Tin-oxide nanoparticles deposited from a beam: what happens to the composition?

The debate around the oxidation states occurring in laboratory-prepared tin-oxide samples has been for a long time an obstacle for an unambiguous assignment of characterization studies performed on such samples. In particular the changes in the Sn core-level energies caused by oxidation - i.e. the chemical shifts - as measured by photoelectron spectroscopy (PES) have been under discussion. The assignment problem is especially pronounced for nanoscale structures, which are important for photovoltaics, electronics, catalysis, and gas sensing. The reasons for the difficulties lie both in the natural properties of tin oxides, which can have substantial deficiencies of oxygen and tin in the lattice, and in the shortcomings of the fabrication and PES-characterization procedures themselves. Our recent PES study on tin-oxide nanoparticles fabricated by vapour-aggregation gave a chemical shift two times larger than earlier reported for Sn(iv) oxide for the Sn 4d level. The implemented fabrication technique forms an in-vacuum beam of particles whose composition can be both controlled and characterized by PES. In the present work SnO and SnO2 nanoparticles fabricated this way were deposited from the beam and probed by PES directly, as well as after exposure to air. The deposited nanoparticle films were also imaged by TEM (Transmission Electron Microscopy). The effects of the deposition process and exposure to air on the chemical composition were studied. The PES study of deposited SnO2 nanoparticles in the Sn 4d and Sn 3d core-level regions revealed the same core level shift as for unsupported nanoparticles, indicating that the chemical composition is preserved in the deposition process. The TEM study demonstrated a crystalline structure of separate SnO2 particles with lattice constants close to the macroscopic Sn(iv)-oxide. The PES study on the particles exposed to air showed changes in the composition. For the film of initially SnO particles a higher intermediate oxide was created. For the SnO2 nanoparticle film a lower, but strong, intermediate oxide was observed, likely at the surface.

Metal-passivated PbS nanoparticles: fabrication and characterization.

Organic-shell-free PbS nanoparticles have been produced in the size range relevant for quantum-dot solar cells (QDSCs) by a vapor aggregation method involving magnetron reactive sputtering. This method creates a beam of free 5-10 nm particles in a vacuum. The dimensions of the particles were estimated after their deposition on a substrate by imaging them using ex situ SEM and HRTEM electron microscopy. The particle structure and chemical composition could be deduced "on the fly", prior to deposition, using X-ray photoelectron spectroscopy (XPS) with tunable synchrotron radiation. Our XPS results suggest that under certain conditions it is possible to fabricate particles with a semiconductor core and 1 to 2 monolayer shells of metallic lead. For this case the absolute energy of the highest occupied molecular orbital (HOMO) in PbS has been determined to be (5.0 ± 0.5) eV below the vacuum level. For such particles deposited on a substrate HRTEM has confirmed the XPS-based conclusions on the crystalline PbS structure of the semiconductor core. Absorption spectroscopy on the deposited film has given a value of ∼1 eV for the lowest exciton. Together with the valence XPS results this has allowed us to reconstruct the energy level scheme of the particles. The results obtained are discussed in the context of the properties of PbS QDSCs.

Dynamic atomic-level rearrangements in small gold particles.

Small metal particles (<5 nanometers), which are widely used in catalysis, have physical and chemical properties that are markedly different from those of the bulk metal. The differences are related to crystal structure, and it is therefore significant that structral rearrangements in small particles have been observed in real time by using high-resolution electron microscopy. A detailed investigation at the atomic level has been made of the factors affecting the dynamic activity of small gold crystals that are supported on thin films of amorphous carbon, silicon, and germanium. The rate of activity depends mainly on the current density of the incident electron beam and the degree of contact of the particle with the substrate, but this rate decreases rapidly as the particle size is increased. The activity of the particles is very similar on either carbon or silicon, but it is generally less marked on germanium because of increased contact between the particle and the substrate. The electron beam effectively heats the particles, and it appears that their dynamic behavior depends on their thermal contact with the substrate.

Structure-activity relationship in HC-SCR of NOx by TEM, O2-chemisorption, and EDXS study of Ag/Al2O3.

Ag/alumina catalysts with different silver loading (1.28-6 wt %) for lean NO reduction activity were prepared by impregnation and the incipient wetness method. Complementary HRTEM, HAADF, O2-chemisorption, and EDXS studies were applied to investigate the dependence between silver particle size and catalytic activities of the prepared materials. The catalyst with the lowest silver loading (1.28 wt %) was found to be the most active catalyst in terms of reacted NO molecules per mole of silver. On the basis of the HRTEM, HAADF, and O2-chemisorption studies it could be concluded that the mean particle size or particle size distribution of the samples alone could not explain the big difference in the activities. EDXS analyses showed on the other hand that all of the samples were very heterogeneous in terms of particle size distribution, e.g., including both small and very big particles. Furthermore, both metallic silver and mainly hexagonal silver oxide (Ag2O) were found to be present in the samples. Despite the valuable information provided by ex situ characterization of the prepared samples, it needs to be emphasized that establishing a structure-reactivity relationship for this type of catalyst requires in situ characterization.

