthesis in SiO₂ by implanting Ag₊ ions with an energy of 30 keV depending on the dose ((2–8)·10¹⁶ cm⁻²) and the ionic current density (4–15 µA/cm²). Analysis of the composite materials formed was performed with the use of optical spectroscopy and atomic-force microscopy (AFM). The NPs synthesized in the glass demonstrate a characteristic absorption line associated with the surface plasma resonance effect. A correlation of the spectral shift of the lines caused by a change in the NP size with the diameter of the hemispherical asperities on the SiO₂ surface registered by the AFM method has been revealed. It has been found that for the case of a fixed current density in the ion beam the silver NP sizes remain practically unaltered with increasing ion dose up to a certain value (6·10¹⁶ cm⁻²), and only an increase in the concentration of NPs is observed thereby. However, a further increase in the dose causes a decrease in both the NP density and size. On the other hand, at a fixed high dose an increase in the ionic current density leads to a gradual enlargement of the NPs. We have considered the mechanisms explaining the change in the NP sizes with increasing dose and ionic current density and evaluated the possibilities of carrying out controlled synthesis by varying the implantation conditions.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 218–223, March–April, 2005.     

Effect of the thermal and hydrothermal treatment on textural properties of Zr-MCM-41 mesoporous molecular sieve

Zr-containing mesoporous molecular sieves were synthesized by hydrothermal method using cetyltrimethyl ammonium bromide as a template and sodium silicate and zirconium sulfate as raw materials. The structure and morphology of the synthesized samples were characterized via various physicochemical methods, including X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, solid state nuclear magnetic resonance (²⁹Si MAS-NMR) techniques, thermal gravimetric-differential scanning calorimeter (TG-DSC) and N₂ physical adsorption, respectively. The effect of the different initial ZrO₂:SiO₂ molar ratio, the different thermal treatment temperature and the different hydrothermal treatment time on textural property was investigated. The experimental results reveal that the as synthesized samples possess a typical mesoporous structure of MCM-41. On the other hand, the specific surface area and pore volume of the synthesized Zr-MCM-41 mesoporous molecular sieve decrease with the increase of the amount of zirconium incorporated in the starting material, the rise of thermal treatment temperature and the prolonging of hydrothermal treatment time, the mesoporous ordering becomes poor. Also, when the molar ratio of ZrO₂:SiO₂ in the starting material is 0.1, the mesoporous structure of the Zr-MCM-41 mesoporous molecular sieve still retains after calcination at 750 °C for 3 h or hydrothermal treatment at 100 °C for 6 d, and have specific surface areas of 423.9 and 563.9 m²/g, respectively.     

Nanospherical Surface‐Supported Seeded Growth of Au Nanowires: Investigation on a New Growth Mechanism and High‐Performance Hydrogen Peroxide Sensors

In this paper, a novel strategy with a new growth mechanism for fast and large‐scale growth of Au long nanowires on high‐curvature SiO₂ nanospherical surfaces has been developed. The synthesis includes three steps, i.e., amino modification of SiO₂ nanospheres, Au seed loading on aminated SiO₂ nanospheres and subsequently, Au seed‐mediated nanowire growth on SiO₂ nanospheres. The prepared Au nanowires (Au NWs) (exhibit long length, high aspect ratio, and good flexibility, and can naturally form the dense nanowire film, which is promising as a stable conductive electrode. In addition, the effect of synthetic conditions such as reactant feeding order, Au seeds and SiO₂@Au seeds on the morphology of Au nanostructures (nanowires, nanoteeth, and nanoflowers) has been investigated. It is found that Au seeds and high‐curvature SiO₂ nanospherical surfaces are necessary conditions for the successful preparation of Au NWs and nanowire films. The different growth mechanisms for Au NWs and nanoteeth have been proposed and discussed. Moreover, the novel nonenzymatic H₂O₂ sensor based on Au NWs exhibits much enhanced performance such as higher sensitivity, stability, and selectivity, wider linear range and lower detection limit, compared with that of Au nanoparticles‐based H₂O₂ sensor.     

Microfabrication of gold dots in SiO2/TiO2 glass films by two-photon absorption

Photogeneration of Au nanoparticles in SiO₂/TiO₂ glass films was carried out by two-photon absorption with a femtosecond pulse laser. Exquisite microdot-arrays of Au with micrometer spatial resolution were achieved by scanning of the focused laser beam. These structures were constructed in SiO₂/TiO₂ glass films by a sol–gel method. The sol–gel method demonstrated that Au dots microarray are fabricated at any position by two-photon absorption in the glass. The results show the utility of a two-photon absorption technique in the fabrication of complicated patterns with metal particles.     

