Considerations on the determining factors of the angular distribution of emitted particles in laser ablation

Simulations of particles which are emitted in laser ablation have been performed by the method of Direct Simulation Monte Carlo to investigate the deposition profiles of the emitted particles. The influences of the temperature, pressure and stream velocity of the initial evaporated layer formed during laser ablation process on the profile of the deposited film have been examined. It is found that the temperature gives a minor influence on the deposition profile, whereas the stream velocity and the pressure of the initial evaporated layer have a greater impact on the deposition profile. The energy in the direction of surface normal (E_⊥) and that in the parallel direction of the surface (E_||) are shown to increase and decrease, respectively after the laser irradiation due to collisions between the emitted particles, and this trend is magnified as the pressure increases. As a consequence, the stream velocity in the direction of surface normal increases with the increase in the pressure. A mechanism of the phenomenon that a metal with a lower sublimation energy shows a broader angular distribution of emitted particles is presented. It is suggested that low density of evaporated layer of a metal with a low sublimation energy at its melting point decreases the number of collisions in the layer, leading to the low stream velocity in the direction of surface normal, which results in the broader deposition profile of the emitted particles.     

Catalyst design using an inverse strategy: From mechanistic studies on inverted model catalysts to applications of oxide-coated metal nanoparticles

Metal-oxide interfaces are of great importance in catalytic applications since each material can provide a distinct functionality that is necessary for efficient catalysis in complex reaction pathways. Moreover, the synergy between two materials can yield properties that exceed the superposition of single sites. While interfaces between metals and metal oxides can play a key role in the reactivity of traditional supported catalysts, significant attention has recently been focused on using “inverted” oxide/metal catalysts to prepare catalytic interfaces with unique properties. In the inverted systems, metal surfaces or nanoparticles are covered by oxide layers ranging from submonolayer patches to continuous films with thickness at the nanometer scale. Inverse catalysts provide an alternative approach for catalyst design that emphasizes control over interfacial sites, including inverted model catalysts that provide an important tool for elucidation of mechanisms of interfacial catalytic reactions and oxide-coated metal nanoparticles that can yield improved stability, activity and selectivity for practical catalysts.This review begins by providing a summary of recent progress in the use of inverted model catalysts in surface science studies, where oxides are usually deposited onto the surface of metal single crystals under ultra-high vacuum conditions. Surface-level studies of inverse systems have yielded key insights into interfacial catalysis and facilitated active site identification for important reactions such as CO oxidation, the water-gas shift reaction, and CO₂ reduction using well-defined model systems, informing strategies for designing improved technical catalysts. We then expand the scope of inverted catalysts, using the “inverse” strategy for preparation of higher-surface area practical catalysts, chiefly through the deposition of metal oxide films or particles onto metal nanoparticles. The synthesis techniques include encapsulation of metal nanoparticles within porous oxide shells to generate core-shell type catalysts using wet chemical techniques, the application of oxide overcoat layers through atomic layer deposition or similar techniques, and spontaneous formation of metal oxide coatings from more conventional catalyst geometries under reaction or pretreatment conditions. Oxide-coated metal nanoparticles have been applied for improvement of catalyst stability, control over transport or binding to active sites, direct modification of the active site structure, and formation of bifunctional sites. Following a survey of recent studies in each of these areas, future directions of inverted catalytic systems are discussed.     

Growth of three-shell onionlike bimetallic nanoparticles

We show by molecular dynamics simulations on three systems (B/A=Pd/Ag, Cu/Ag, and Ni/Ag) that three-shell metallic nanoparticles made by a core of a metal A, an intermediate shell of metal B and an external shell of metal A (A-B-A nanoparticles) can be grown by deposition of B atoms onto an A core. The growth of the intermediate B shell is triggered by the fact that the most favorable positions for isolated B impurities inside A clusters are located just one layer below the cluster surface.     

