Nanoparticles from the Gas Phase as Building Blocks for Electrical Devices

Electrical device development is driven by miniaturization and possibilities to use new chemical and physical effects. Nanotechnology offers both aspects. The structural dimensions of materials and devices are small and because of that large exchange surfaces are provided but also effects like quantum effects may occur and be used to get new or at least improved properties of nanostructured materials and devices.Nanoparticles are of special interest because of their nanodimensions in all three directions, so that nanoeffects become most prominent. They can be synthesized in solid materials, in liquids and in gases. Gas synthesis has several advantages compared to the other phases, especially the high cleanliness which can be achieved. In case of electrical devices the particles have to be deposited onto substrates in a structured way.The substrate may consist out of microelectronic devices in which the deposited nanoparticles are introduced for the basic function. In case of a transistor this would be the gate function, in case of a sensor this would be the sensing layer, where the contact with the measurement object takes place. For two kinds of particles SnO₂ and PbS, synthesized in the gas phase, we demonstrate the way how to create devices with improved sensor properties.     

The Effect of Substrate Temperature on the Properties of Nanostructured Silicon Carbide Films Deposited by Hypersonic Plasma Particle Deposition

Nanostructured silicon carbide films have been deposited on molybdenum substrates by hypersonic plasma particle deposition. In this process a thermal plasma with injected reactants (SiCl₄ and CH₄) is expanded through a nozzle leading to the nucleation of ultrafine particles. Particles entrained in the supersonic flow are then inertially deposited in vacuum onto a temperature-controlled substrate, leading to the formation of a consolidated film. In the experiments reported, the deposition substrate temperature T_s has ranged from 250°C to 700°C, and the effect of T_s on film morphology, composition, and mechanical properties has been studied. Examination of the films by scanning electron microscopy has shown that the grain sizes in the films did not vary significantly with T_s. Micro-X-ray diffraction analysis of the deposits has shown that amorphous films are deposited at low T_s, while crystalline films are formed at high T_s. Rutherford backscattering spectrometry has indicated that the films are largely stoichiometric silicon carbide with small amounts of chlorine. The chlorine content decreases from 8% to 1.5% when the deposition temperature is raised from 450°C to 700°C. Nanoindentation and microindentation tests have been performed on as-deposited films to measure hardness, Young's modulus and to evaluate adhesion strength. The tests show that film adhesion, hardness and Young's modulus increase with increasing T_s. These results taken together demonstrate that in HPPD, as in vapor deposition processes, the substrate temperature may be used to control film properties, and that better quality films are obtained at higher substrate temperatures, i.e. T_s700°C.     

Research in Korea on Gas Phase Synthesis and Control of Nanoparticles

Research activity into the gas phase synthesis of nanoparticles has witnessed rapid growth on a worldwide basis, which is also reflected by Korean research efforts. Nanoparticle research is inherently a multi-disciplinary activity involving both science and engineering. In this paper, the recent studies undertaken in Korea on the gas phase synthesis and control of nanoparticles are reviewed. Studies on the synthesis of various kinds of nanoparticles are first discussed with a focus on the different types of reactors used. Recent experimental and theoretical studies and newly developed methods of measuring and modeling nanoparticle growth are also reviewed.     

Aggregation and Deposition Characteristics of Fullerene Nanoparticles in Aqueous Systems

The propensity of n-C₆₀ to aggregate and deposit will play a key role in determining its longevity in aquatic systems, and therefore the potential exposure and risk presented by these colloids. We consider the origin of n-C₆₀ stability and compare the aggregation and deposition characteristics of n-C₆₀ under conditions of variable ionic strength using an indifferent electrolyte. Relatively weak electrolyte solutions (0.001 M) were observed to destabilize suspensions of n-C₆₀ resulting in the formation of settleable aggregates. This behavior supports the hypothesis that the stabilizing mechanism for n-C₆₀ clusters is electrostatic in origin. Similarly, the deposition of n-C₆₀ in porous media increased as ionic strength increased. These observations suggest that under some conditions present in natural aquatic systems, these materials may have limited mobility as they form large aggregates that may settle out of suspension or deposit on surfaces. These phenomena may, at least partially, offset any risk presented by n-C₆₀ toxicity due to a reduced potential for exposure.     

