Interlaboratory Comparison on Absolute Photoluminescence Quantum Yield Measurements of Solid Light Converting Phosphors with Three Commercial Integrating Sphere Setups.

Scattering luminescent materials dispersed in liquid and solid matrices and luminescent powders are increasingly relevant for fundamental research and industry. Examples are luminescent nano- and microparticles and phosphors of different compositions in various matrices or incorporated into ceramics with applications in energy conversion, solid-state lighting, medical diagnostics, and security barcoding. The key parameter to characterize the performance of these materials is the photoluminescence/fluorescence quantum yield (Φf), i.e., the number of emitted photons per number of absorbed photons. To identify and quantify the sources of uncertainty of absolute measurements of Φf of scattering samples, the first interlaboratory comparison (ILC) of three laboratories from academia and industry was performed by following identical measurement protocols. Thereby, two types of commercial stand-alone integrating sphere setups with different illumination and detection geometries were utilized for measuring the Φf of transparent and scattering dye solutions and solid phosphors, namely, YAG:Ce optoceramics of varying surface roughness, used as converter materials for blue light emitting diodes. Special emphasis was dedicated to the influence of the measurement geometry, the optical properties of the blank utilized to determine the number of photons of the incident excitation light absorbed by the sample, and the sample-specific surface roughness. While the Φf values of the liquid samples matched between instruments, Φf measurements of the optoceramics with different blanks revealed substantial differences. The ILC results underline the importance of the measurement geometry, sample position, and blank for reliable Φf data of scattering the YAG:Ce optoceramics, with the blank's optical properties accounting for uncertainties exceeding 20%.

Energy Transfer in Dy3+ and Tb3+ Double-Doped Barium Borate Glass.

In this work, single- and double-doped Dy3+ and Tb3+ barium borate glasses are investigated for their potential as light converters. The density and the absorption coefficient show linearly increasing trends with an increasing lanthanide content. The external quantum efficiency of the double-doped samples is a combination of the respective single-doped samples. The strong energy transfer from Dy3+ to Tb3+ results in an intense Tb3+-related emission, i.e., an intense green luminescence. Thus, excitation at a Dy3+-related wavelength of 452 nm enables a Tb3+-related emission, at which a single-doped Tb3+ sample barely shows any luminescence. Lifetime measurements show that there is not only an energy transfer from Dy3+ to Tb3+, but also vice versa.

The Role of Silicate Enrichment on the Discharge Duration of Silicon-Air Batteries.

Silicon-air batteries are candidates for next generation batteries from non-critical raw materials. However, current silicon-air batteries with alkaline electrolytes suffer from premature termination of the discharge process. To understand this process, we investigated the correlation of dissolved silicon in the electrolyte and the discharge duration until passivation. The air- and Si-electrode could be excluded as the source of the voltage drop, while the concentration of silicates in the electrolyte was identified as the decisive factor. A low silicate concentration in the electrolyte was found to be crucial for a sustained discharge of silicon-air batteries with alkaline electrolytes and full consumption of the silicon electrode used in these conditions was shown.

Atomic Layer Deposition of Cobalt Phosphide for Efficient Water Splitting.

Transition-metal phosphides (TMP) prepared by atomic layer deposition (ALD) are reported for the first time. Ultrathin Co-P films were deposited by using PH3 plasma as the phosphorus source and an extra H2 plasma step to remove excess P in the growing films. The optimized ALD process proceeded by self-limited layer-by-layer growth, and the deposited Co-P films were highly pure and smooth. The Co-P films deposited via ALD exhibited better electrochemical and photoelectrochemical hydrogen evolution reaction (HER) activities than similar Co-P films prepared by the traditional post-phosphorization method. Moreover, the deposition of ultrathin Co-P films on periodic trenches was demonstrated, which highlights the broad and promising potential application of this ALD process for a conformal coating of TMP films on complex three-dimensional (3D) architectures.

