Size-dependent transformation from Ag templates to Au–Ag nanoshells via galvanic replacement reaction in organic medium

The transformation from Ag templates to Au?CAg nanoshells via galvanic replacement reaction with HAuCl₄ was systematically studied in an organic medium in the presence of oleylamine. Decahedral (~43?nm in size) and triangular prism (~53?nm in edge length) Ag templates transformed into equiaxed and triangular prismatic Au?CAg nanoshells, respectively. The first step involved structural and morphological changes from Ag templates to Au?CAg nanoshells with an interior cavity. In the second step, the growth of the shells continued through the deposition of Au. The shell thickness increased from ~5 to ~10?nm for the equiaxed Au?CAg nanoshells (~39-nm interior cavity) and ~5 to ~8?nm for the triangular prismatic Au?CAg nanoshells (~52-nm interior edge length). Oleylamine not only served as a surfactant but also removed AgCl precipitates and reduced HAuCl₄. For the nanoshells derived from the ~20-nm Ag decahedrons, further reaction in excess HAuCl₄ collapsed the nanoshells into Au-rich solid fragments. However, the nanoshells derived from the ~43-nm Ag decahedrons, the nanoshell structure not only persisted in excess HAuCl₄, but its shell thickness also increased. The size-dependent transformation of these nanoshells is discussed.     

Multilayer Au/TiO2Composite Films with Ultrafast Third-Order Nonlinear Optical Properties

We report on the ultrafast third-order optical nonlinearity in multilayer Au/TiO2 composite films fabricated on quartz substrates by pulsed laser deposition technique. The linear optical properties of the films are determined and optical absorption peaks due to surface plasmon resonance of Au particles are observed at about 590hm. The third-order optical nonlinearities of the films are investigated by z-scan method using a femtosecond laser （50 fs） at the wavelength of 800 nm. The sample showed fast nonlinear optical responses with nonlinear absorption coefficient and nonlinear refractive index being -3.66 × 10^-10 m/W and -2.95 × 10^-17 m^2/W, respectively. The results also show that the nonlinear optical effects increase with the increasing Au concentration in the composite films.     

Nonlinear optical response of Au and Ag nanoparticles doped polyvinylpyrrolidone thin films

Colloidal Au and colloidal Ag were prepared by chemical reaction method and the nonlinear optical properties of Au and Ag nanoparticles doped polyvinylpyrrolidone (PVP) composite films were investigated using Z-scan technique with 38 ps pulses at 532 nm. Open aperture Z-scan measurements indicated that both the Au/PVP and Ag/PVP composite films exhibited reverse saturable absorption. Nonlinear absorption coefficients and third-order nonlinear refractive indices were determined. The mechanisms accounting for the process of nonlinear refractions were analyzed and the figures of merit W and T of the Au/PVP and Ag/PVP composite films were evaluated.     

Facile preparation of Au/Ag bimetallic hollow nanospheres and its application in surface-enhanced Raman scattering

In this paper, an Au/Ag bimetallic hollow nanostructure was obtained by using SiO₂ nanospheres as sacrificial templates. The nanostructure was fabricated via a three steps method. SiO₂@Au nanospheres were first synthesized by the layer-by-layer technique, and then they were coated with a layer of Ag particles, finally, the Au/Ag bimetallic hollow nanospheres were obtained by dissolution of the SiO₂ core by exposure in HF solution. Several characterizations, such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and UV visible absorption spectroscopy were used to investigate the prepared nanostructures. The effectiveness of these Au/Ag bimetallic hollow nanospheres as substrates toward surface-enhanced Raman scattering (SERS) detection was evaluated by using rhodamine 6G (R6G) as a probe molecule. We show that such Au/Ag bimetallic hollow nanospheres structure films which consisting of larger interconnected aggregates are highly desirable as SERS substrates in terms of high Raman intensity enhancement. The Au/Ag bimetallic hollow nanostructured aggregate, interconnected nanostructured aggregate and nanoscale roughness are important factors responsible for this large SERS enhancement ability.     