Analysis of the state and size of silver on alumina in effective removal of NOx from oxygen rich exhaust gas.

Ag/alumina catalysts with different silver contents for octane-SCR were prepared by impregnation and incipient wetness methods. Activity tests revealed that the decisive factor for high activity is not only a high dispersion of silver, but also the ability of the system to redisperse clustered silver. Determination of dispersion by TEM/HAADF and O2-chemisorption experiments resulted in values close to each other even if the results were not directly comparable. This is suggested to be due to not complete silver reduction below 700 degrees C and the samples being very heterogeneous in terms of particle size, e.g., having a bimodal size distribution. Small charged Agsigman+ clusters containing 2-8 silver atoms highly prevailed in the samples containing <2 wt% Ag and exhibiting high octane-SCR activity. In highly loaded Ag/alumina samples or those reduced and reoxidized at high temperature (>400 degrees C), large metallic particles are stabilized, resulting in poor conversion of NOx to N2.

InAs1-xPx nanowires for device engineering.

We present the growth of homogeneous InAs(1-x)P(x) nanowires as well as InAs(1-x)P(x) heterostructure segments in InAs nanowires with P concentrations varying from 22% to 100%. The incorporation of P has been studied as a function of TBP/TBAs ratio, temperature, and diameter of the wires. The crystal structure of the InAs as well as the InAs(1-x)P(x) segments were found to be wurtzite as determined from high-resolution transmission electron microscopy. Furthermore, temperature-dependent electrical transport measurements were performed on individual heterostructured wires to extract the conduction band offset of InAs(1-x)P(x) relative to InAs as a function of composition. From these measurements we extract a value of the linear coefficient of the conduction band versus x of 0.6 eV and a nonlinear coefficient, or bowing parameter, of 0.2 eV. Finally, homogeneous InAs(0.8)P(0.2) nanowires were shown to have a nondegenerate n-type doping and function as field-effect transistors at room temperature.

Effect of cold exposure of free water reabsorption in hydropenic man.

With clearance technique, changes in tubular reabsorption of solute free water (TcH2O), were studied in a group of 9 healthy hydropenic volunteers during a cold stress of 1 h at +15 degrees C. Increases were found in TcH2O and in fractional excretion of sodium and osmoles during cold. Since TcH2O was used as an index of sodium reabsorption in the ascending limb of Henle's loop, the findings indicated that under the conditions used in this study, the concentrating ability of the kidney was not negatively influenced by cold, despite a significant increase in arterial pressure. It is suggested that the reabsorption by the ascending limb of the loop was increased secondary to a reduced proximal tubular reabsorption of sodium.

Tubular sodium handling in cold-exposed man during inhibition of distal tubular reabsorption of sodium.

In 8 healthy volunteers in stable water diuresis, exposed to cold at +15 degrees C for 60 min, changes in excretion and tubular reabsorption of sodium and osmoles were studied by the clearance technique during inhibition of distal tubular sodium reabsorption following chlorothiazide infusion at 2 mg/kg/hr. Inhibition of distal tubular sodium reabsorption by chlorothiazide increased fractional sodium excretion to 6.5% and fractional excretion of osmoles to 7.5% of the filtered amount. The superimposed cold exposure did not further increase these figures, despite a significant cold-induced increase in arterial blood pressure.

Cardiovascular and renal responses to acute cold exposure in water-loaded man.

Changes in oxygen uptake, cardiac output, heart rate, stroke volume, central blood volume, arteriovenous oxygen difference, aortic, pulmonary arterial, and right atrial blood pressure, systemic vascular resistance, hematocrit, circulating plasma volume, urine flow, fractional sodium excretion, and free water clearance were studied in eight healthy volunteers in stable water diuresis, exposed to cold by means of air at +15 degrees C and at a speed of 0.5 m/sec. A decrease in circulating plasma volume and systemic vascular resistance was found during cold stress. Mean aortic blood pressure, sodium excretion, cardiac output, oxygen uptake, arteriovenous oxygen difference, and hematocrit increased. No changes in urine flow or in clearance of free water could be demonstrated. Heart rate, stroke volume, and central blood volume showed significant increases in cold. The results are interpreted to suggest that exposure to cold raises the arterial blood pressure by an increase in cardiac output, thereby increasing capillary hydrostatic pressure in certain vascular areas, including the renal vascular bed. This negatively affects capillary reabsorption processes in the kidney, causing a reduction in tubular sodium reabsorption, thus giving rise to a natriuresis. In other areas it seems to cause a shift of fluid towards the intersitial space.

Structural characterization of the metal/glass interface in bioactive glass coatings on Ti-6Al-4V.

Coating Ti-based implants with bioactive materials promotes joining between the prostheses and the bone as well as increasing long-term implant stability. In the present work, the interface between Ti-6Al-4V and bioactive silicate glass coatings, prepared using a simple enameling technique, is analyzed. High-resolution transmission electron microscopy of the glass/alloy interface shows the formation of a reaction layer ( approximately 150 nm thick) composed of Ti5Si3 nanoparticles with a size of approximately 20 nm. This nanostructured interface facilitates the formation of a stable joint between the glass coating and the alloy.