Pixelated phosphors for high-resolution and high-contrast white light sources: erratum.

Erroneous absolute luminance values of the pixelated phosphor structure B25 (pixel size of 25 microns by 25 microns) have been corrected. The updated figure shows clearly the potential of the investigated structure as light-converter for high-resolution lighting systems.

Pixelated phosphors for high-resolution and high-contrast white light sources.

Porous phosphor microstructures are studied for their potential as light converter in laser-based, high-resolution lighting systems. Phosphor particles are filled into pre-patterned silicon molds and coated by an atomic layer deposition with a thin layer of Al2O3 for mechanical stability. Pixel sizes of 2 mm by 2 mm down to 25 µm by 25 µm are fabricated. The structures show a significant drop in luminance between the illuminated and the non-illuminated, adjacent pixel. The high thermal conductivity of the silicon allows an efficient cooling of the structures. Having removed the backside silicon, an active air flow cooling of the porous phosphor structure is possible.

Characterization of Luminescent Materials with 151Eu Mössbauer Spectroscopy.

The application of Mössbauer spectroscopy to luminescent materials is described. Many solids doped with europium are luminescent, i.e., when irradiated with light they emit light of a longer wavelength. These materials therefore have practical applications in tuning the light output of devices like light emitting diodes. The optical properties are very different for the two possible valence states Eu 2 + and Eu 3 + , the former producing ultraviolet/visible light that shifts from violet to red depending on the host and the latter red light, so it is important to have a knowledge of their behavior in a sample environment. Photoluminescence spectra cannot give a quantitative analysis of Eu 2 + and Eu 3 + ions. Mössbauer spectroscopy, however, is more powerful and gives a separate spectrum for each oxidation state enabling the relative amount present to be estimated. The oxidation state can be identified from its isomer shift which is between - 12 and - 15 mm/s for Eu 2 + compared to around 0 mm/s for Eu 3 + . Furthermore, within each oxidation state, there are changes depending on the ligands attached to the europium: the shift is more positive for increased covalency of the bonding ligand X, or Eu concentration, and decreases for increasing Eu⁻X bond length.

Calcium fluoride based multifunctional nanoparticles for multimodal imaging.

New multifunctional nanoparticles (NPs) that can be used as contrast agents (CA) in different imaging techniques, such as photoluminescence (PL) microscopy and magnetic resonance imaging (MRI), open new possibilities for medical imaging, e.g., in the fields of diagnostics or tissue characterization in regenerative medicine. The focus of this study is on the synthesis and characterization of CaF2:(Tb3+,Gd3+) NPs. Fabricated in a wet-chemical procedure, the spherical NPs with a diameter of 5-10 nm show a crystalline structure. Simultaneous doping of the NPs with different lanthanide ions, leading to paramagnetism and fluorescence, makes them suitable for MR and PL imaging. Owing to the Gd3+ ions on the surface, the NPs reduce the MR T1 relaxation time constant as a function of their concentration. Thus, the NPs can be used as a MRI CA with a mean relaxivity of about r = 0.471 mL·mg-1·s-1. Repeated MRI examinations of four different batches prove the reproducibility of the NP synthesis and determine the long-term stability of the CAs. No cytotoxicity of NP concentrations between 0.5 and 1 mg·mL-1 was observed after exposure to human dermal fibroblasts over 24 h. Overall this study shows, that the CaF2:(Tb3+,Gd3+) NPs are suitable for medical imaging.

Opportunities for Fluorochlorozirconate and Other Glass-Ceramic Detectors in Medical Imaging Devices.

This article gives an overview of fluorochlorozirconate glass-ceramic scintillators and storage phosphor materials: how they are synthesized, what their properties are, and how they can be used in medical imaging. Such materials can enhance imaging in x-ray radiography, especially mammography and dental imaging, computed tomography, and positron emission tomography. Although focusing on fluorochlorozirconate materials, the reader will find the discussion is relevant to other luminescent glass and glass-ceramic systems.