Air Stability of Cs2CO3:Ag/Ag Cathode for Organic Light-Emitting Diodes

We report the superior stability of the composite Cs2CO3 ：Ag/Ag cathode structure, which can be used in efficient organic light-emitting diodes （OLEDs）. Devices with the Cs2CO3：Ag （1：10, 5nm）/Ag （95nm） cathode show a considerably improved lifetime compared with the control device with the Cs2CO3 （0.5 nm）/Ag （100 nm） cathode. The composite Cs2CO3 ：Ag/Ag film is proved to be stable in the atmosphere. X-ray diffraction （XRD） is applied to analyze the crystalline structure of the Cs2CO3：Ag film, and it is demonstrated that CsAg alloy is formed, leading to the improved stability of the thin film and the devices.     

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.     

Preparation of large-area surface-enhanced Raman scattering active Ag and Ag/Au nanocomposite films

Ag films on tinning glass substrates were fabricated by modified silver-mirror (Tollen’s) reaction with the advantage of low-cost, simple and quick fabrication process. The obtained Ag films were served as sacrificial materials for preparation of Ag/Au nanocomposite films by immersing in a chlorauric acid (HAuCl₄) solution at room temperature. After a short time of galvanic replacement reaction, Ag/Au bimetallic nanostructures were synthesized with “concave” structures. The morphology, properties and composition of the Ag and Ag/Au nanocomposite films were analyzed by using scanning electron microscopy (SEM), UV-visible spectroscopy, X-ray diffraction (XRD), energy-dispersive X-ray spectrometry (EDS) and surface enhanced Raman scattering (SERS). SEM images displayed that the large area of Ag film and Ag/Au bimetallic nanostructures experienced structural evolution process during galvanic reaction. The UV-Vis spectra showed the absorbencies characterization of Ag film and Ag/Au nanocomposite films. SERS measurements using methylene blue as an analyte showed that SERS intensities of bimetallic films were enhanced significantly compared with that of pure Ag films. The SERS enhancement ability of Ag/Au bimetallic films was dependent on the immersion time for galvanic replacement reaction.     

“Hot spots” induced near-field enhancements in Au nanoshell and?Au nanoshell dimer

The influence of “hot spots” on the near-field properties of Au nanoshell and Au nanoshell dimers have been investigated by means of the finite element method. It is found with increasing the pinhole radius R that the maximal enhancement of near-field for Au nanoshell with pinhole parallel to the polarization increases from 17.906 at R=0 nm to 36.979 at R=0.8 nm, and then almost shows a negligible radius dependence. Large electric fields also can be observed inside the pinhole perpendicular to the polarization, which increases with increasing the pinhole radius. The near-field of Au nanoshell dimer depends strongly on the polarization and propagation directions of the incident light. Exponential decay behavior is found for the maximal enhancement of the electric field in the dimer junction as a function of the dimer separation. Furthermore, a very strong electric field is found in the junction between two Au nanoshells when the pinholes are located near the gap between the nanoshells.     

Novel fabrication and catalytic application of poly(ethylenimine)-stabilized gold–silver alloy nanoparticles

Novel synthesis of amine-stabilized Au–Ag alloy nanoparticles with controlled composition has been devised using poly(ethylenimine) (PEI) as a reducing and a stabilizing agent simultaneously. The composition of Au–Ag alloy nanoparticles was readily controlled by varying the initial relative amount of HAuCl₄ and AgNO₃. Due to the presence of abundant amine functional groups in PEI, which could act as the dissolving ligand for AgCl, the precipitation problem of Ag⁺ in the presence of Cl⁻ from the gold salt was avoided. On this basis, the relatively high concentrations of HAuCl₄ and AgNO₃ salts were used for the fabrication of Au–Ag alloy nanoparticles. The PEI thus plays triple roles in this study that include the co-reducing agents for HAuCl₄ and AgNO₃, the stabilizing agents for Au–Ag alloy nanoparticles, and even the dissolving agents for AgCl. As a novel material for use in catalysis, the Au–Ag alloy nanoparticles including pure Au and Ag samples were exploited as catalysts for the reduction of 4-nitrophenol in the presence of NaBH₄. As the Au content was increased in the Au–Ag alloy nanoparticles, the rate constant of the reduction was exponentially increased from pure Ag to pure Au.     