Interface Colloidal Deposition of Nanoparticle Wire Structures

Inspired by natural dewetting phenomena, such as the coffee‐ring effect, researchers are developing strategies for the controlled assembly of colloidal particles into functional nanoparticle conglomerates. Colloidal assembly techniques are regarded as green methods as they reduce or eliminate the use or generation of hazardous substances involved in other manufacturing modalities. This review discusses several recent developments in interface colloidal deposition for preparing nanoparticle wires and integrated nanoparticle wire arrays. Moreover, this review covers real applications of these structures for electric detection of chemical and biological molecules among other functions.     

气相爆炸流场中TiO_2纳米颗粒生长的数值分析初探

气相爆炸制备TiO2纳米颗粒的实验成果在近年来多有报道,但对颗粒成长的模拟尚不多见。引入一种气溶胶的单分散性物理模型(Kruis模型),将其应用于气相爆炸流场中TiO2纳米颗粒生长的数值模拟,结合气相爆炸制备实验进行对比分析。结果表明,通过控制前驱体反应组分,气相爆轰合成了直径范围为20~150nm的球形TiO2纳米颗粒。数值模拟得到的颗粒大小与实验观测结果基本一致。影响纳米颗粒生长的主要因素包括反应温度、颗粒浓度及反应时间。     

Thermodynamic-Controlled Gas Phase Process for the Synthesis of Nickel Nanoparticles of Adjustable Size and Morphology

Gas phase processes are a successful route for the synthesis of nano materials. Nickel particles are used in applications ranging from catalysis to nano electronics and energy storage. The application field defines the required particle size, morphology, crystallinity and purity. Nickel tetracarbonyl is the most promising precursor for the synthesis of high purity nickel particles. Due to the toxicity of this precursor and to obtain an optimal process control we developed a two-step flow type process. Nickel carbonyl and nickel particles are synthesized in a sequence of reactions. The particles are formed in a hot wall reactor at temperatures below 400°C in different gas compositions. Varying the process conditions enables the adjustment of the particle size in a range from 3 to 140 nm. The controllable crystalline habits are polycrystalline, single crystals or multiple twinned particles (MTP). Spectroscopic investigations show an excellent purity. We report about the process and first investigations of the properties of the synthesized nickel nanomaterial.     

Gold Nanoparticles: Production,Reshaping, and Thermal Charging

Gold nanoparticles are of great interest for various nanoelectronic applications, e.g., for making single electron transistors or very fine leads to molecular size entities. For this and other applications, it is important that all particles have controllable size and shape. In this paper, we describe the production of size-selected gold aerosol particles in the 20nm range made by evaporation in a high-temperature tube furnace and subsequent size selection. To obtain spherical particles, it was necessary to reshape the particles at high temperature, which was investigated for temperatures between 25°C and 1200°C. High-resolution transmission electron microscopy showed that the degree of crystallinity became higher for higher reshaping temperature. During reshaping at high temperature, an anomalous charging behavior was discovered, whereby negatively as well as positively charged particles became multiply negatively charged. Possible mechanisms for explaining this thermally activated phenomenon are discussed.     

A High Efficiency,High Throughput Unipolar Aerosol Charger for Nanoparticles

A novel aerosol charger has been developed, which has high efficiency and high throughput especially for nanometer particles in the size range of 3–50nm. Unipolar charging with high ion concentration and long charging time is used to obtain the high charging efficiency. High throughput is achieved by reducing particle loss within the charger. This is accomplished by directing ion flow and aerosol flow in the same direction and by the use of sheath air flow. The charger configuration is of a longitudinal design – the direction of aerosol stream and ion stream are flowing parallel along the longitudinal axis of the charger. The charger consists of four sections: the inlet zone, the ion production zone, the unipolar charging zone, and the exit zone. In the inlet and ion production zones, unipolar ions are generated using Po²¹⁰ radioactive sources with an electric field designed to separate the positive and negative ions, and to focus the selected unipolar ions into the core region of the charger. The ions with the selected polarity is then attracted to the charging zone by an uniform electric field created by a series of ring electrodes applied with a linear ramped voltage. Aerosol entering the charger is sheathed with clean gas flow in order to keep the aerosol in the core region. A novel exit design with a reversed electric field is incorporated in order to minimize the charged particles loss. The performance of the charger is first evaluated using computer simulation and then constructed for experimental validation. Experiment data have demonstrated that the charger achieves 90% and 95% charged-particles penetration efficiency and with 22% and 48% extrinsic charging efficiency at 3 and 5nm particle sizes, respectively. These performance data represent significant improvement, over a factor of 10, compared with the existing chargers.     