Photoelectrochemical hydrogen evolution of tapered silicon nanowires.

The origin of the photocurrent enhancement and the overpotential reduction in solar water splitting employing nanostructured silicon is still a matter of debate. A set of tapered Si nanowires (SiNWs) has been designed for clarifying the impact of nanostructured Si on the hydrogen evolution reaction (HER) while precisely tailoring several interference factors such as surface area, light absorption and surface defect density. We find that defect passivation by KOH achieved by tapering is much more beneficial than the optical gain. Surfactant-mediated modification of SiNWs is capable of engineering the band structure. As a result, we suggest a guideline for nanostructured Si photoelectrodes optimized for the HER.

CMOS-compatible metal-stabilized nanostructured Si as anodes for lithium-ion microbatteries.

The properties of fully complementary metal-oxide semiconductor (CMOS)-compatible metal-coated nanostructured silicon anodes for Li-ion microbatteries have been studied. The one-dimensional nanowires on black silicon (nb-Si) were prepared by inductively coupled plasma (ICP) etching and the metal (Au and Cu) coatings by successive magnetron sputtering technique. The Cu-coated nb-Si show the most promising electrochemical performance enhancements for the initial specific capacity as well as their cyclability compared to pristine nb-Si. The electrochemical and microstructural properties before and after cycling of the metal-coated nb-Si compared to their pristine counterparts are discussed in detail.

Automated spray coating process for the fabrication of large-area artificial opals on textured substrates.

3D photonic crystals, such as opals, have been shown to have a high potential to increase the efficiency of solar cells by enabling advanced light management concepts. However, methods which comply with the demands of the photovoltaic industry for integration of these structures, i. e. the fabrication in a low-cost, fast, and large-scale manner, are missing up to now. In this work, we present the spray coating of a colloidal suspension on textured substrates and subsequent drying. We fabricated opaline films of much larger lateral dimensions and in much shorter times than what is possible using conventional opal fabrication methods.

Upgraded silicon nanowires by metal-assisted etching of metallurgical silicon: a new route to nanostructured solar-grade silicon.

Through metal-assisted chemical etching (MaCE), superior purification of dirty Si is observed, from 99.74 to 99.9884% for metallurgical Si and from 99.999772 to 99.999899% for upgraded metallurgical Si. In addition, large area of silicon nanowires (SiNW) are fabricated. The purification effect induces a ∼35% increase in photocurrent for SiNW based photoelectrochemical cell.

Effect of pH on the synthesis and properties of luminescent SiO2/calcium phosphate:Eu3+ core-shell nanoparticles.

A novel method for the synthesis of luminescent SiO(2)/calcium phosphate (CaP):Eu(3+) core-shell nanoparticles (NPs) was developed via a sol-gel route followed by annealing at a temperature of 800 °C. The object of this study was the investigation of the effect of pH on the formation of a CaP shell around the silica core. The resulting annealed NPs exhibited an amorphous SiO(2) core and a crystalline luminescent shell. The formation of a CaP layer was possible at pH below 4.5 and above 6.5 during the coating step. The crystal structure of the shell was studied by X-ray diffraction analysis. Hydroxyapatite (HAp) and α-tricalcium phosphate were detected as crystal phases of the surrounding layer. However, NPs produced under basic conditions exhibited a higher crystallinity of the CaP layer than did samples coated at pH below 4.5. In the pH interval between 4.5 and 6.5, no shell growth but the formation of secondary NPs containing CaO and Ca(OH)(2) was observed. Furthermore, SiO(2)/CP:Eu(3+) core-shell NPs were investigated by transmission electron microscopy, dynamic light scattering, Fourier transform infrared spectroscopy, inductively coupled plasma optical emission spectrometry, and photoluminescence spectroscopy. The resulting HAp-coated NPs were successfully tested by a cell-culture-based viability assay with respect to a later application as a luminescent marker for biomedical applications.

