In Situ Formation of Ge Nanoparticles by Annealing of Al-Ge-N Thin Films Followed by HAXPES and XRD.

Ge nanoparticles embedded in thin films have attracted a lot of attention due to their promising optical and electronic properties that can be tuned by varying the particle size and choice of matrix material. In this study, Ge nanoparticle formation was investigated for Al-Ge-N based thin films by simultaneous measurements of HAXPES and grazing incidence XRD during in situ annealing in vacuum conditions. As-deposited Al-Ge-N thin films, synthesized by reactive dc magnetron sputtering, consisted of a nanocrystalline (Al1-xGex)Ny solid solution and an amorphous tissue phase of Ge3Ny. Upon annealing to 750 °C, elemental Ge was formed shown by both HAXPES and XRD measurements, and N2 gas was released as measured by a mass spectrometer. Postannealed ex situ analysis by SEM and TEM showed that the elemental Ge phase formed spherical nanoparticles on the surface of the film, with an average size of 210 nm. As the annealing temperature increased further to 850 °C, the Ge particles on the film surface evaporated, while the phase segregation of Ge still could be observed within the film. Thus, these results show the possibility for a controlled synthesis of Ge nanoparticles through annealing of Al-Ge-N thin films to produce materials suitable for use in electronic or optoelectronic devices.

In Situ Synchrotron X-ray Diffraction Analysis of the Setting Process of Brushite Cement: Reaction and Crystal Growth.

Brushite cements are fast self-setting materials that can be used as bone substitute materials. Although tracing their fast setting process is a challenge, it is important for the understanding of the same, which in turn is important for the material's further development and use in the clinics. In this study, the setting rate, phase formation, and crystal growth of brushite cements were quantitatively studied by in situ synchrotron powder X-ray diffraction (SXRD) on a time scale of seconds. The influence of reactant ratios and a retardant (citric acid) on the setting reaction were analyzed. To complement the in situ investigations, scanning electron microscopy was carried out for ex situ morphological evolution of crystals. The initial reaction followed a four-step process, including a fast nucleation induction period, nucleation, crystal growth, and completion of the setting. The brushite crystal size grew up to the micro scale within 1 min, and the brushite content increased linearly after the nucleation until all monocalcium phosphate monohydrate (MCPM; Ca(H2PO4)2·H2O) had dissolved within minutes, followed by a slow increase until the end of the monitoring. By adjusting the MCPM to the ß-tricalcium phosphate (ß-TCP, ß-Ca3(PO4)2) ratio in the starting powders, the brushite/monetite ratio in the cements could be modified. In the presence of citric acid, the formation of brushite nuclei was not significantly retarded, whereas the increase in brushite content and the growth of crystal size were effectively hindered. The amount of monetite also increased by adding citric acid. This is the first time that the brushite setting process has been characterized in the first seconds and minutes of the reaction by SXRD.

Solid-Liquid Interface Structure of Muscovite Mica in CsCl and RbBr Solutions.

The solid-liquid interface formed by single terminated muscovite mica in contact with two different ionic solutions is analyzed using surface X-ray diffraction. Specular and nonspecular crystal truncation rods of freshly cleaved mica immersed in CsCl or RbBr aqueous solution were measured. The half monolayer of the surface potassium ions present after the cleavage is completely replaced by the positive ions (Cs+ or Rb+) from the solution. These ions are located in the ditrigonal surface cavities with small outward relaxations with respect to the bulk potassium position. We find evidence for the presence of a partly ordered hydration shell around the surface Cs+ or Rb+ ions and partly ordered negative ions in the solution. The lateral liquid ordering induced by the crystalline surface vanishes at distances larger than 5 Å from the surface.

Tracking the shape-dependent sintering of platinum-rhodium model catalysts under operando conditions.

Nanoparticle sintering during catalytic reactions is a major cause for catalyst deactivation. Understanding its atomic-scale processes and finding strategies to reduce it is of paramount scientific and economic interest. Here, we report on the composition-dependent three-dimensional restructuring of epitaxial platinum-rhodium alloy nanoparticles on alumina during carbon monoxide oxidation at 550 K and near-atmospheric pressures employing in situ high-energy grazing incidence x-ray diffraction, online mass spectrometry and a combinatorial sample design. For platinum-rich particles our results disclose a dramatic reaction-induced height increase, accompanied by a corresponding reduction of the total particle surface coverage. We find this restructuring to be progressively reduced for particles with increasing rhodium composition. We explain our observations by a carbon monoxide oxidation promoted non-classical Ostwald ripening process during which smaller particles are destabilized by the heat of reaction. Its driving force lies in the initial particle shape which features for platinum-rich particles a kinetically stabilized, low aspect ratio.

Concentration and strain fields inside a Ag/Au core-shell nanowire studied by coherent X-ray diffraction.