Grafting of PMMA brushes on titania nanoparticulate surface via surface-initiated conventional radical and “controlled” radical polymerization (ATRP)

Stable dispersion of titania nanoparticles in organic solvents are obtained by grafting poly(methyl methacrylate) layer on to the surface. Titania nanoparticles are synthesized through the hydrolysis of titanium (IV) isopropoxide. The average size of the titania particles is found to be 15 ± 2 nm. The polymer layer was introduced onto the surface by immobilizing the initiating moiety. Azo initiator moiety required for surface-initiated conventional free radical polymerization and a tertiary bromide initiator moiety required for ATRP are attached covalently to the titania nanoparticulate surface through the surface hydroxyl groups. The “encapsulation” of PMMA layer results in the steric stabilization of the titania nanoparticles. Another important finding is that it is possible to grow polymer layer in a controlled fashion.     

Robust dithiocarbamate-anchored amine functionalization of Au nanoparticles

We introduce an effective and facile technique that achieves robust amine functionalization of Au nanoparticles by binding the polyamine poly(allylamine hydrochloride) (PAH) to the surface using a dithiocarbamate (DTC) modification of the side group amines. The DTC anchor confers superior short- and long-term colloidal stability compared to a physisorbed layer of the same polymer. We also demonstrate that the surface amines are available for further functionalization and that at least four alternately charged polyelectrolyte layers can be assembled onto the particles. The latter modification could not be performed on a physisorbed functional layer, so this demonstrates the effectiveness of the DTC groups in robustly anchoring the polymer to the particle surface. At the same time, the DTC-anchored polymer layer is less than 2 nm thick in the dry state. This is one-third of the thickness of a physisorbed polyamine layer deposited under the same conditions, and sufficiently thin that the plasmonic field enhancement on the metal particle remains accessible to the outside environment. We attribute the difference in thickness to multiple DTC bonds on each polymer chain forcing it into much closer conformity to the particle surface than in the physisorbed case.     

Sensitized Fluorescence of Silver Nanoparticles in the Presence of Pyrene

The fluorescence of pyrene adsorbed onto the surface of the cetyltrimethylammonium-coated silver nanoparticles was studied. Pyrene molecules adsorbed on freshly prepared silver particles were found to be in close proximity to silver surface thus providing the possibility of energy transfer from excited pyrene to silver cores of the particles. In that case along with the expected fluorescence of pyrene we observed the fluorescence of the silver nanoparticles induced by the excited pyrene molecules. In due course the restructuring of the cetyltrimethylammonium layer resulted in moving of pyrene molecules away from silver surface and simultaneous disappearance of the silver nanoparticles fluorescence band. These data strongly support the recent hypothesis of fluorophore-plasmon coupled emission.     

Enhancement of photoluminescence of the CdSe/CdS quantum dots on quartz substrates in the presence of silver nanoparticles

Multilayer systems consisting of layers of hybrid quantum dots are fabricated. The quantum dots with the CdSe/CdS core/shell structure are chemically synthesized and deposited on the surface of quartz glass that contains ion-synthesized silver nanoparticles in the near-surface region. Silver nanoparticles exhibit optical absorption owing to the localized surface plasmon resonance. Variations in the photoluminescence intensity of the layer related to an increase in the distance from the quartz surface with metal nanoparticles are studied. An increase in the photoluminescence intensity is observed under excitation in the spectral region of the plasmon absorption of silver nanoparticles. An optimal distance between the layers is determined to maximize the enhancement of the photoluminescence of quantum dots in the presence of the near field of metal nanoparticles.     

Growth and characterization of ZnO multipods on functional surfaces with different sizes and shapes of Ag particles

Three-dimensional ZnO multipods are successfully synthesized on functional substrates using the vapor transport method in a quartz tube. The functional surfaces, which include two different distributions of Ag nanoparticles and a layer of commercial Ag nanowires, are coated onto silicon substrates before the growth of ZnO nanostructures. The structures and morphologies of the ZnO/Ag heterostructures are investigated using X-ray diffraction and field emission scanning electron microscopy. The sizes and shapes of the Ag particles affect the growth rates and initial nucleations of the ZnO structures, resulting in different numbers and shapes of multipods. They also influence the orientation and growth quality of the rods. The optical properties are studied by photoluminescence, UV-vis, and Raman spectroscopy. The results indicate that the surface plasmon resonance strongly depends on the sizes and shapes of the Ag particles.     