XANES studies on Eu-doped fluorozirconate based glass ceramics.

The influence of adding InF3 as a reducing agent on the oxidation state of Eu in fluorochloro- (FCZ) and fluorobromozirconate (FBZ) glass ceramics was investigated using x-ray absorption near edge (XANES) and photoluminescence (PL) spectroscopy. For both materials, it was found that InF3 decreases the Eu2+-to-Eu3+ ratio significantly. PL spectroscopy proved that an annealing step leads to the formation of Eu-doped BaCl2 and BaBr2 nanocrystals in the FCZ and FBZ glasses, respectively. In the case of FCZ glass ceramics the hexagonal phase of BaCl2 could be detected in indium-free and InF3-doped ceramics, but only for InF3 containing FCZ glass ceramics a phase transition of the nanoparticles from hexagonal to orthorhombic structure is observed. For the FBZ glass ceramics, the hexagonal phase of BaBr2 can be formed with and without indium doping, but only in the indium-free case a phase transition to orthorhombic BaBr2 could be found.

Zr and Ba edge phenomena in the scintillation intensity of fluorozirconate-based glass-ceramic X-ray detectors.

The energy-dependent scintillation intensity of Eu-doped fluorozirconate glass-ceramic X-ray detectors has been investigated in the energy range from 10 to 40 keV. The experiments were performed at the Advanced Photon Source, Argonne National Laboratory, USA. The glass ceramics are based on Eu-doped fluorozirconate glasses, which were additionally doped with chlorine to initiate the nucleation of BaCl(2) nanocrystals therein. The X-ray excited scintillation is mainly due to the 5d-4f transition of Eu(2+) embedded in the BaCl(2) nanocrystals; Eu(2+) in the glass does not luminesce. Upon appropriate annealing the nanocrystals grow and undergo a phase transition from a hexagonal to an orthorhombic phase of BaCl(2). The scintillation intensity is investigated as a function of the X-ray energy, particle size and structure of the embedded nanocrystals. The scintillation intensity versus X-ray energy dependence shows that the intensity is inversely proportional to the photoelectric absorption of the material, i.e. the more photoelectric absorption the less scintillation. At 18 and 37.4 keV a significant decrease in the scintillation intensity can be observed; this energy corresponds to the K-edge of Zr and Ba, respectively. The glass matrix as well as the structure and size of the embedded nanocrystals have an influence on the scintillation properties of the glass ceramics.

[Theories of stages of life within the anthropology of romanticism]. / Lebensaltertheorien in der Anthropologie der Romantik.

The essay discusses the importance and prominence of theories about different stages of life in the anthropological and medical discourse of romanticism. This discourse has clearly a stabilising and restaurative function, favouring the age of moderate manhood. The political and social regulative implications of these theories demand a restaurative roll-back. The essay is based on a concept of sociology of knowledge formation.

Stereoselective synthesis of anti-alpha-(difluoromethyl)-beta-amino alcohols by boronic acid based three-component condensation. Stereoselective preparation of (2S,3R)-difluorothreonine.

Starting from optically active 3,3-difluorolactaldehyde, an alkenyl or aryl boronic acid, and an amine, a one-step three-component methodology was developed for the stereoselective preparation of anti-alpha-(difluoromethyl)-beta-amino alcohols. beta-Furyl-substituted anti-alpha-(difluoromethyl)-beta-amino alcohol was further elaborated to form (2S,3R)-difluorothreonine in high yield and ee.

Two New Modes of Pd-Catalyzed Domino-Tetracyclization of Bromodienynes-5-exo-trig Cyclization Wins over ß-Hydride Elimination.

Remarkable increases of molecular complexity in a single procedural step are achieved with the title reaction. Only a slight modification in the substitution pattern on the acyclic precursor 2 can change the mode of tetracyclization to either yield skeletons of type 1 or 3 exclusively.