Preparation and Optical Properties of Nd:Bi2Ti2O7 Laser Crystal with Disordered Structure and Attractive Multiwavelength Emission Characteristics.

Laser crystals with multiwavelength emission characteristics are potential light sources for terahertz radiation. Herein, the pure and Nd-doped Bi2Ti2O7 (BTO) laser crystals with sizes up to 16 × 13 × 5 mm3 were successfully grown using the flux method in the KF-B2O3-CaBi4Ti4O15 growth system. The crystal structure, ideal morphology, chemical, mechanical, and thermal properties, optical transmission and Raman spectra, refractive index, absorption, and fluorescence spectra, as well as fluorescence lifetimes, were systematically studied. Besides, the spectral parameters of Nd3+ ions in the BTO crystal were systematically calculated based on the Judd-Ofelt theory. The Nd:BTO crystal has a wide transmittance range (0.44-7.30 µm), a small coefficient of thermal expansion (5.80 × 10-6 K-1), and a large absorption full width at half-maximum (fwhm) (31.2 nm) at around ∼804 nm, making it more potential for use in high-power laser systems. Moreover, fluorescence spectra show four emission peaks at 1054, 1062, 1104, and 1112 nm. The strong multiwavelength emission property makes Nd:BTO a promising laser crystal, serving as a potential light source for terahertz radiation.

The Local and Electronic Structure Study of LuxGd1-xVO4 (0 ≤ x ≤ 1) Solid Solution Nanocrystals.

Rare-earth-doped mixed crystals have demonstrated tunable optical properties, and it is of great importance to study the structural characteristics of the mixed-crystal hosts. Herein, LuxGd1-xVO4 (0 ≤ x ≤ 1) solid solution nanocrystals were synthesized by a modified sol-gel method, with a pure crystalline phase and element composition. The X-ray diffraction (XRD) and Rietveld refinement results showed that LuxGd1-xVO4 nanocrystals are continuous solid solutions with a tetragonal zircon phase (space group I41/amd) and the lattice parameters strictly follow Vegard's law. The detailed local structures were studied by extended X-ray absorption fine structure (EXAFS) spectra, which revealed that the average bond length of Gd-O fluctuates and decreases, while the average bond length of Lu-O gradually decreases with the increase in Lu content. Furthermore, the binding energy differences of core levels indicate that the covalent V-O bond is relatively stable, while the ionicity of the Lu-O bond decreases with the increasing x value, and the ionicity of the Gd-O bond fluctuates with small amplitude. The valence band structures were further confirmed by the first-principles calculations, indicating that the valence band is contributed to by the O 2p nonbonding state, localized Gd 4f and Lu 4f states, and the hybridized states between the bonding O 2p and V 3d. The binding energies of the Lu core and the valence levels tend to decrease gradually with the increase in Lu content. This work provides insight into the structural features of mixed-crystal hosts, which have been developed in recent years to improve laser performance by providing different positions for active ions to obtain inhomogeneous broadening spectra.

Growth, Structure and Optical Characterization of Rb3Ti3P5O20 Single Crystal.

Phosphate crystals attract much attention on account of their rich crystal structures and excellent physical and chemical properties. Herein, Rb3Ti3P5O20 single crystals were grown by the high temperature solution method using Rb2CO3 and NH4H2PO4 as the fluxes. This crystal, with non-centrosymmetric Pca21 space group, presents a three-dimensional framework structure composed of [TiO6] octahedron, [PO4] tetrahedra, and [P2O7] dimers. The electronic structure was measured via X-ray photoelectron spectroscopy. The measurements found that Rb3Ti3P5O20 has stronger Ti-O ionic bonding properties and weaker P-O covalent bonding properties compared to RbTiOPO4. Optical measurements indicated that Rb3Ti3P5O20 has a 3.54 eV band gap and a wide transmission range (0.33-4.5 µm). Theoretical calculations showed that Rb3Ti3P5O20 crystals have a moderate birefringence of 0.079 at 1064 nm. In addition, the relationship of the structure-property was studied using first-principles method. The results demonstrated that TiO6 octahedron played a significant role for the optical properties.

Synthesis, Electronic Structure, and Electrochemical Properties of the Cubic Mg2MnO4 Spinel with Porous-Spongy Structure.

Mg2MnO4 nanoparticles with cubic spinel structure were synthesized by the sol-gel method using polyvinyl alcohol (PVA) as a chelating agent. X-ray powder diffraction, infrared spectrum (IR), scanning electron microscope (SEM), and transmission electron microscope (TEM) were used to characterize the crystalline phase and particle size of as-synthesized nanoparticles. The electronic structure of Mg2MnO4 spinel was studied by X-ray photoelectron spectroscopy (XPS). The results showed that pure cubic Mg2MnO4 spinel nanoparticles were obtained when the annealing temperature was 500-700 °C. The samples had a porous-spongy structure assembled by nanoparticles. XPS studies indicated that Mg2MnO4 nanoparticles were mixed spinel structures and the degree of cation inversion decreased with increasing annealing temperature. Furthermore, the performance of Mg2MnO4 as lithium anode material was studied. The results showed that Mg2MnO4 samples had good cycle stability except for the slight decay in the capacity at 50 cycles. The coulombic efficiency (ratio of discharge and charge capacity) in most cycles was near 100%. The sample annealed at 600 °C exhibited good electrochemical properties, the first discharge capacity was 771.5 mAh/g, and the capacity remained 340 mAh/g after 100 cycles. The effect of calcination temperature on the charge-discharge performance of the samples was studied and discussed.

