Superstructure of Fe5-xGeTe2 Determined by Te K-Edge Extended X-ray Absorption Fine Structure and Te Kα X-ray Fluorescence Holography.

The local structure of the two-dimensional van der Waals material, Fe5-xGeTe2, which exhibits unique structural/magnetic phase transitions, was investigated by Te K-edge extended X-ray absorption fine structure (EXAFS) and Te Kα X-ray fluorescence holography (XFH) over a wide temperature range. The formation of a trimer of Te atoms at low temperatures has been fully explored using these methods. An increase in the Te-Fe distance at approximately 150 K was suggested by EXAFS and presumably indicates the formation of a Te trimer. Moreover, XFH displayed clear atomic images of Te atoms. Additionally, the distance between the Te atoms shortened, as confirmed from the atomic images reconstructed from XFH, indicating the formation of a trimer of Te atoms, i.e., a charge-ordered superstructure. Furthermore, Te Kα XFH provided unambiguous atomic images of Fe atoms occupying the Fe1 site; the images were not clearly observed in the Ge Kα XFH that was previously reported because of the low occupancy of Fe and Ge atoms. In this study, EXAFS and XFH clearly showed the local structure around the Te atom; in particular, the formation of Te trimers caused by charge-ordered phase transitions was clearly confirmed. The charge-ordered phase transition is fully discussed based on the structural variation at low temperatures, as established from EXAFS and XFH.

Extended X-ray Absorption Fine Structure (EXAFS) Measurements on Alkali Metal Superatoms of Ta-Atom-Encapsulated Si16 Cage.

The silicon cage nanoclusters encapsulating a tantalum atom, termed Ta@Si16, exhibit characteristics of alkali metal "superatoms (SAs)". Despite this conceptual framework, the precise structures of Ta@Si16 and Ta@Si16+ remain unclear in quantum calculations due to three energetically close structural isomers: C3v, Td, and D4d structures. To identify the geometrical structure of Ta@Si16 SAs, structural analysis was conducted using extended X-ray absorption fine structure (EXAFS) with a high-intensity monochromatic X-ray source, keeping anaerobic conditions. Focusing on "superordered" films, which constitute amorphous thin films composed solely of Ta@Si16 SAs, this analysis preserved locally ordered structures. Spectral comparisons between experimental and simulated Ta L3-edge EXAFS unveil that Ta@Si16 SAs on a substrate adopt a C3v-derived structure, while Si K-edge EXAFS introduces spectral ambiguity in structural identifications, attributed to both intracluster and intercluster scatterings. These findings underscore the significance of locally ordered structure analyses in understanding and characterizing novel nanoscale materials.

Combinatorial characterization of metastable luminous silver cations.

Thermodynamically metastable glasses that can contain metastable species are important functional materials. X-ray absorption near-edge structure (XANES) spectroscopy is an effective technique for determining the valence states of cations, especially for the doping element in phosphors. Herein, we first confirm the valence change of silver cations from monovalent to trivalent in aluminophosphate glasses by X-ray irradiation using a combination of Ag L3-edge XANES, electron spin resonance, and simulated XANES spectra based on first-principles calculations. The absorption edge of the experimental and simulated XANES spectra demonstrate the spectral features of Ag(III), confirming that AgO exists as Ag(I)Ag(III)O2. A part of Ag(I) changes to Ag(III) by X-ray irradiation, and the generation of Ag(III) is saturated after high irradiation doses, in good agreement with conventional radiophotoluminescence (RPL) behaviour. The structural modelling based on a combination of quantum beam analysis suggests that the local coordination of Ag cations is similar to that of Ag(III), which is confirmed by density functional theory calculations. This demonstration of Ag(III) in glass overturns the conventional understanding of the RPL mechanism of silver cations, redefining the science of silver-related materials.

Siliceous zeolite-derived topology of amorphous silica.

The topology of amorphous materials can be affected by mechanical forces during compression or milling, which can induce material densification. Here, we show that densified amorphous silica (SiO2) fabricated by cold compression of siliceous zeolite (SZ) is permanently densified, unlike densified glassy SiO2 (GS) fabricated by cold compression although the X-ray diffraction data and density of the former are identical to those of the latter. Moreover, the topology of the densified amorphous SiO2 fabricated from SZ retains that of crystalline SZ, whereas the densified GS relaxes to pristine GS after thermal annealing. These results indicate that it is possible to design new functional amorphous materials by tuning the topology of the initial zeolitic crystalline phases.

Densification in transparent SiO2 glasses prepared by spark plasma sintering.

