Fabrication of Rh based solid-solution bimetallic alloy nanoparticles with fully-tunable composition through femtosecond laser irradiation in aqueous solution

Many late transition binary alloy nanoparticles (NPs) have been fabricated through a wide variety of techniques. Various steps are involved in the fabrication of such NPs. Here, we used a simple and green route to fabricate solid-solution Rh–Pd and Rh–Pt bimetallic alloy NPs through femtosecond laser irradiation in a solution without any chemicals like reducing agents. X-ray diffraction (XRD) peaks of NPs obtained in the solutions with different ratios of Rh–Pd and Rh–Pt ions monotonically varied from the position of pure Rh to those of Pd and to Pt which respectively indicated that these NPs were alloy. Composition of fabricated NPs was fully tuned over the entire range of Rh_1?x –Pd _x , and Rh_1?x –Pt _x with varying the mixing ratio of metal ions in the solution. Studies of Rh–Pd and Rh–Pt solid-solution system suggest that the alloy formation occurs through the nucleation of Rh and then followed by the diffusion of Rh, Pd and Rh, Pt to form a homogeneous alloy. The variety of average size of the alloy NPs for different compositions could be attributed to different reduction rate and surface energies of metal ions. Our result implies that femtosecond laser irradiation in aqueous solution is one of the potential methodologies to form multimetallic solid-solution alloy NPs with fully tunable composition.     

激光诱导玻璃内部金纳米颗粒的析出及光谱

使用钛宝石飞秒激光引发和热处理相结合，实现了在含有金离子的硅酸盐玻璃内部，有空间选择性地析出金纳米颗粒。对吸收光谱的研究表明，随着热处理温度的升高，吸收峰强度增大且红移；随着激光功率密度的增大，金纳米颗粒也增大。在特定的激光和热处理条件作用下，可以在玻璃内部有空间选择性的使金离子还原后聚集，形成金纳米颗粒，具有量子尺寸效应。改变激光功率和热处理温度可以控制所析出的金属纳米粒子的尺寸，从而实现多色显示，飞秒激光诱导金纳米颗粒具有稳定性，颜色具有持久性。     

Laser-Assisted Formation of Elongated Au Nanoparticles and Subsequent Dynamics of Their Morphology under Pulsed Irradiation in Water

The processes of laser-assisted formation of elongated Au nanoparticles and their subsequent agglomeration and fragmentation have been experimentally investigated. Elongated gold nanoparticles were formed by laser ablation of a solid target in water. IR radiation of ytterbium-doped fiber laser with a pulse width of 200 ns and a pulse energy of 0.5 to 1 mJ was used to this end. The extinction spectra and transmission electron microscopy images indicate the formation of elongated gold nanoparticles. The interaction of laser radiation with aqueous colloids of elongated nanoparticles in dependence of the pulse energy and exposure time has been analyzed. Possible processes of laser-assisted formation of elongated Au nanoparticles and their subsequent transition from agglomeration to fragmentation of gold nanoparticles, induced by laser irradiation are discussed.     

Radiation induced synthesis of gold/iron-oxide composite nanoparticles using high-energy electron beam

Composite nanoparticles consisting of gold and iron oxide were synthesized in aqueous solution systems by using a high-energy electron beam. The electron irradiation induces radiation-chemical reaction to form metallic gold nanoparticles. These gold nanoparticles were firmly immobilized on the surface of the support iron oxide nanoparticles. Surface of the support iron oxide nanoparticles are almost fully coated with fine gold nanoparticles. The size of these gold nanoparticles depended on the concentrations of gold ions, polymers and iron oxide nanoparticles in the solutions before the irradiation.     

Nanocomposite ZnO/Au formation by pulsed laser irradiation

The ZnO/Au nanocomposite formation involves synthesis of Au and ZnO colloidal solutions by 532 nm pulse laser ablation of metal targets in deionized water followed by laser irradiation of the mixed colloidal solution. The transmission electron microscope (TEM) and high-resolution transmission electron microscope (HRTEM) images show evolution of spherical particles into ZnO/Au nanonetworks with irradiation time. The formation mechanism of the nanonetwork can be explained on the basis of near resonance absorption of 532 nm irradiation by gold nanoparticles which can cause selective melting and fusion of gold nanoparticles to form network. The ZnO/Au nanocomposites show blue shift in the ZnO exciton absorption and red shift in the Au plasmon resonance absorption due to interfacial charge transfer.     