Identification of Metal Contaminants on FCC Catalyst

FCC Catalyst deactivation is a major source of expense in the refining industry. Of concern is the deposition of contaminant metals onto the catalyst particles, leading to premature deactivation. Samples of used catalyst were collected from a working refinery using the standard sampling ports. These samples were subjected to surface examination by Scanning Electron Microscope, and to X‐ray Micro Analysis to determine elementary composition of key metals. Particle mapping was conducted to obtain cross sectional composition of both used and fresh catalyst. It was found that metals preferentially deposit onto the outside of the catalyst particles, presumably causing premature de‐activation to occur. Although the particles are found in a high attrition environment, the metal deposits formed a rough outer surface on the particle. Mild attrition of these particles was found to remove this outside layer of material and help to restore the original chemical make up of the particles surface. This work has shown how refineries can investigate metal deposition onto particles surfaces which will help them better manage FCCU catalyst usage.     

Carbohydrate particles as protein carriers and scaffolds: physico-chemical characterization and collagen stability

We report a simple and effective supercritical fluid route to uniformly load ultrafine metal nanoparticles on the hydrophobic surfaces of graphene sheets. In the presence of supercritical carbon dioxide, PtRu alloy nanoparticles are decorated evenly on functionalized graphene sheets (FGSs) upon the reduction of organic platinum (II) and ruthenium (III) precursors, and its application as an electrocatalyst for methanol oxidation is studied. Transmission electron microscopy observation shows that highly dispersed PtRu metallic nanoparticles with an average size of about 3.11?nm are uniformly and densely distributed on the hydrophobic surface of FGSs. X-ray diffraction patterns demonstrate that the particles had a face-centered cubic crystal structure, and X-ray photoelectron spectroscopy analysis indicates the existence of zero-valence metals. Compared with the widely used Vulcan XC-72 carbon black, the PtRu/FGS composites exhibit superior catalytic activity and stability for methanol oxidation. The huge surface area of graphene and uniform distribution of nanosized metal particles are two critical factors for the significantly enhanced electrocatalytic efficiency. The findings suggest that the supercritical fluid method is highly efficient in preparing graphene-supported metallic catalysts, and FGSs serve as a favorable electrocatalytic carrier for direct methanol fuel cells.     

Nanostructured Deposition of Nanoparticles from the Gas Phase

For many applications, nanoparticles from the gas phase are of interest due to their physical properties. Especially for electronic or optoelectronic applications, the transfer from their random distribution in the gas phase onto flat substrate surfaces has to be controlled because the particles are needed in exactly defined areas on the substrate. We demonstrate a parallel process for the transfer of charge patterns on oxidized silicon surfaces followed by the deposition of monodisperse singly charged nanoparticles, which allows the creation of particle arrangements reaching from 100 nm resolution up to structures in the upper micrometer range. The charge patterns are transferred using a polydimethylsiloxane (PDMS) stamp, which is covered with a metal layer. By applying different voltages to the stamp, negative or positive charges can be transferred. Thus, nanoparticles of different polarities can be guided to certain places.     

Surface functionalization of silica-coated magnetic nanoparticles for covalent attachment of cholesterol oxidase