银纳米链状材料的制备及近红外吸收性质

报道了利用水/油相界面反应,采用湿化学法合成银纳米链状材料的方法,并对这种材料的近红外吸收性质和光热转换性质进行了研究。TEM分析表明,银纳米材料为链状结构,直径约为50nm,长度分布范围较宽,从几十纳米至几百纳米。这种材料具有强的近红外吸收特性,随着还原剂加入量的增加,吸收带逐渐展宽(800～1300nm),而且平坦。这种材料具有优异光热转换性质,一经808nm激光照射,温度迅速提高。该材料优异的近红外吸收和光热转换性质,使其在红外断层成像和近红外热疗等领域具有广阔的应用前景。     

Synthesis and photo physical properties of Au @ Ag (core @ shell) nanoparticles disperse in poly vinyl alcohol matrix

Synthesis of core @ shell (Au @ Ag) nanoparticle with varying silver composition has been carried out in aqueous poly vinyl alcohol (PVA) matrix. Core gold nanoparticle (~15 nm) has been synthesized through seed-mediated growth process. Synthesis of silver shell with increasing thickness (~1–5 nm) has been done by reducing Ag⁺ over the gold sol in the presence of mild reducing ascorbic acid. Characterization of Au @ Ag nanoparticles has been done by UV–Vis, High resolution transmission electron microscope (HRTEM) and energy dispersive X-ray (EDX) spectroscopic study. The blue shift of surface plasmon resonance (SPR) band with increasing mole fraction of silver has been interpreted due to dampening of core, i.e. Au SPR by Ag. The dependence of nonlinear optical response of spherical core @ shell nanoparticles has been investigated as a function of relative composition of each metal. Simulation of SPR extinction spectra based on quasi-static theory is done. A comparison of our experimental and the simulated extinction spectra using quasi-static theory of nanoshell suggests that our synthesized bimetallic particles have core @ shell structure rather than bimetallic alloy particles.     

High-Temperature Characteristics of Ti/Al/Ni/Au Ohmic Contacts to n-GaN

We present the high-temperature characteristics of Ti/Al/Ni/Au（15 nm/220 nm/40 nm/50 nm） multiplayer contacts to n-type GaN （Nd = 3.7 × 10^17 cm^-3, Nd = 3.0 × 10^18 cm^-3）. The contact resistivity increases with the measurement temperature. Furthermore, the increasing tendency is related to doping concentration. The higher the doped, the slower the contact resistivity with decreasing measurement temperature. Ti/Al/Ni/Au ohmic contact to heavy doping n-GaN takes on better high temperature reliability. According to the analyses of XRD and AES for the n-GaN/Ti/Al/Ni/Au, the Au atoms permeate through the Ni layer which is not thick enough into the AI layer even the Ti layer.     

Au:TiO2和Au:Al2O3纳米颗粒复合膜的线性和非线性光学特性

主要从实验和理论两个方面,探讨了不同Au颗粒尺寸和不同基质对Au：TiO₂和Au：Al₂O₃复合膜线性和非线性光学性质的影响.用吸收光谱研究了Au颗粒尺寸和基质与Au复合膜表面等离子体共振带之间的关系;用皮秒Z扫描技术研究了共振和非共振情况下(激发光波长分别为532nm和1064nm),Au颗粒尺寸和基质与复合膜三阶非线性极化率的关系.基于表面等离子体共振理论和局域场增强理论对复合膜进行了分析,得到了不同Au颗粒大小和不同基质时Au复合膜的 关键词： 金属纳米颗粒 复合膜 三阶非线性 表面等离子体共振     

Optical properties of mixed clusters: comparative study of Ni/Ag and Pt/Ag clusters

The optical properties of mixed (Ni_0.5Ag_0.5)_n and Pt/Ag clusters are investigated in the size range 2-5 nm. Low Energy Ion Spectroscopy (LEIS) experiments show that the cluster surface is entirely covered by silver atoms for the two systems. The optical spectra of Ni/Ag clusters exhibit a large Surface Plasmon Resonance (SPR), damped and widened when the cluster size decreases, in agreement with a classical model assuming a core-shell geometry and including the reduction of the conduction electron mean-free path in the silver shell. For Pt/Ag clusters, no SPR emerges in the size range 2-5 nm, although it is predicted within a classical model, a pronounced SPR appearing only for clusters larger than 10 nm in diameter.     

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.     