Recently, spark plasma sintering (SPS) has become an attractive method for the preparation of solid-state ceramics. As SPS is a pressure-assisted low-temperature process, it is important to examine the effects of temperature and pressure on the structural properties of the prepared samples. In the present study, we examined the correlation between the preparation conditions and the physical and structural properties of SiO2 glasses prepared by SPS. Compared with the conventional SiO2 glass, the SPS-SiO2 glasses exhibit a higher density and elastic modulus, but a lower-height first sharp diffraction peak of the X-ray total structure factor. Micro-Raman and micro-IR spectra suggest the formation of heterogeneous regions at the interface between the SiO2 powders and graphite die. Considering the defect formation observed in optical absorption spectra, reduction reaction mainly affects the densification of SPS-SiO2 glass. Hence, the reaction at the interface is important for tailoring the structure and physical properties of solid-state materials prepared by the SPS technique.

Glass-Crystallized Luminescence Translucent Ceramics toward High-Performance Broadband NIR LEDs.

Near-infrared (NIR) phosphor-converted light-emitting diodes (pc-LEDs) are newly emergent broadband light sources for miniaturizing optical systems like spectrometers. However, traditional converters with NIR phosphors encapsulated by organic resins suffer from low external quantum efficiency (EQE), strong thermal quenching as well as low thermal conductivity, thus limiting the device efficiency and output power. Through pressureless crystallization from the designed aluminosilicate glasses, here broadband Near-infrared (NIR) emitting translucent ceramics are developed with high EQE (59.5%) and excellent thermal stability (<10% intensity loss and negligible variation of emission profile at 150 °C) to serve as all-inorganic visible-to-NIR converters. A high-performance NIR phosphor-converted light emitting diodes is further demonstrated with a record NIR photoelectric efficiency (output power) of 21.2% (62.6 mW) at 100 mA and a luminescence saturation threshold up to 184 W cm-2 . The results can substantially expand the applications of pc-LEDs, and may open up new opportunity to design efficient broadband emitting materials.

Relationship between diffraction peak, network topology, and amorphous-forming ability in silicon and silica.

The network topology in disordered materials is an important structural descriptor for understanding the nature of disorder that is usually hidden in pairwise correlations. Here, we compare the covalent network topology of liquid and solidified silicon (Si) with that of silica (SiO2) on the basis of the analyses of the ring size and cavity distributions and tetrahedral order. We discover that the ring size distributions in amorphous (a)-Si are narrower and the cavity volume ratio is smaller than those in a-SiO2, which is a signature of poor amorphous-forming ability in a-Si. Moreover, a significant difference is found between the liquid topology of Si and that of SiO2. These topological features, which are reflected in diffraction patterns, explain why silica is an amorphous former, whereas it is impossible to prepare bulk a-Si. We conclude that the tetrahedral corner-sharing network of AX2, in which A is a fourfold cation and X is a twofold anion, as indicated by the first sharp diffraction peak, is an important motif for the amorphous-forming ability that can rule out a-Si as an amorphous former. This concept is consistent with the fact that an elemental material cannot form a bulk amorphous phase using melt quenching technique.

Examination of structure and optical properties of Ce3+-doped strontium borate glass by regression analysis.

Amorphous materials with non-periodic structures are commonly evaluated based on their chemical composition, which is not always the best parameter to evaluate physical properties, and an alternative parameter more suitable for performance evaluation must be considered. Herein, we quantified various structural and physical properties of Ce-doped strontium borate glasses and studied their correlations by principal component analysis. We found that the density-driven molar volume is suitable for the evaluation of structural data, while chemical composition is better for the evaluation of optical and luminescent data. Furthermore, the borate-rich glasses exhibited a stronger luminescence due to Ce3+, indicating a higher fraction of BO3/2 ring and larger cavity. Moreover, the internal quantum efficiency was found to originate from the local coordination states of the Ce3+ centres, independent of composition or molar volume. The comparison of numerical data of the matrix is useful not only for ensuring the homogenous doping of amorphous materials by activators, but also for determining the origin of physical properties.

Low melting oxide glasses prepared at a melt temperature of 500 °C.

Transparent low-melting inorganic glass is an attractive industrial material based on its high thermal and light resistance compared with conventional engineering plastics. If the melting temperature of inorganic glass could be decreased, the doping of guest materials or compression moulding on the glass surface would be easier. Although phosphate glass is considered as a potential candidate because of its transparency in the visible region and low-melting behaviour, water durability often becomes a problem for implementation. Here, we prepared inorganic low-melting phosphate glass at a temperature of 500 °C via a melting and quenching methodology. It was found that tin-doped phosphate glasses exhibited higher thermal and light resistance properties than polycarbonates. Colourless transparent oxide glasses without organic components are capable of bringing about new possibilities for the application of inorganic glasses.

Oxidation suppression of Cu in alkaline aluminophosphate glass and the effects for radiation-induced luminescence characteristics.

