Low Temperature Precursor Route for Highly Efficient Spherically Shaped LED-Phosphors M2Si5N8:Eu2+ (M = Eu, Sr, Ba)

The highly efficient nitridosilicate phosphors M2Si5N8 (M = Sr, Ba, Eu) for phosphor-converted pc-LEDs were synthesized at low temperatures using a novel precursor route involving metal amides M(NH2)2. These precursors have been synthesized by dissolution of the respective metals in supercritical ammonia at 150°C and 300 bar. The thermal behavior and decomposition process of the amides were investigated with temperature programmed powder X-ray diffractometry and thermoanalytical measurements (DTA/TG). These investigations rendered the amides as suitable intermediates for reaction with silicon diimide (Si(NH)2). Thus, the desired nitridosilicate phosphors were obtained at relatively low temperatures around 1150−1400°C which is approximately 300°C lower compared to common synthetic approaches starting from metals or oxides. The influence of the thermal treatment on the phosphor morphology has been studied extensively. The accessibility of spherical phosphor particles represents another striking feature of this route since it improves light extraction from the crystallites due to decreasing light guiding and decreasing re-absorption inside the phosphor particle. The synthesized luminescent materials M2Si5N8:Eu2+ (M = Sr, Ba) exhibit quantum efficiencies and emission band widths (FWHM 70−90 nm) comparable to standard phosphor powders. Employment of Eu(NH2)2 as dopant reagent for synthesis of Ba2Si5N8:Eu2+ proved favorable for the formation of spherical crystallites compared to doping with Eu metal, halides, or oxide

Synthesis of YVO4:Eu3+/YBO3Heteronanostructures with Enhanced Photoluminescence Properties

Novel YVO4:Eu3+/YBO3core/shell heteronanostructures with different shell ratios (SRs) were successfully prepared by a facile two-step method. X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy were used to characterize the heteronanostructures. Photoluminescence (PL) study reveals that PL efficiency of the YVO4:Eu3+nanocrystals (cores) can be improved by the growth of YBO3nanocoatings onto the cores to form the YVO4:Eu3+/YBO3core/shell heteronanostructures. Furthermore, shell ratio plays a critical role in their PL efficiency. The heteronanostructures (SR = 1/7) exhibit the highest PL efficiency; its PL intensity of the5D0–7F2emission at 620 nm is 27% higher than that of the YVO4:Eu3+nanocrystals under the same conditions

Multicomponent imaging of the

The gamma-ray sky as seen by the Large Area Telescope (LAT) on board the Fermi satellite is a superposition of emissions from many processes. To study them, a rich toolkit of analysis methods for gamma-ray observations has been developed, most of which rely on emission templates to model foreground emissions. Here, we aim to complement these methods by presenting a template-free spatio-spectral imaging approach for the gamma-ray sky, based on a phenomenological modeling of its emission components. It is formulated in a Bayesian variational inference framework and allows a simultaneous reconstruction and decomposition of the sky into multiple emission components, enabled by a self-consistent inference of their spatial and spectral correlation structures. Additionally, we formulated the extension of our imaging approach to template-informed imaging, which includes adding emission templates to our component models while retaining the “data-drivenness” of the reconstruction. We demonstrate the performance of the presented approach on the ten-year Fermi LAT data set. With both template-free and template-informed imaging, we achieve a high quality of fit and show a good agreement of our diffuse emission reconstructions with the current diffuse emission model published by the Fermi Collaboration. We quantitatively analyze the obtained data-driven reconstructions and critically evaluate the performance of our models, highlighting strengths, weaknesses, and potential improvements. All reconstructions have been released as data products

Energy Transfer and Emission Decay Kinetics in Mixed Microporous Lanthanide Silicates with Unusual Dimensionality

We have investigated the energy transfer dynamics in mixed lanthanide open-framework silicates, known as Ln-AV-20 materials, with the stoichiometric formula Na1.08K0.5Ln1.14Si3O8.5·1.78H2O (Ln = Gd3+, Tb3+, Eu3+), using steady-state and time-resolved luminescence spectroscopy. Energy transfer between donor and acceptor Ln3+ ions is extremely efficient, even at low molar ratios of the acceptor Ln3+ (<5%). The presence of two different Ln3+ environments makes the Ln-AV-20 intralayer structure intermediate between purely one-dimensional (1D) and two-dimensional (2D). The unusual dimensionality of the Ln-AV-20 layers prevents modeling of energy transfer kinetics by conventional kinetic models. We have developed a computer modeling program for the analysis of energy transfer kinetics in systems of unusual dimensions and show how it may be applied successfully to the AV-20 system. Using the program, nearest neighbor energy transfer rate constants are calculated as (5.30 ± 0.07) × 106 and (6.00 ± 0.13) × 106 s-1, respectively, for Gd/Tb- and Tb/Eu-AV-20 at 300 K. With increasing acceptor concentration, the energy transfer dynamics tend toward purely one-dimensional behavior, and thus, with careful selection of the ratio of individual Ln3+ ions, it is possible to tune the energy transfer dimensionality of the AV-20 layers from pure 1D to something intermediate between 1D and 2D

Mechanisms of VUV Damage in BaMgAl10O17:Eu2+

We have studied vacuum ultraviolet (VUV)-induced damage processes in BaMgAl10O17:Eu2+ using a unique accelerated life-testing device. Emission, excitation, and reflectance spectra of doped and undoped samples before and after VUV damage reveal two independent mechanisms of degradation. The observed color shift in damaged materials is due to the migration of Eu2+ ions to metastable sites in the lattice. The observed loss of brightness is due in part to the formation of color centers in the spinel layer that act as energy traps and also absorb the exciton emission of the host lattice, thus interrupting the transfer of energy from the host to the activator. Several modes of energy transfer to Eu2+ are available depending on the excitation energy

An N-bridged high-valent diiron-oxo species on a porphyrin platform that can oxidize methane.

International audienceHigh-valent oxo-metal complexes are involved in key biochemical processes of selective oxidation and removal of xenobiotics. The catalytic properties of cytochrome P-450 and soluble methane monooxygenase enzymes are associated with oxo species on mononuclear iron haem and diiron non-haem platforms, respectively. Bio-inspired chemical systems that can reproduce the fascinating ability of these enzymes to oxidize the strongest C-H bonds are the focus of intense scrutiny. In this context, the development of highly oxidizing diiron macrocyclic catalysts requires a structural determination of the elusive active species and elucidation of the reaction mechanism. Here we report the preparation of an Fe(IV)(µ-nitrido)Fe(IV) = O tetraphenylporphyrin cation radical species at -90 °C, characterized by ultraviolet-visible, electron paramagnetic resonance and Mössbauer spectroscopies and by electrospray ionization mass spectrometry. This species exhibits a very high activity for oxygen-atom transfer towards alkanes, including methane. These findings provide a foundation on which to develop efficient and clean oxidation processes, in particular transformations of the strongest C-H bonds