Size control synthesis of starch capped-gold nanoparticles

Metallic gold nanoparticles have been synthesized by the reduction of chloroaurate anions [AuCl₄]⁻ solution with hydrazine in the aqueous starch and ethylene glycol solution at room temperature and at atmospheric pressure. The characterization of synthesized gold nanoparticles by UV–vis spectroscopy, high resolution transmission electron microscopy (HRTEM), electron diffraction analysis, X-ray diffraction (XRD), and X-rays photoelectron spectroscopy (XPS) indicate that average size of pure gold nanoparticles is 3.5 nm, they are spherical in shape and are pure metallic gold. The concentration effects of [AuCl₄]⁻ anions, starch, ethylene glycol, and hydrazine, on particle size, were investigated, and the stabilization mechanism of Au nanoparticles by starch polymer molecules was also studied by FT-IR and thermogravimetric analysis (TGA). FT-IR and TGA analysis shows that hydroxyl groups of starch are responsible of capping and stabilizing gold nanoparticles. The UV–vis spectrum of these samples shows that there is blue shift in surface plasmon resonance peak with decrease in particle size due to the quantum confinement effect, a supporting evidence of formation of gold nanoparticles and this shift remains stable even after 3 months.     

Effect of Ultrashort Pulsed Laser and X-Ray Irradiation on Au+ -Doped Glass

Au nanoparticles were precipitated inside Au+-doped glass samples after irradiation by femtosecond laser or x-ray. Femtosecond laser and X-ray irradiation result in decreasing of anneal temperature and critical size for the precipitation of Au nanoparticles.     

飞秒激光作用下金掺杂硅酸盐玻璃的光致晶化研究

研究了金掺杂硅酸盐玻璃在飞秒激光辐照和热处理作用下的光致晶化行为，分析探讨了其机理和激光辐照条件的影响.吸收光谱测试表明玻璃内部析出金纳米颗粒. 金纳米颗粒掺杂玻璃在近共振纳秒脉冲作用下显示了强的光限幅效应, 且改变飞秒激光诱导参数可改变该复合玻璃的光学非线性. 关键词： 光致晶化 飞秒激光 金纳米颗粒 硅酸盐玻璃 光限幅     

Intensity-Dependent Optical Nonlinear Absorption and Refraction of Gold Nanorods

Au nanorods dispersed in aqueous solution were prepared with the electrochemical method. The absorption spectrum shows two absorption peaks corresponding to the perpendicular and transverse surface plasma resonance absorption of the nanorods. The third-order optical nonlinear properties are investigated by Z-scans. The signs of the nonlinear absorption coemcient and refractive index are reversed as the intensity of incident laser increases, which is due to the shape change of the gold nanoparticles melted by the intense laser pulses.     

辐照还原法制备Au掺杂MF气凝胶

利用辐照还原法在500 kGy辐照剂量下制备了Au掺杂MF有机气凝胶。通过X射线衍射（XRD）、能量色散光谱仪（EDX）和透射电子显微镜（TEM）测试证实了辐照法成功地制备出Au掺杂MF有机气凝胶复合物。EDX和TEM照片表明辐照处理后Au纳米颗粒均匀地分布在MF气凝胶骨架中,并且Au纳米颗粒的平均尺寸为5.8 nm。N2吸附数据分析表明掺入Au纳米颗粒后,MF气凝胶的比表面积、总孔体积、微孔体积和介孔体积都有所下降。     