A glass phosphor is an attractive material for applications in radiation detections because of its high workability and availability with a wide range of chemical compositions. Recently, X-ray-induced luminescence of glasses containing various luminescent activators are actively investigated worldwide. In applications as phosphor, tailoring valence state of activators, which can take multiple valence states in glass, is very important. In this research, we studied effects of glass melting atmosphere on the valence state of copper-activator ion in alkaline aluminophosphate glasses and the radiation-induced luminescence characteristics. Optical absorption and X-ray absorption near edge structure spectra of Cu-doped glasses showed that the glass fused in Ar atmosphere contains higher concentration of Cu+ than those prepared in air. In addition, the presence of Cu+ enhances the photoluminescence (PL) quantum yield and PL kinetic constant. Furthermore, the increase of Cu+ concentration resulted an improvement of the X-ray-induced scintillation and thermally-stimulated luminescence intensity.

Photocatalytic hydrogen generation of monolithic porous titanium oxide-based glass-ceramics.

A large relative surface area is crucial for high catalytic activity. Monolithic catalysts are important catalytic materials because of minimal self-degradation. Regarding large surface area catalysts, the glass-ceramics (GCs) with high formability, obtained by heat-treatment of the precursor glass, are plausible candidates. This study examines the photocatalytic behaviour of porous GCs obtained after acid leaching of MgO-TiO2-P2O5 GCs. After heat-treatment, anatase TiO2 was precipitated along with other phases. The diffraction intensity ratio between anatase and other phases was the maximum for a heat-treatment temperature of 900 °C. After acid leaching of the GCs, the relative surface area decreased with increasing TiO2 fraction; the surface area was also affected by the sample morphology. H2 generation was observed from porous GCs, while GCs without etching exhibited approximately zero activity. Thus, it was demonstrated that high surface area and prevention of the reduction reaction to Ti(III) are important for tailoring monolithic photocatalytic materials.

Structural origin of high-density Gd2O3-MoO3-B2O3 glass and low-density ß'-Gd2(MoO4)3 crystal: a study conducted using high-energy x-ray diffraction and EXAFS at high temperatures.

In this study, the short- and medium-range ordering of 21.25Gd2O3-63.75MoO3-15B2O3 glass (GM15B glass) was studied at temperatures ranging from 297 K to above the crystallization temperature. This was achieved using extended x-ray absorption fine structure and high-energy x-ray diffraction analyses to elucidate the structural origin of the higher glass density (d) as compared to that of precipitated crystals, i.e. GM15B glass with d = 4.762 g cm-3 and ß'-Gd2(MoO4)3 crystal with d = 4.555 g cm-3, and the self-powdering phenomenon in GM15B glass. The bond lengths in the short-range order, i.e. Gd-O, Mo-O, and Gd-Mo in GM15B, were extremely similar to those in the ß-phase; Gd-Gd and Mo-Mo bonds in Gd-O-Gd and Mo-O-Mo, respectively, were not found. The distance between the Gd-Gd pairs in Gd-O-Mo-O-Gd in GM15B glass, r(Gd-Gd) = 6.19 Å, was considerably smaller than that in ß-Gd2(MoO4)3 crystals (6.71 Å) in the crystallized glass at 808 K. This indicates that the glass had a more packed structure than did the precipitated crystals. The probable origin of the self-powdering phenomenon in GM15B glass was the large expansion of the structure during crystallization, which is due to the formation of an open structure with long Gd-Gd pairs and varying bond angles.

Validity of Valence Estimation of Dopants in Glasses using XANES Analysis.

X-ray absorption near edge structure (XANES) measurement is one of the most powerful tools for the evaluation of a cation valence state. XANES measurement is sometimes the only available technique for the evaluation of the valence state of a dopant cation, which often occurs in phosphor materials. The validity of the core excitation process should be examined as a basis for understanding the applicability of this technique. Here, we demonstrate the validity of valence estimation of tin in oxide glasses, using Sn K-edge and L-edge XANES spectra, and compare the results with 119Sn Mössbauer analysis. The results of Sn K-edge XANES spectra analysis reveal that this approach cannot evaluate the actual valence state. On the contrary, in LII-edge absorption whose transition is 2p1/2-d, the change of the white line corresponds to the change of the valence state of tin, which is calculated from the 119Sn Mössbauer spectra. Among several analytical approaches, valence evaluation using the peak area, such as the absorption edge energy E 0 at the fractions of the edge step or E 0 at the zero of the second derivative, is better. The observed findings suggest that the valence state of a heavy element in amorphous materials should be discussed using several different definitions with error bars, even though L-edge XANES analyses are used.

X-ray-induced Scintillation Governed by Energy Transfer Process in Glasses.

