A portable on-axis laser-heating system for near-90° X-ray spectroscopy: application to ferropericlase and iron silicide.

A portable IR fiber laser-heating system, optimized for X-ray emission spectroscopy (XES) and nuclear inelastic scattering (NIS) spectroscopy with signal collection through the radial opening of diamond anvil cells near 90°with respect to the incident X-ray beam, is presented. The system offers double-sided on-axis heating by a single laser source and zero attenuation of incoming X-rays other than by the high-pressure environment. A description of the system, which has been tested for pressures above 100 GPa and temperatures up to 3000 K, is given. The XES spectra of laser-heated Mg0.67Fe0.33O demonstrate the potential to map the iron spin state in the pressure-temperature range of the Earth's lower mantle, and the NIS spectra of laser-heated FeSi give access to the sound velocity of this candidate of a phase inside the Earth's core. This portable system represents one of the few bridges across the gap between laser heating and high-resolution X-ray spectroscopies with signal collection near 90°.

Microscopic structure of water at elevated pressures and temperatures.

We report on the microscopic structure of water at sub- and supercritical conditions studied using X-ray Raman spectroscopy, ab initio molecular dynamics simulations, and density functional theory. Systematic changes in the X-ray Raman spectra with increasing pressure and temperature are observed. Throughout the studied thermodynamic range, the experimental spectra can be interpreted with a structural model obtained from the molecular dynamics simulations. A spatial statistical analysis using Ripley's K-function shows that this model is homogeneous on the nanometer length scale. According to the simulations, distortions of the hydrogen-bond network increase dramatically when temperature and pressure increase to the supercritical regime. In particular, the average number of hydrogen bonds per molecule decreases to ≈ 0.6 at 600 °C and p = 134 MPa.

Ge-Si-O phase separation and Ge nanocrystal growth in Ge:SiO(x)/SiO(2) multilayers--a new dc magnetron approach.

Ge:SiO(x)/SiO(2) multilayers are fabricated using a new reactive dc magnetron sputtering approach. The influence of the multilayer stoichiometry on the ternary Ge-Si-O phase separation and the subsequent size-controlled Ge nanocrystal formation is explored by means of x-ray absorption spectroscopy, x-ray diffraction, electron microscopy and Raman spectroscopy. The ternary system Ge-Si-O reveals complete Ge-O phase separation at 400 °C which does not differ significantly to the binary Ge-O system. Ge nanocrystals of < 5 nm size are generated after subsequent annealing below 700 °C. It is shown that Ge oxides contained in the as-deposited multilayers are reduced by a surrounding unsaturated silica matrix. A stoichiometric regime was found where almost no GeO(2) is present after annealing. Thus, the Ge nanocrystals become completely embedded in a stoichiometric silica matrix favouring the use for photovoltaic applications.

Dissolution of iron oxide nanoparticles inside polymer nanocapsules.

The structure of poly(organosiloxane) nanocapsules partially filled with iron oxide cores of different sizes was revealed by small angle X-ray scattering and X-ray diffraction. The nanocapsules are synthesized by the formation of a poly(organosiloxane) shell around iron oxide nanoparticles and the simultaneous partial dissolution of these cores. Due to the high scattering contrast of the iron oxide cores compared to the polymer shell, the particle size distribution of the cores inside the capsules can be measured by small angle X-ray scattering. Additional information can be revealed by X-ray diffraction, which gives insights into the formation of the polymer network and the structure of the iron oxide cores. The study shows how the crystallinity and size of the nanoparticles as well as the shape and width of the size distribution can be altered by the synthesis parameters.

Influence of hydrogen on thermally induced phase separation in GeO/SiO2 multilayers.

The influence of the annealing atmosphere on the temperature induced phase separation of Ge oxide in GeO(x)/SiO(2) multilayers (x≈1), leading to size controlled growth of Ge nanocrystals, is explored by means of x-ray absorption spectroscopy at the Ge K-edge. Ge sub-oxides contained in the as-deposited multilayers diminish with increasing annealing temperature, showing complete phase separation at approximately 450 °C using inert N(2) ambient. The use of reducing H(2) in the annealing atmosphere influences the phase separation even at an early stage of the disproportionation. In particular, the temperature regime where the phase separation occurs is lowered by at least 50 °C. At temperatures above 400 °C the sublayer composition, and thus the density of the Ge nanocrystals, can be altered by making use of the reduction of GeO(2) by H(2).