Gold nanoparticles produced in a microalga

An efficient biological route to production of gold nanoparticles which allows the nanoparticles to be easily recovered remains elusive. Live cells of the green microalga Chlorella vulgaris were incubated with a solution of gold chloride and harvested by centrifugation. Nanoparticles inside intact cells were identified by transmission electron microscopy and confirmed to be metallic gold by synchrotron based X-ray powder diffraction and X-ray absorption spectroscopy. These intracellular gold nanoparticles were 40–60 nm in diameter. At a concentration of 1.4% Au in the alga, a better than 97% recovery of the gold from solution was achieved. A maximum of 4.2% Au in the alga was obtained. Exposure of C. vulgaris to solutions containing dissolved salts of palladium, ruthenium, and rhodium also resulted in the production of the corresponding nanoparticles within the cells. These were surmised to be also metallic, but were produced at a much lower intracellular concentration than achieved with gold. Iridium was apparently toxic to the alga. No nanoparticles were observed using platinum solutions. C. vulgaris provides a possible route to large scale production of gold nanoparticles.     

A simple and effective route for the preparation of poly(vinylalcohol) (PVA) nanofibers containing gold nanoparticles by electrospinning method

Poly(vinylalcohol) (PVA) nanofibers containing gold nanoparticles have been simply obtained by electrospinning a solution containing gold nanoparticles without the additional step of introducing other stabilizing agents. The optical property of gold nanoparticles in PVA aqueous solution was observed by UV-visible absorption spectra. Morphology of the Au/PVA nanofibers and distribution of the gold nanoparticles were characterized by transmission electron microscopy (TEM). The structure transformation was characterized from PVA to PVA/Au composite by Fourier transform infrared spectroscopy (FTIR).     

金纳米颗粒的有序制备及其光学特性

采用纳米球蚀刻技术在石英衬底上制备了不同高度的金纳米颗粒阵列.通过扫描电子显微镜对其表面形貌进行了观测,表明金纳米颗粒为有序分布的三棱柱结构.通过红外—紫外吸收光谱仪在190—900nm波长范围内对其光吸收特性进行了测量, 并成功观测到了金纳米颗粒表面等离子体振荡效应引起的光吸收峰,结果表明随着金纳米颗粒高度的增加,其吸收峰的位置向短波方向移动(蓝移).同时对金纳米颗粒的光吸收特性进行了基于离散偶极子近似的理论计算,并与实验结果进行了比较. 关键词： 纳米球蚀刻技术 金纳米颗粒 离散偶极子近似     

Fabrication of platinum particles by intense, femtosecond laser pulse irradiation of aqueous solution

Platinum nano-particles were directly fabricated through molecular dissociation process induced by tightly focused femtosecond laser pluses in hydrogen hexachloroplatinate (IV) hexahydrate (H₂PtCl₆·6H₂O) aqueous solution. After irradiation, it was found that UV-visible absorption spectrum of the solution was changed and a large number of small platinum particles were synthesized. The variation of absorbance in the spectrum and the yield the particle synthesis depended on the concentration of the solution. The most effective condition for particle synthesis was 0.1 wt%. Black precipitates of platinum particles were observed in the bottom of the vessel after irradiation in some cases. The dispersibility of the particles was greatly improved by the addition of polyvinylpyrrolidone (PVP) as a dispersant, and no precipitates were found in the solution with 1.0 × 10⁻² wt% PVP. Consequently, highly monodispersed platinum nano-particles with the mean size of about 3 nm were successfully fabricated.     

Study on optical and electrical properties of gold-doped silicon fabricated by femtosecond laser

Microstructured silicon (Si) materials have been fabricated by femtosecond (fs) laser ablation and have been hyperdoped with gold (Au) impurities. The ablated Si materials showed large and thermostable infrared absorption at 1.1–2.5 μm wavelengths, which was contributed by sub-band absorption and laser-induced defects absorption. The Au–Si alloy was formed after laser irradiation onto the Au-coated Si surface, which was determined by XRD characterization. Using N-type Si substrate, the fabricated Au-doped Si performed lower sheet carrier density due to the self-compensation effect between deep donor and acceptor energy lever of Au in bulk Si material. From Hall measurement, both the p- and n- types of Au-doped Si samples can be obtained by controlling the type of Si substrate.     