Formation of ultrathin nanocomposite SiO2:nc-Au structures by Pulsed Laser Deposition

A method for the formation of Au nanocrystal (nc) arrays embedded in an ultrathin SiO₂ layer in one vacuum cycle is proposed. The method is based on the co-deposition in vacuum of ∼1 nm thick uniform Si-Au amorphous layer at a specific composition ratio by Pulsed Laser Deposition on the pre-oxidized Si(1 0 0) substrate, followed by its oxidation in the glow discharge oxygen plasma at room temperature, resulting in the precipitation of Au ncs at the bottom interface and/or at the surface of the forming SiO₂ layer. The capping SiO₂ layer is formed by the glow discharge plasma oxidation of further deposited ultrathin Si layer. Au ncs 2-5 nm in size and with the separation of ∼3-20 nm from each other segregate during the oxidation of Au-Si mixture as evidenced by transmission electron microscopy (TEM). The evolution of Au and Si chemical state upon each step of the SiO₂:nc-Au nanocomposite structure formation is monitored in situ by X-ray photoelectron spectroscopy (XPS). The metrology of nanocomposite SiO₂:nc-Au structures describing the space distribution of Au ncs as a function of Au/Si ratio is presented.     

High–Yield Production of Uniform Gold Nanoparticles with Sizes from 31 to 577 nm via One‐Pot Seeded Growth and Size‐Dependent SERS Property

In this work, uniform, quasi‐spherical gold nanoparticles (Au NPs) with sizes of 31–577 nm are prepared via one‐pot seeded growth with the aid of tris‐base (TB). Distinct from the seeded growth methods available in literature, the present method can be simply implemented by subsequently adding the aqueous dispersion of the 17 nm Au‐NP seeds and the aqueous solution of HAuCl₄ into the boiling aqueous TB solution. It is found that at the optimal pH range, the sizes of the final Au NPs and their concentrations are simply controlled by either the particle number of the Au seed dispersion or the concentration of the HAuCl₄ solution, while the latter enables us to produce large Au NPs at very high concentration. Moreover, as‐prepared Au NPs of various sizes are coated on glass substrates to test their surface‐enhanced Raman scattering (SERS) activities by using 4‐aminothiophenol (4‐ATP) molecules as probes, which exhibit “volcano type” dependence on the Au NP sizes at fixed excitation wavelength. Furthermore, the Au NPs with sizes of ≈97 and 408 nm exhibit the largest SERS enhancement at the excitation wavelength of 633 and 785 nm, respectively.     

Enhanced nonlinear optical absorption of Au/SiO2 nano-composite thin films

Nano metal-particle dispersed glasses are the attractive candidates for nonlinear optical material applications.Au/SiO 2 nano-composite thin films with 3 vol% to 65 vol% Au are prepared by inductively coupled plasma sputtering.Au particles as perfect spheres with diameters between 10 nm and 30 nm are uniformly dispersed in the SiO 2 matrix.Optical absorption peaks due to the surface plasmon resonance of Au particles are observed.The absorption property is enhanced with the increase of Au content,showing a maximum value in the films with 37 vol% Au.The absorption curves of the Au/SiO 2 thin films with 3 vol% to 37 vol% Au accord well with the theoretical optical absorption spectra obtained from Mie resonance theory.Increasing Au content over 37 vol% results in the partial connection of Au particles,whereby the intensity of the absorption peak is weakened and ultimately replaced by the optical absorption of the bulk.The band gap decreases with Au content increasing from 3 vol% to 37 vol % but increases as Au content further increases.     

Investigation of the electronic properties of Au nanoclusters in SiO<Subscript>2</Subscript> by combined scanning tunneling/atomic force microscopy

The tunneling of electrons through Au nanoc lusters formed by pulsed laser deposition in a SiO₂ thin film on a Si substrate has been investigated by combined scanning/atomic force microscopy (STM/AFM). Conducting Pt-coated Si cantilevers were used. The feedback was maintained via the AFM channel, and the current-voltage (I-V) characteristics of the tunnel contact between the AFM probe and the n ⁺-Si substrate through a =4-nm-thick SiO₂ film with Au nanoclusters =2 nm in diameter were measured simultaneously. The current image of the structure contained areas of increased current (tunnel-current channels) 2–15 nm in size, related to tunneling of electrons through Au nanoclusters in SiO₂. The I-V characteristics recorded in the tunnel-current channels exhibit specific features related to the Coulomb blockade of electron tunneling through Au nanoclusters.     

