A. Schmidt-Ott

Nanoparticle Formation by Laser Ablation

The properties of nanoparticle aerosols of size ranging from 4.9 nm to 13 nm, generated by laser ablation of solid surfaces are described. The experimental system consisted of a pulsed excimer laser, which irradiated a rotating target mounted in a cylindrical chamber 4 cm in diameter and 18-cm long. Aerosols of oxides of aluminum, titanium, iron, niobium, tungsten and silicon were generated in an oxygen carrier gas as a result of a reactive laser ablation process. Gold and carbon aerosols were generated in nitrogen by non-reactive laser ablation. The aerosols were produced in the form of aggregates of primary particles in the nanometer size range. The aggregates were characterized using a differential mobility analyzer and electron microscopy. Aggregate mass and number concentration, electrical mobility size distribution, primary particle size distribution and fractal dimension were measured. System operating parameters including laser power (100 mJ/pulse) and frequency (2 Hz), and carrier gas flow rate (1 l/min) were held constant.A striking result was the similarity in the properties of the aerosols. Primary particle size ranged between 4.9 and 13 nm for the eight substances studied. The previous studies with flame reactors produced a wider spread in primary particle size, but the order of increasing primary particle size follows the same trend. While the solid-state diffusion coefficient probably influences the size of the aerosol in flame reactors, its effect is reduced for aerosols generated by laser ablation. It is hypothesized that the reduced effect can be explained by the collision-coalescence mechanism and the very fast quenching of the laser generated aerosol.

Mass and size determination of nanometer particles by means of mobility analysis and focused impaction

Abstract Particles in the size range of a few nanometers are characterized by means of a differential mobility analyzer (DMA) of the Eichler type in tandem with a focusing impactor with electrostatic blowing. One application of the DMA-impactor combination is determination of particle mass m p without knowledge of the relation Z ( d p ) between particle mobility Z and diameter d p . With Z ( d p ) known, also the size and density ρ p of spherical particles can be determined. A mobility versus diameter relation Z ( d p ) for the range of a few nanometers is derived from the literature. It considers the effect of the finite diameter d of gas molecules, neglected in conventional studies. According to this relation, plots of Z −1/2 versus m p 1/3 yield straight lines, and the intersection with the Z −1/2 axis is linearly related to the effective diameter d of the carrier gas molecules. Experimental data recorded with the DMA-impactor combination for silver particles are consistent with this relation. The same applies for values from literature for fullerenes and proteins. For air, d is approximately 0.53 nm , not far from the 0.6 nm estimated by Tammet (1995) . The particle density ρ p is derived from m p and the diameter inferred from Z ( d p ). Measurement of ρ p on silver particles showed that charging devices may introduce contamination leading to formation of an adsorbed layer on the particles, reducing their measured density. The DMA-Impactor combination applied has sufficient resolving power to observe occurrence of different shapes of particles prepared by vapor condensation.

Toward industrial scale synthesis of ultrapure singlet nanoparticles with controllable sizes in a continuous gas-phase process

Continuous gas-phase synthesis of nanoparticles is associated with rapid agglomeration, which can be a limiting factor for numerous applications. In this report, we challenge this paradigm by providing experimental evidence to support that gas-phase methods can be used to produce ultrapure non-agglomerated “singlet” nanoparticles having tunable sizes at room temperature. By controlling the temperature in the particle growth zone to guarantee complete coalescence of colliding entities, the size of singlets in principle can be regulated from that of single atoms to any desired value. We assess our results in the context of a simple analytical model to explore the dependence of singlet size on the operating conditions. Agreement of the model with experimental measurements shows that these methods can be effectively used for producing singlets that can be processed further by many alternative approaches. Combined with the capabilities of up-scaling and unlimited mixing that spark ablation enables, this study provides an easy-to-use concept for producing the key building blocks for low-cost industrial-scale nanofabrication of advanced materials.