A novel method of nanocrystal fabrication based on laser ablation in liquid environment

Metal nanoparticles can be prepared by a novel technique that consists of the laser ablation of a solid target immersed in a water solution of a metal salt. Silicon was chosen as the most adequate target to synthesize silver and gold nanoparticles from a water solution of either AgNO₃ or HAuCl₄. The influence of both the silver nitrate concentrations and the irradiation time of the Si target on the optical properties of the Au and Ag nanoparticles have been investigated. The crystalline nature of the metal nanoparticles has been determined by X-ray diffraction (XRD). Average size and particle size distribution have been measured by means of TEM. The absorbance spectra show the characteristic band of the surface resonant plasmon of silver and gold nanoparticles.     

Synthesis and characterization of composite Au/TiO2 nanoparticles by laser irradiation

Composite Au/TiO₂ nanoparticles were synthesized by laser ablation of gold plate in TiO₂ sol. The nanoparticles were characterized by UV-visible spectroscopy, transmission electron microscopy, X-ray diffraction, and atomic force microscopy. The peak of surface plasmon is at 550 nm with a red shift of 30 nm compared with that of Au nanoparticles in water. Monolayers of composite Au/TiO₂ nanoparticles were obtained by dip-coating technique. The XRD pattern of Au/TiO₂ powders resembles a mixture of anatase TiO₂ and gold.     

Study of Au-Pd core-shell nanoparticles by using slow positron beam

Binary Au-Pd nanoparticles were synthesized by ultrasonic irradiation of solutions containing Au³⁺ and Pd²⁺ ions (the ion ratio from 0.3:0.7 to 0.9:0.1 mM) and cationic surfactant (SDS: sodium dodecyl sulfate). In each case the core-shell structure (Au core, Pd shell) was confirmed by scanning transmission electron microscopy (STEM). The mean diameters of them were all about 9 nm, and the thickness of the Pd shell depends on the ratio of Pd²⁺ and Au³⁺ ions in solution. In order to study the electronic states of core-shell nanoparticles and their dependence on shell thickness, Doppler broadening measurements were performed for Au-Pd core-shell nanoparticles by using slow positron beam technique. The ratio curves of Au-Pd particles did not match with those of pure Pd and pure Au, but a small difference in the low electron momentum region was observed among nanoparticles depending on Pd shell thickness.     

Synthesis of composite gold/tin-oxide nanoparticles by nano-soldering

Composite Au–SnO₂ nanoparticles (NPs) are synthesized by nano-soldering of pure Au and SnO₂ NPs. The multi-step process involves synthesis of pure Au and SnO₂ NPs separately by nanosecond pulse laser ablation of pure gold and pure tin targets in deionized water and post-ablation laser heating of mixed solution of Au colloidal and SnO₂ colloidal to form nanocomposite. Transmission Electron Microscopy (TEM) and High-Resolution Transmission Electron Microscopy (HRTEM) were used to study the effect of laser irradiation time on morphology of the composite Au–SnO₂ NPs. The spherical particles of 4 nm mean size were obtained for 5 min of post-laser heating. Increased mean size and elongated particles were observed on further laser heating. UV–vis spectra of Au–SnO₂ nanocomposites show red shift in the plasmon resonance absorption peak and line shape broadening with respect to pure Au NPs. The negative binding energy shift of Au 4f_7/2 peak observed in X-ray Photoelectron Spectra (XPS) indicates charge transfer in the nano-soldered Au–SnO₂ between gold and tin oxide and formation of soldered nanocomposite.     

Optical properties of structurally modified glasses doped with gold ions

We report on the optical properties of a structurally modified silicate glass doped with Au ions. The area in the vicinity of the focal point of an 800-nm femtosecond laser in a glass sample became gray as a result of the formation of color centers after laser irradiation and turned red because of precipitation of Au nanoparticles after further annealing at 550 degrees C for 30 min. When the glass was excited by UV light at 365 nm, yellowish-white and orange-yellow emissions were observed in the laser-irradiated and the Au-nanoparticle-precipitated area, respectively. An optical Kerr shutter experiment showed that the Au nanoparticle-precipitated glass had an ultrafast nonlinear optical response, and the third-order nonlinear susceptibility was estimated to be approximately 10(-11) esu.