Highly selective fluorescent chemosensor for detecting Hg(II) in water based on pyrene functionalized core–shell structured mesoporous silica

Novel pyrene functionalized mesoporous core–shell structured silica (denoted as SiO₂@mSiO₂/Py-Si) was designed and synthesized as a highly selective fluorescent chemosensor for detecting Hg²⁺ in water. The core–shell structured silica was prepared by a simple sol–gel process through coating SiO₂ nanospheres with a layer of ordered mesoporous silica. The surface of outer mesoporous silica shell was then further functionalized by the fluorescent chromophore alkoxysilane modified pyrene (Py-Si). XRD data confirmed that the hexagonal ordered mesoporous structure was preserved after functionalization. The chemosensing material successfully exhibited a remarkable “turn on” response toward Hg²⁺ over miscellaneous metal ions. A good linear response towards Hg²⁺ in the concentration range of 10^?8–10^?4 M was constructed with R²=0.9913. Most importantly, a satisfactory detection limit of 3.4×10^?9 g mL^?1 (down to ppb level) was obtained, which is 100 times lower than our previous report of covalently grafted Py-OH to the bulk mesoporous silica SBA-15. These results indicated that SiO₂@mSiO₂/Py-Si can be used as a highly selective and sensitive fluorescence sensor for Hg²⁺.     

Size-Dependent HCl Generation of PVC/SiO2 Micro- and Nanocomposites

In this study HCl generation of polyvinyl (chloride) (PVC)/SiO₂ composites during its combustion was investigated. SiO₂ with different particle sizes were used as HCl absorbers and their HCl uptake ability results were compared to that of CaCO₃. It was found that the amount of released HCl gas during PVC combustion decreased in the presence of SiO₂. The HCl uptake ability of SiO₂ improved with decreasing of its particle size. Although thermogravimetric analysis (TGA) results showed that SiO₂ particles decreased the first thermal degradation temperature (T _onset) of PVC by initiating dehydrochlorination of PVC at lower temperatures, SiO₂ particles had more effective HCl uptaking ability than that of CaCO₃. Scanning electron microscopy (SEM) micrographs showed that some aggregates whose size was less than 100 nm were formed when Si-25 nm was used as filler. When SiO₂ with micron size was added to PVC as filler, more uniform and better distribution of the SiO₂ on the surface was observed.     

Au/SiO2纳米多层薄膜的制备及其性质表征

利用多靶磁控溅射技术制备了Au/SiO₂纳米颗粒分散氧化物多层复合薄膜.研究了在保持Au单层颗粒膜沉积时间一定时薄膜厚度一定、变化SiO₂的沉积时间及SiO₂的沉积时间一定而改变薄膜厚度时，多层薄膜在薄膜厚度方向的微观结构对吸收光谱的影响.研究结果表明：具有纳米层状结构的Au/SiO₂多层薄膜在560 nm波长附近有明显的表面等离子共振吸收峰，吸收峰的强度随Au颗粒的浓度增加而增强，在Au颗粒浓度相同的情况下，复合薄膜 关键词： 2纳米复合薄膜')" href="#">Au/SiO₂纳米复合薄膜 多靶磁控溅射 吸收光谱 有效介质理论     

Temperature dependent optical properties of Si nanocrystals embedded in SiO2 matrix

The optical properties of Si nanocrystals (nc-Si) with different sizes (2～5 nm) embedded in a SiO₂ matrix synthesized by the SiO _x /SiO₂ superlattice approach were studied in a temperature range from room temperature to 600 K by spectroscopic ellipsometry. The Maxwell–Garnett effective medium approximation and Lorentz oscillator model were employed to extract the dielectric function of nc-Si. The results show that the temperature dependence of optical properties of nc-Si is sensitive to its size. An empirical expression of Varshni approximation was obtained to characterize the band-gap energy change of nc-Si at different temperatures.     

Photocatalytic degradation of methyl orange by gold silver nano-core/silica nano-shell

The silica nanoparticles (SiO₂ NPs), silver (Ag) NPs and gold (Au) NPs coated with SiO₂ NPs (core-shell) were prepared. The sizes and morphology of the particles were indicated. The three prepared NPs were used for photocatalytic degradation of methyl orange (MO) dye by xenon lamp. Rate of photocatalytic degradation reaction constant and lifetime were calculated for each catalyst. Moreover, the mechanism of the photocatalytic reaction was studied.