A Rapid Method for Growth of Metal Nanoparticles on Nanowire Substrates

The production of nickel and platinum nanoparticles on silica nanowire substrates using plasma-enhanced chemical vapor deposition has been investigated. Determination of particle size and particle size distribution was done using transmission electron microscopy (TEM). Ni nanoparticle diameters were found to be between 2 and 6 nm, with particle size increasing as the substrate temperature increased from 573 to 873 K. The size of Ni nanoparticles was found to be dependent on the chamber pressure during growth. The results indicate a competition between pressure-related diffusion within the vapor and dissociation of the precursor. Pt nanoparticle diameters were consistently found to be 2.5–3.0 nm at all deposition conditions. Insufficient thermal energy within the studied range results in a minimal contribution from surface diffusion, the primary mechanism for nanoparticle growth.     

3D Nanostructured Polypyrrole/Sodium Alginate Conducting Hydrogel from self-assembly with High Supercapacitor Performance

Due to their possible ideal three dimensional (3D) nanostructures and excellent electrochemical properties, conducting hydrogels have attracted much attention in recent years. Herein, pyrrole monomer was directly dissolved in an aqueous solution of sodium alginate (SA), and was allowed to undergo in-situ polymerization to form polypyrrole (Ppy), resulting in formation of Ppy/SA, a conducting hydrogel, via self-assembly between the polymers. Observation by SEM indicated that the microstructure of the Ppy/SA hydrogel was a typical 3D nano-cylinder network, with the cylinders formed by entanglements of the Ppy and SA molecular chains (cylinder diameter was ～100 nm). The electrochemical measurements of cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy indicated that the Ppy/SA hydrogel possessed typical pseudocapacitance, good charging and discharging rate performance, and favorable capacitive behavior; the specific capacity reached up to 249 F/g at the current density of 0.2 A/g. We suggest it has great potential in the field of high-performance electrode materials for supercapacitors.     

燃气透平叶片表面颗粒沉积特性数值研究进展

污染物颗粒在燃气透平叶片表面及冷却通道内的沉积将影响透平叶片的冷却特性和安全服役寿命。国外许多研究机构对燃气透平叶片表面污染物颗粒沉积特性及其与叶片气膜冷却的相互作用机制进行了持续研究。本文首次系统总结了近年来燃气透平叶片表面污染物颗粒沉积特性数值研究进展,重点介绍了燃气透平叶栅流道内污染物颗粒的沉积机制、颗粒沉积和脱离物理模型以及颗粒沉积与透平叶片冷却特性相互作用的数值模拟方法和研究成果。基于当前研究热点和发展趋势,结合作者的研究经历,指出了国内在研发先进燃气轮机透平冷却结构时应注意的问题和方向,为高效、燃料适应性更广的燃气轮机技术自主开发奠定基础。     

利用脉冲激光沉积法制备高Mg掺杂的六方相MgZnO薄膜

选用Mg0.2Zn0.8O陶瓷靶,利用脉冲激光沉积(PLD)法,在单晶Si(100)和石英衬底上生长了一系列MgZnO薄膜(MZO)。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱(EDS)和紫外可见光透射光谱(UV-Vis)等实验手段,研究了在不同工作压强下生长的薄膜样品的晶体结构、微观形貌和光学性能的变化。结果表明:所有的薄膜样品都是单一的ZnO六方相,禁带宽度随生长压强的升高而增加,变化范围在3.83～4.05eV之间,最短吸收边接近300nm。     

Solid-state Water-mediated Transport Reduction of Nanostructured Iron Oxides

The Fe²⁺/Fe³⁺ ratio in two-dimensional iron oxide nanosructures (nanolayers with a thickness of 0.3–1.5 nm on silica surface) may be precisely controlled using the transport reduction (TR) technique. The species –O–Fe(OH)₂ and (Si–O–)₂–FeOH forming the surface monolayer are not reduced at 400–600°C because of their covalent bonding to the silica surface, as demonstrated by Mössbauer spectroscopy. Iron oxide microparticles (microstructures) obtained by the impregnation technique, being chemically unbound to silica, are subjected to reduction at T 500°C with formation of metallic iron in the form of -Fe. Transport reduction of supported nanostructures (consisting of 1 or 4 monolayers) at T 600°C produces bulk iron(II) silicate and metallic iron phases. The structural-chemical transformations occurring in transport reduction of supported iron oxide nanolayers are proved to be governed by specific phase processes in the nanostructures themselves.     