Ag:Bi2O3复合膜的线性和非线性光学性质

从实验和理论两个方面，探讨了金属Ag不同掺杂浓度对Ag:Bi₂O₃复合膜线性和非线性光学性质的影响. 用吸收光谱研究了Ag浓度与Ag:Bi₂O₃复合膜表面等离子体共振带之间的关系；用皮秒Z-扫描技术研究了共振和非共振情况下(激发光波长分别为532nm和1064nm)，金属Ag浓度与复合膜三阶非线性极化率的关系. 基于表面等离子体共振理论和局域场增强理论对复合膜进行了分析，得到了不同Ag浓度时Ag:Bi₂O₃复合膜的三阶非线性效应，研究了激发波长和金属浓度对复合膜线性和非线性光学性质的影响. 结果表明，等离子体共振增强和合适的金属掺杂浓度使得三阶极化率增强二个量级，在Ag浓度为35％左右和接近等离子体共振频率(相应吸收带位于560nm—622nm)的532nm激发时，χ⁽³⁾具有最大值2.4×10^-9esu. 关键词： 金属纳米颗粒 复合膜 三阶非线性 表面等离子体共振     

Fabrication of optically tunable silica nanocapsules containing Ag/Au nanostructures by confined galvanic replacement reaction

Abstract  

Silica nanocapsules containing Ag/Au alloy nanostructures (SNCAs) are fabricated by galvanic replacement (GR) reactions between silver core nanoparticles within silica shells and aqueous HAuCl₄ in a confined nano-space. The structure and morphology of the resulting SNCAs are diversified by controlling the relative amount of Ag/Au, exhibiting tunable optical absorptions in visible region. The GR reactions in a confined nano-space include alloying and de-alloying processes that determine the evolution of morphology and optical absorption of SNCAs.     

Chloride ion refined galvanic replacement: Boosting monodispersity of Au-Ag hollow nanoparticles & their enhanced applications

In this present work, we have redesigned the well-known Turkevich protocol for promoting versatile galvanic replacement, resulting in the synthesis of hollow Au nanostructures by the sacrificial reduction of HAuCl₄ on the as-prepared Ag nanoparticles in the presence of slight excess NaCl in order to dictate their core size to cavity ratio in a highly reproducible manner. The significance of chloride ion interaction in tuning the size/shape control was corroborated with the contrasting effect of other halide ions, namely bromine and iodine. The structure-property functional relationship of these artificial hollow metal nanostructures were not only established using the systematic optical absorption and TEM measurements, but also through enhanced spectroscopy measurements such as SEIRA and SERS, elucidating the dynamic advantage of hollow nanostructures over and above their solid monometallic counterparts. Further, the familiar 4-NA to p-PDA catalytic reduction kinetics demonstrate the unusual zeroth order characteristics in the presence of hollow metal nanostructures, unequivocally distinguishing it from the common first order characteristics associated with the corresponding solid metal nanoparticles, essentially attributed to the morphology tuned accessible higher total surface area, thus exemplifying the aesthetic compliance for future technological applications.     

Femtosecond Third-Order Optical Nonlinearity of Au：Bi203 Nanocomposite Films

Ultrafast third-order optical nonlinearities of the as-deposited and annealed Au：Bi2O3 nanocomposite films deposited by magnetron cosputtering are investigated by using femtosecond time-resolved optical Kerr effect （OKE） and pump probe techniques. The third-order optical nonlinear susceptibility is estimated to be 2.6Ф×10^- 10 esu and 1.8 × 10.9 esu at wavelength of 800nm, for the as-deposited and the annealed film, respectively. The OKE signal of the as-deposited film is nearly temporally symmetrical with a peak centred at zero delay time, which indicates the dominant contribution from intraband transition of conduction electrons. For the annealed film, the existence of a decay process in OKE signal implies the important contribution of hot electrons. These characteristics are in agreement with the hot electron dynamics observed in pump probe measurement.     

Metal enhanced photoluminescence of near-infrared CdTexSe1−x quantum dots

High-quality alloyed near-infrared CdTe_xSe_1?x quantum dots were synthesized by a modified organometallic method. The emission wavelength of the alloyed quantum dots were turned from visible to near-infrared range by changing the composition of the precursor. The photoluminescence intensity of the alloyed quantum dots was further enhanced by coupling through localized surface plasmons from Au nanoparticles. The alloyed CdTeSe quantum dots coupled with Au nanoparticles exhibited a 4 times photoluminescence enhancement than that of bare CdTeSe quantum dots by turning the localized surface plasmons resonant absorption of Au nanoparticles consistent to the excitation wavelength. This method will be beneficial for the potential applications in the biological imaging and detection.