The efficiency of X-ray-induced scintillation in glasses roughly depends on both the effective atomic number Zeff and the photoluminescence quantum efficiency Qeff of glass, which are useful tools for searching high-performance phosphors. Here, we demonstrate that the energy transfer from host to activators is also an important factor for attaining high scintillation efficiency in Ce-doped oxide glasses. The scintillation intensity of glasses with coexisting fractions of Ce3+ and Ce4+ species is found to be higher than that of a pure-Ce3+-containing glass with a lower Zeff value. Values of total attenuation of each sample indicate that there is a non-linear correlation between the scintillation intensity and the product of total attenuation and Qeff. The obtained results illustrate the difficulty in understanding the luminescence induced by ionizing radiation, including the energy absorption and subsequent energy transfer. Our findings may provide a new approach for synthesizing novel scintillators by tailoring the local structure.

Formation of metallic cation-oxygen network for anomalous thermal expansion coefficients in binary phosphate glass.

Understanding glass structure is still challenging due to the result of disorder, although novel materials design on the basis of atomistic structure has been strongly demanded. Here we report on the atomic structures of the zinc phosphate glass determined by reverse Monte Carlo modelling based on diffraction and spectroscopic data. The zinc-rich glass exhibits the network formed by ZnOx (averaged x<4) polyhedra. Although the elastic modulus, refractive index and glass transition temperature of the zinc phosphate glass monotonically increase with the amount of ZnO, we find for the first time that the thermal expansion coefficient is very sensitive to the substitution of the phosphate chain network by a network consisting of Zn-O units in zinc-rich glass. Our results imply that the control of the structure of intermediate groups may enable new functionalities in the design of oxide glass materials.

Local coordination state of rare earth in eutectic scintillators for neutron detector applications.

Atomic distribution in phosphors for neutron detection has not been fully elucidated, although their ionization efficiency is strongly dependent on the state of the rare earth in the matrix. In this work, we examine optical properties of Eu-doped 80LiF-20CaF2 eutectics for neutron detector applications based on the Eu distribution. At low concentrations, aggregation of Eu cations is observed, whereas homogeneous atomic dispersion in the CaF2 layer, to substitute Ca(2+) ions, is observed in the eutectics at high concentrations. Eu LIII edge X-ray absorption fine structure (XAFS) analysis suggests that neutron responses do not depend on the amount of Eu(2+) ions. However, transparency, which depends on an ordered lamellar structure, is found to be important for a high light yield in neutron detection. The results confirm the effectiveness of the basic idea concerning the separation of radiation absorbers and activators in particle radiation scintillation and present potential for further improvement of novel bulk detectors.

Tin-Doped Inorganic Amorphous Films for Use as Transparent Monolithic Phosphors.

Although inorganic crystalline phosphors can exhibit high quantum efficiency, their use in phosphor films has been limited by a reliance on organic binders that have poor durability when exposed to high-power and/or high excitation energy light sources. To address this problem, Sn(2+)-doped transparent phosphate films measuring several micrometers in thickness have been successfully prepared through heat treatment and a subsequent single dip-coating process. The resulting monolithic inorganic amorphous film exhibited an internal quantum efficiency of over 60% and can potentially utilize transmitted light. Analysis of the film's emissivity revealed that its color can be tuned by changing the amount of Mn and Sn added to influence the energy transfer from Sn(2+) to Mn(2+). It is therefore concluded that amorphous films containing such emission centers can provide a novel and viable alternative to conventional amorphous films containing crystalline phosphors in light-emitting devices.

Narrow energy gap between triplet and singlet excited states of Sn2+ in borate glass.

Transparent inorganic luminescent materials have attracted considerable scientific and industrial attention recently because of their high chemical durability and formability. However, photoluminescence dynamics of ns(2)-type ions in oxide glasses has not been well examined, even though they can exhibit high quantum efficiency. We report on the emission property of Sn(2+)-doped strontium borate glasses. Photoluminescence dynamics studies show that the peak energy of the emission spectrum changes with time because of site distribution of emission centre in glass. It is also found that the emission decay of the present glass consists of two processes: a faster S1-S0 transition and a slower T1-S0 relaxation, and also that the energy difference between T1 and S1 states was found to be much smaller than that of (Sn, Sr)B6O10 crystals. We emphasize that the narrow energy gap between the S1 and T1 states provides the glass phosphor a high quantum efficiency, comparable to commercial crystalline phosphors.

Photoluminescence of a Te4+ center in zinc borate glass.

Photoluminescent (PL) properties related to Te(4+) species in zinc borate glasses are examined. Broad emission was observed by the excitation of the PL excitation peak of Te(4+) present at the optical absorption edge. The emission intensity of Te(4+) in 5TeO(2)-50ZnO-45B(2)O(3) glass was thermally quenched in a temperature region over 100 K, suggesting that concentration quenching preferentially occurred. The lifetime of the emission was approximately 2.5 µs, which is characteristic of relaxation from the triplet excitation state of an ns(2)-type center.