A systematic approach towards the fabrication of highly functionalized silica shell magnetic nanoparticles, presently used for enzyme immobilization, is herein fully presented. The synthesis of bare maghemite (γ-Fe₂O₃) nanoparticles was accomplished by thermal co-precipitation of iron ions in ammonia alkaline solution at harsh reaction conditions, respectively. Primary surface engineering of maghemite nanoparticles was successfully performed by the proper deposition of silica onto nanoparticles surface under strictly regulated reaction conditions. Next, the secondary surface functionalization of the particles was achieved by coating the particles with organosilane followed by glutaraldehyde activation in order to enhance protein immobilization. Covalent immobilization of cholesterol oxidase was attempted afterwards. The structural and magnetic properties of magnetic silica nanocomposites were characterized by TEM and vibrating sample magnetometer (VSM) instruments. X-ray diffraction measurements confirmed the spinel structure and average size of uncoated maghemite nanoparticles to be around 20 nm in diameter. SEM-EDS spectra indicated a strong signal for Si, implying the coating procedure of silica onto the particles surface to be successfully accomplished. Fourier transform infrared (FT-IR) spectra analysis confirmed the binding of amino silane molecules onto the surface of the maghemite nanoparticles mediated Si-O-Si chemical bonds. Compared to the free enzyme, the covalently bound cholesterol oxidase retained 50% of its activity. Binding of enzyme onto chemically modified magnetic nanoparticles via glutaraldehyde activation is a promising method for developing biosensing components in biomedicine.     

Graphene layer number dependent size distribution of silver nanoparticles

We observe that silver atoms deposited by thermal evaporation deposition onto n-layer graphene films condense upon annealing to form nanoparticles with an average diameter and density that is determined by the layer numbers of graphene films. The optical microscopy and Raman spectroscopy were utilized to identify the number of the graphene layers and the SEM (scanning electron microscopy) was used to observe the morphologies of the particles. Systematic analysis revealed that the average sizes of the nanoparticles increased with the number of graphene layers. The density of nanoparticles decreased as the number of graphene layers increased, revealing a large variation in the surface diffusion strength of nanoparticles on the different substrates. The mechanisms of formation of these layer-dependent morphologies of silver nanoparticles are related to the surface free energy and surface diffusion of the n-layer graphenes.     

Ar环境气压对纳米Si晶粒成核区范围的影响

为了研究不同环境气压条件下纳米Si晶粒成核区的范围,采用波长为308 nm的 XeCl脉冲准分子激光器,分别在1-200 Pa的Ar气环境下, 烧蚀高阻抗单晶Si靶,在距离烧蚀点正下方2.0 cm处水平放置一系列单晶Si 或玻璃衬底,沉积制备了纳米Si薄膜. Raman谱和X射线衍射谱测量证实了薄膜中纳米Si晶粒已经形成. 扫描电子显微镜的测量结果表明,环境气压的变化影响了衬底上纳米Si晶粒的平均尺寸及其分布范围. 根据成核区位置的确定方法,计算得出随着环境气压的增加纳米Si晶粒成核区的范围先变宽后变窄的规律. 从烧蚀动力学的角度对实验结果进行了分析.     

Surface composition of the steel powders pre-alloyed with manganese

The determination of the surface oxide layer composition is vital to facilitate the adjustment of the sintering conditions for sufficient removal of the surface oxides for providing strong metal bonding between the metal particles during sintering. To systematically investigate the composition, morphology and thickness of the surface oxide the influence of manganese content from 0.3 to 1.8 wt.% on the surface products composition in the case of water atomized steel powder was evaluated. Analysis of the powder surfaces by X-ray photoelectron spectroscopy and high-resolution scanning electron microscopy in combination with X-ray microanalysis showed that powder particles in all cases are covered by heterogeneous oxide layer, composed of particulate features of thermodynamically stable oxides (Cr-Mn-Si) and homogeneous iron surface oxide layer in between. For increasing alloying content the fraction of stable oxide cations in the surface layer increases linearly, whereas the thickness of the iron oxide layer decreases. Moreover, from the investigation of the sintering and degassing behavior by thermal analysis coupled with mass-spectrometry (TG/DTA + MS), three different stages of carbothermal reduction process were observed and their correlation with surface oxides composition was established during sintering in argon.     