Plasmonic nanoparticle-semiconductor composites for efficient solar water splitting

Photoelectrochemical (PEC) water splitting is a promising technology that uses light absorbing semiconductors to convert solar energy directly into a chemical fuel (i.e., hydrogen). PEC water splitting has the potential to become a key technology in achieving a sustainable society, if high solar to fuel energy conversion efficiencies are obtained with earth abundant materials. This review article discusses recent developments and discoveries in the mechanisms by which the localized surface plasmon resonance (LSPR) in metallic nanoparticles can increase or complement a neighbouring semiconductor in light absorption for catalytic water splitting applications. These mechanisms can mitigate the intrinsic optical limitations of semiconductors (e.g., metal oxides) for efficient solar water splitting. We identify four types of enhancement mechanisms in the recent literature: (i) light scattering, (ii) light concentration, (iii) hot electron injection (HEI), and (iv) plasmon-induced resonance energy transfer (PIRET). (i) Light scattering and (ii) light concentration are light trapping mechanisms that can increase the absorption of light with energies above the semiconductor optical band-edge. These two mechanisms are ideal to enhance the absorption of promising semiconductors with narrow bandgap energies that suffer from limited absorption coefficients and bulk charge recombination. On the other hand, (iii) HEI and the recently discovered (iv) PIRET are mechanisms that can enhance the absorption also below the semiconductor optical band-edge. Therefore, HEI and PIRET have the potential to extend the light utilization to visible and near-infrared wavelengths of semiconductors with excellent electrochemical properties, but with large bandgap energies. New techniques and theories that have been developed to elucidate the above mentioned plasmonic mechanisms are presented and discussed for their application in metal oxide photoelectrodes. Finally, other plasmonic and non-plasmonic effects that do not increase the device absorption, but affect the electrochemical properties of the semiconductor (e.g., charge carrier transport) are also discussed, since a complete understanding of these phenomena is fundamental for the design of an efficient plasmonic NP-semiconductor water splitting device.

Performance of a hypersonic impactor with silver particles in the 2 nm range

Abstract The performance of a hypersonic impactor is studied in the diameter range down to 2 nm with condensation particles from silver vapors. Particles of a single mobility are selected with a differential mobility analyzer, and sized from the measured mobility on the assumption that the usual size-mobility relations hold in the nanometer range. The inferred “aerodynamic density“ is between 2 and 3 times smaller than that of crystalline Ag, so that the particles are either non-spherical or non-pure crystalline Ag, or the usual size-mobility relations fail in this size range. Yet, this aerosol provides a source for the smallest particles yet analyzed aerodynamically. New results are that: (a) the resolving power of the instrument does not diminish at decreasing particle size, at least down to 2 nm; (b) the minimum capture efficiency η min observed below the critical Stokes number (6.5–8%) is nearly independent of particle diameter in all the range above 2 nm and (c) the characteristic response curves of the impactor do not improve upon sheathing a core aerosol flow with clean air. A provisional conclusion is that the origine of η min is probably turbulent diffusion.

A Cost-Effective Electrostatic Precipitator for Aerosol Nanoparticle Segregation

Copyright 2015 American Association for Aerosol Research

Atomic Cluster Generation with an Atmospheric Pressure Spark Discharge Generator

A new method for generating metal clusters in the gas phase is described and characterized in this work. The method is based on material evaporation by spark ablation at atmospheric pressure. The characterization of atomic clusters was done by measuring their electrical mobility. The measured mobilities were compared with values found in literature in order to identify the cluster species. We show that silver clusters consisting from one up to 25 atoms can be produced in helium at atmospheric pressure. In addition, the effect of oxygen concentration on the resulting cluster mobility distribution was investigated. Results show that at higher oxygen level, the mobility distribution is dominated by the abundance of stable clusters (i.e., magic number clusters). This can be attributed to an oxidation etching effect. Copyright 2015 American Association for Aerosol Research

Characterization of Tungsten Oxide Thin Films Produced by Spark Ablation for NO2 Gas Sensing