Effect of Particle Size and Phase Composition of Titanium Dioxide Nanoparticles on the Photocatalytic Properties

Titanium dioxide (TiO₂) nanoparticles were prepared by the oxidation of titanium tetrachloride (TiCl₄) in a diffusion flame reactor. The average diameter of particles was 15–30 nm and mass fraction of anatase ranged from 40% to 80%. Effects of particle size and phase composition of those TiO₂ nanoparticles on photocatalytic properties such as decomposition of methylene blue, bacteria and ammonia gas were investigated. The degree of decomposition of methylene blue by the TiO₂ nanoparticles under the illumination of the black light was directly proportional to the anatase mass fraction, but inversely to the particle size. The decomposition of bacteria and ammonia gas by the TiO₂ nanoparticles under the illumination of the fluorescent light showed the same trend as in the case of the methylene blue.     

The Formation of Porous Membranes by Filtration of Aerosol Nanoparticles

Flame-generated aerosol particles of Al₂O₃ were deposited by gas filtration on two types of porous and ceramic tubes of -Al₂O₃ with mean pore diameters of 450 and 2700nm, respectively. The particles were aggregates with average mobility diameters in the range of 30–100nm and primary particle diameters of 4–8nm. The particles are characterized by differential mobility analysis, transmission electron microscopy, and by their specific surface area. The deposited membranes are characterized by gas permeability measurements, scanning electron microscopy, and by their pore size distribution from nitrogen capillary condensation. The particles form a distinct, homogeneous membrane layer with a porosity of 90% on top of the substrate surface and only penetrate slightly into the substrate structure. The mean pore sizes of the deposited membranes determined by nitrogen condensation agree approximately with those determined by gas permeation and the specific surface area. The mean pore diameter varies in the range of 30–70nm. The gas permeability of the deposited membranes is related to the specific surface area but influenced by the high porosity. The mean pore size and the permeability of the membranes are almost independent of the substrate structure.The development of a membrane with uniform properties is preceded by a short initial period in which the deposited particles, with an equivalent membrane thickness of roughly 2m, have a significantly lower permeability than the ultimately developed uniform membrane layer. This effect is particularly significant for the aerosol particles with the lowest mean size, probably due to particles deposited in the pore mouths of the substrate.The particles and the deposited membranes are X-ray amorphous but retain their specific surface area on heating to even high temperatures. When the membranes are heated to 1473K for 10h, X-ray diffraction shows a mixture of - and -alumina, accompanied by a partial disintegration of the membrane and a considerable loss of surface area.     

液相沉积法制备的二氧化硅薄膜及其钝化性能

采用液相沉积法在硅基底上成功制备了二氧化硅薄膜,利用扫描电子显微镜、光电子能谱和少子寿命测试仪等对二氧化硅薄膜的组织结构和钝化性能进行了研究,结果表明,液相生长的二氧化硅薄膜致密平整,含有少量的F元素;对硅具有较好的减反和钝化作用,平均反射率由28.87%降低至10.88%,表面复合速度由6 923 cm/s降低至2 830 cm/s。     

ZnO纳米颗粒受激发射的时间分辨特性

在飞秒脉冲激光激发下,观察到了均匀沉积法获得的ZnO纳米颗粒的受激辐射现象,并从频域和时域两方面研究了ZnO纳米多晶的室温激射特性。氧化锌纳米颗粒中出现激子-激子散射导致的激射阈值为7.2 GW·cm-2,激射模式类似于F-P谐振腔模式,时域谱则表现为寿命曲线中出现快速衰减成分。与荧光的时间衰减曲线不同,P带时间衰减具有对称结构,高斯拟合结果只有几个ps,接近条纹相机的时间分辨率极限。研究ZnO纳米颗粒的受激发射与激光特性对揭示ZnO晶体的内部结构和激子激发态的性质、激光产生的机理等有重要意义。     

Nanostructured sapphire vicinal surfaces as templates for the growth of self-organized oxide nanostructures

Vicinal substrates of sapphire with miscut angle of 10° from the (0 0 1) planes towards the [1 1 0] direction have been annealed in air in the range from 1000 to 1500 °C. The behaviour of these surfaces has been characterized as a function of the temperature and the thermal treatment time by Atomic Force Microscopy observations. A thermal treatment at 1250 °C allows to stabilize a surface made of periodically spaced nanosized step-bunches. Such stepped surfaces were used as template to grow self-patterned epitaxial oxide nanoparticles by thermal annealing of yttria-stabilized zirconia thin films produced by sol-gel dip-coating. Grazing Incidence Small Angle X-ray Scattering and High-Resolution Transmission Electron Microscopy were used to study the morphology of the nanoparticles and their epitaxial relationships with the substrate.