Preparation and application of polymer-grafted magnetic nanoparticles for lipase immobilization

Functionalized superparamagnetic particles were prepared by graft polymerization of glycidyl methacrylate and methacryloxyethyl trimethyl ammonium chloride onto the surface of modified-Fe₃O₄ nanoparticles. The resultant particles were characterized by X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, and vibrating sample magnetometry. The results indicate that the polymer chains had been effectively grafted onto the surface of Fe₃O₄ nanoparticles. The functionalized particles remained dispersive and superparamagnetic. Lipase was immobilized on the magnetic particles under mild conditions by electrostatic adsorption and covalent binding with the activity recovery up to 70.4%. The immobilized lipase had better thermal stability compared to free lipase.     

Surface influence on the behavior of stabilized zirconia nanoparticles under pressure

The surface state of partially stabilized zirconia with nanoparticles of sizes 10–30 nm after temperature and pressure treatments was investigated by Fourier transform infrared spectroscopy, X-ray diffraction and small-angle X-ray scattering. It is shown that the synthesized nanoparticles are surface fractals and the fractal dimensions non-monotonically change with nanoparticles size change. The martensite tetragonal-to-monoclinic transition of the partially stabilized zirconia nanoparticles under hydrostatic pressure (100–1000 MPa) was investigated. It was shown that the character of the martensite transition in nanoparticles’ system depends on the pressure values. Three ranges of pressures were revealed. It was shown that the stability of martensite tetragonal–monoclinic transition decreases with the increase in size of the nanoparticles only for the pressures range of 300–500 MPa. Below 200 MPa, the character of the martensite transition is extreme and has a maximum for the particle size of 17 nm. In pressure range of 600–1000 MPa, the degree of martensite transition is dependent on the fractal dimension of the surface.     

Electron photoemission in plasmonic nanoparticle arrays: analysis of collective resonances and embedding effects

We theoretically study the characteristics of photoelectron emission in plasmonic nanoparticle arrays. Nanoparticles are partially embedded in a semiconductor, forming Schottky barriers at metal/semiconductor interfaces through which photoelectrons can tunnel from the nanoparticle into the semiconductor; photodetection in the infrared range, where photon energies are below the semiconductor band gap (insufficient for band-to-band absorption in semiconductor), is therefore possible. The nanoparticles are arranged in a sparse rectangular lattice so that the wavelength of the lattice-induced Rayleigh anomalies can overlap the wavelength of the localized surface plasmon resonance of the individual particles, bringing about collective effects from the nanoparticle array. Using full-wave numerical simulations, we analyze the effects of lattice constant, embedding depth, and refractive index step between the semiconductor layer and an adjacent transparent conductive oxide layer. We show that the presence of refractive index mismatch between media surrounding the nanoparticles disrupts the formation of a narrow absorption peak associated with the Rayleigh anomaly, so the role of collective lattice effects in the formation of plasmonic resonance is diminished. We also show that 5–20 times increase of photoemission can be achieved on embedding of nanoparticles without taking into account dynamics of ballistic electrons. The results obtained can be used to increase efficiency of plasmon-based photodetectors and photovoltaic devices. The results may provide clues to designing an experiment where the contributions of surface and volume photoelectric effects to the overall photocurrent would be defined.     

Surface modification of ceria nanoparticles and their chemical mechanical polishing behavior on glass substrate

To improve their chemical mechanical polishing (CMP) performance, ceria nanoparticles were surface modified with γ-aminopropyltriethoxysilane (APS) through silanization reaction with their surface hydroxyl group. The compositions, structures and dispersibility of the modified ceria particles were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), laser particle size analyzer, zeta potential measurement and stability test, respectively. The results indicated that APS had been successfully grafted onto the surface of ceria nanoparticles, which led to the modified ceria nanoparticles with better dispersibility and stability than unmodified ceria particles in aqueous fluids. Then, CMP performance of the modified ceria nanoparticles on glass substrate was investigated. Experimental results showed that the modified ceria particles exhibited lower material removal rate (MRR) but much better surface quality than unmodified ceria particles, which may be explained by the hardness reduction of ceria particles, the enhancement of lubrication of the particles and substrate surfaces, and the elimination of the agglomeration among the ceria particles.