Three-dimensional coherent diffraction patterns of an isolated, single-crystalline Ag/Au core-shell nanowire were recorded at different X-ray beam energies close to the Au LIII absorption edge. Two-dimensional slices of the three-dimensional diffraction pattern, with the diffraction vector oriented perpendicular to the wire axis, were investigated in detail. In reciprocal space, facet streaks with thickness fringes were clearly observed in the two-dimensional diffraction patterns, from which the shape and size of the corresponding cross sections of the nanowire could be revealed. Comparison with simulated diffraction patterns exhibited the coherency strain field in the nanowire. During in situ annealing at temperatures which would lead to significant intermixing by volume diffusion in bulk material, according to literature data, a core-shell morphology was preserved; that is, intermixing in the nanowire was pronouncedly decelerated compared to bulk diffusion.

Reversible formation of a PdC(x) phase in Pd nanoparticles upon CO and O2 exposure.

The structure and chemical composition of Pd nanoparticles exposed to pure CO and mixtures of CO and O(2) at elevated temperatures have been studied in situ by a combination of X-ray Diffraction and X-ray Photoelectron Spectroscopy in pressures ranging from ultra high vacuum to 10 mbar and from room temperature to a few hundred degrees celsius. Our investigation shows that under CO exposure, above a certain temperature, carbon dissolves into the Pd particles forming a carbide phase. Upon exposure to CO and O(2) mixtures, the carbide phase forms and disappears reversibly, switching at the stoichiometric ratio for CO oxidation. This finding opens new scenarios for the understanding of catalytic oxidation of C-based molecules.

Dynamic response of chlorine atoms on a RuO(2)(110) model catalyst surface.

The dynamic behavior of surface accommodated chlorine atoms on RuO(2)(110) was studied by a variety of experimental methods including high resolution core level shift, thermal desorption-, and in situ infrared spectroscopy as well as in situ surface X-ray diffraction in combination with state-of-the-art density functional theory calculations. On the chlorinated RuO(2)(110) surface the undercoordinated oxygen atoms have been selectively replaced by chlorine. These strongly bound surface chlorine atoms shift from bridging to on-top sites when the sample is annealed in oxygen, while the reverse shift of Cl from on-top into bridge positions is observed during CO exposure; the vacant bridge position is then occupied by either chlorine or CO. For the CO oxidation reaction over chlorinated RuO(2)(110), the reactant induced site switching of chlorine causes a site-blocking of the catalytically active one-fold coordinatively unsaturated (1f-cus) Ru sites. This site blocking reduces the number of active sites and, even more important, on-top Cl blocks the free migration of the adsorbed reactants along the one-dimensional 1f-cus Ru rows, thus leading to a loss of catalytic activity.

The role of steps in surface catalysis and reaction oscillations.

Atomic steps at the surface of a catalyst play an important role in heterogeneous catalysis, for example as special sites with increased catalytic activity. Exposure to reactants can cause entirely new structures to form at the catalyst surface, and these may dramatically influence the reaction by 'poisoning' it or by acting as the catalytically active phase. For example, thin metal oxide films have been identified as highly active structures that form spontaneously on metal surfaces during the catalytic oxidation of carbon monoxide. Here, we present operando X-ray diffraction experiments on a palladium surface during this reaction. They reveal that a high density of steps strongly alters the stability of the thin, catalytically active palladium oxide film. We show that stabilization of the metal, caused by the steps and consequent destabilization of the oxide, is at the heart of the well-known reaction rate oscillations exhibited during CO oxidation at atmospheric pressure.

Self-healing and self-organized gold nanoparticle films at a water/organic solvent interface.

Gold nanoparticles (5 nm and 20 nm) have been synthesized and stabilized with mercaptoundecanol. These particles, although insoluble in water or common organic solvents, spread as a thin film at the liquid-liquid interface between a water phase and an organic phase. Films of these gold nanoparticles have been observed both by conventional transmission electron microscopy of deposited samples and by cryo-transmission electron microscopy of plunge-frozen samples. The film can be monolayered and extend over centimeter-sized areas. The particle films spontaneously re-assemble and self-organize at the interface when disrupted. This self-healing capacity of the film should make it possible to build a device for continuous production and deposition of the film.

Imaging atomic structure in metal nanoparticles using high-resolution cryo-TEM.

It has been shown, by imaging gold (200) planes, that it is possible to achieve better than 0.20-nm structural resolution in cryo-transmission electron microscopy (cryo-TEM). This has been done using commercially available cryo equipment and using a 300-kV field emission gun (FEG) TEM. The images of 15-nm gold particles embedded in amorphous frozen water clearly show the (111) planes (separated by 0.235 nm) in gold. Fourier transform demonstrates the presence of (200) planes in the image, proving a resolution of better than 0.20 nm. The experimental results are supported by image simulations using the multislice method. These simulations suggest that it should be possible to achieve the same resolution even in smaller particles and particles of lighter elements. The crucial experimental problem to overcome is keeping the thickness of the amorphous film low and to work at low electron dose conditions.