Tungsten oxides (WOx) thin films are currently used in electro-chromic devices, solar-cells and gas sensors as a result of their versatile and unique characteristics. In this study, we produce nanoparticulate WOx films by spark ablation and focused inertial deposition, and demonstrate their application for NO2 sensing. The primary particles in the as-deposited film samples are amorphous with sizes ranging from 10 to 15 nm. To crystallize the samples, the as-deposited films are annealed at 500 °C in air. This also caused the primary particles to grow to 30-50 nm by sintering. The morphologies and crystal structures of the resulting materials are studied using scanning and transmission electron microscopy and X-ray diffraction, whereas information on composition and oxidation states are determined by X-ray photoemission spectroscopy. The observed sensitivity of the resistance of the annealed films is ∼100 when exposed to 1 ppm of NO2 in air at 200 °C, which provides a considerable margin for employing them in gas sensors for measuring even lower concentrations. The films show a stable and repeatable response pattern. Considering the numerous advantages of spark ablation for fabricating nanoparticulate thin films, the results reported here provide a promising first step toward the production of high sensitivity and high accuracy sensors.

Hot Carrier Generation and Extraction of Plasmonic Alloy Nanoparticles

The conversion of light to electrical and chemical energy has the potential to provide meaningful advances to many aspects of daily life, including the production of energy, water purification, and optical sensing. Recently, plasmonic nanoparticles (PNPs) have been increasingly used in artificial photosynthesis (e.g., water splitting) devices in order to extend the visible light utilization of semiconductors to light energies below their band gap. These nanoparticles absorb light and produce hot electrons and holes that can drive artificial photosynthesis reactions. For n-type semiconductor photoanodes decorated with PNPs, hot charge carriers are separated by a process called hot electron injection (HEI), where hot electrons with sufficient energy are transferred to the conduction band of the semiconductor. An important parameter that affects the HEI efficiency is the nanoparticle composition, since the hot electron energy is sensitive to the electronic band structure of the metal. Alloy PNPs are of particular importance for semiconductor/PNPs composites, because by changing the alloy composition their absorption spectra can be tuned to accurately extend the light absorption of the semiconductor. This work experimentally compares the HEI efficiency from Ag, Au, and Ag/Au alloy nanoparticles to TiO2 photoanodes for the photoproduction of hydrogen. Alloy PNPs not only exhibit tunable absorption but can also improve the stability and electronic and catalytic properties of the pure metal PNPs. In this work, we find that the Ag/Au alloy PNPs extend the stability of Ag in water to larger applied potentials while, at the same time, increasing the interband threshold energy of Au. This increasing of the interband energy of Au suppresses the visible-light-induced interband excitations, favoring intraband excitations that result in higher hot electron energies and HEI efficiencies.

Fractal disperse hydrogen sorption kinetics in spark discharge generated Mg/NbOx and Mg/Pd nanocomposites

Isothermal hydrogen desorption of spark discharge generated Mg/NbOx and Mg/Pd metal hydride nanocomposites is consistently described by a kinetic model based on multiple reaction rates, in contrast to the Johnson-Mehl-Avrami-Kolmogorov [M. Avrami, J. Phys. Chem. 9, 177 (1941); W. A. Johnson and R. F. Mehl, Trans. Am. Inst. Min., Metal. Eng. 135, 416 (1939); A. N. Kolmogorov, Izv. Akad. Nauk SSSR, Ser. Mat. 3, 355 (1937); F. Liu, F. Sommer, C. Bos, and E. J. Mittemeijer, Int. Mat. Rev. 52, 193 (2007)] model which is commonly applied to explain the kinetics of metal hydride transformations. The broad range of reaction rates arises from the disperse character of the particle size and the dendritic morphology of the samples. The model is expected to be generally applicable for metal hydrides which show a significant variation in particle sizes, in configuration and/or chemical composition of local surroundings of the reacting nanoparticles.