Role of Synthesis Method on Luminescence Properties of Europium(II, III) Ions in ß-Ca2SiO4: Probing Local Site and Structure.

The europium ion probes the symmetry disorder in the crystal structure, although the distortion due to charge compensation in the case of aliovalent dopant remains interesting, especially preparation involves low and high temperatures. This work studies the preparation of the ß-Ca2SiO4 (from here on C2S) particle from Pechini (C2SP) and hydrothermal (C2SH) methods, and its luminescence variance upon doping with Eu2+ and Eu3+ ions. The blue shift of the charge-transfer band (CTB) in the excitation spectra indicates a larger Eu3+-O2- distance in Eu3+ doped C2SH. The changes in vibrational frequencies due to stretching and bending vibrations in the FTIR and the Raman spectra and binding energy shift in the XPS analysis confirmed the distorted SiO44- tetrahedra in C2SH. The high hydrothermal temperature and pressure produce distortion, which leads to symmetry lowering although doping of aliovalent ion may slightly change the position of the Ca atoms. The increasing asymmetry ratio value from C2SP to C2SH clearly indicates that the europium ion stabilized in a more distorted geometry. It is also supported by Judd-Ofelt analysis. The concentration quenching and site-occupancy of Eu3+ ions in two nonequivalent sites of C2S were discussed. The charge state and concentration of europium ions in C2SP and C2SH were determined using X-ray photoelectron spectroscopy measurements. The C2S particles were studied by X-ray powder diffraction, FTIR, Raman, BET surface area, TGA/DTA, electron microscopy, XPS, and luminescence spectroscopy. The impact of citrate ion on the morphology and particle size of C2SH has been hypothesized on the basis of the microscopy images. This study provides insights that are needed for further understanding the structure of C2S and thereby improves the applications in optical and biomedical areas and cement hydration.

Structural and compositional analysis of a casting mold sherd from ancient China.

Casting had symbolic significance and was strictly controlled in the Shang dynasty of ancient China. Vessel casting was mainly distributed around the Shang capital, Yin Ruins, which indicates a rigorous centralization of authority. Thus, for a casting mold to be excavated far from the capital region is rare. In addition to some bronze vessel molds excavated at the Buyao Village site, another key discovery of a bronze vessel mold occurred at Daxinzhuang. The Daxinzhuang site was a core area in the east of Shang state and is an important site to study the eastward expansion of the Shang. Here, combining synchrotron X-rays and other physicochemical analysis methods, nondestructive three-dimensional structure imaging and different elemental analyses were conducted on this mold sherd. Through high penetration X-ray tomography, we obtained insights on the internal structure and discovered some pores. We infer that the generation of pores inside the casting mold sherd was used to enhance air permeability during casting. Furthermore, we suppose that the decorative patterns on the surface were carved and not pasted onto it. Considering the previous compositional studies of bronze vessels, the copper and iron elements were analyzed by different methods. Unexpectedly, a larger amount of iron than of copper was detected on the surface. According to the data analysis and archaeological context, the source of iron on the casting mold sherd could be attributed to local soil contamination. A refined compositional analysis confirms that this casting mold was fabricated locally and used for bronze casting.

Selection for Oil Content During Soybean Domestication Revealed by X-Ray Tomography of Ancient Beans.

When and under what circumstances domestication related traits evolved in soybean (Glycine max) is not well understood. Seed size has been a focus of archaeological attention because increased soybean seed weight/size is a trait that distinguishes most modern soybeans from their ancestors; however, archaeological seed size analysis has had limited success. Modern domesticated soybean has a significantly higher oil content than its wild counterpart so oil content is potentially a source of new insight into soybean domestication. We investigated soybean oil content using X-ray computed tomography (CT; specifically, synchrotron radiation X-ray CT or SRX-CT) of charred, archaeological soybean seeds. CT identified holes in the specimens that are associated with oil content. A high oil content facilitates the development of small holes, whereas a high protein content results in larger holes. The volume of small holes increased slowly from 7,500 to 4,000 cal B.P. We infer that human selection for higher oil content began as early as 7,500 cal B.P. and that high oil content cultivars were well established by 4,000 cal B.P.

Single-pulse enhanced coherent diffraction imaging of bacteria with an X-ray free-electron laser.

High-resolution imaging offers one of the most promising approaches for exploring and understanding the structure and function of biomaterials and biological systems. X-ray free-electron lasers (XFELs) combined with coherent diffraction imaging can theoretically provide high-resolution spatial information regarding biological materials using a single XFEL pulse. Currently, the application of this method suffers from the low scattering cross-section of biomaterials and X-ray damage to the sample. However, XFELs can provide pulses of such short duration that the data can be collected using the "diffract and destroy" approach before the effects of radiation damage on the data become significant. These experiments combine the use of enhanced coherent diffraction imaging with single-shot XFEL radiation to investigate the cellular architecture of Staphylococcus aureus with and without labeling by gold (Au) nanoclusters. The resolution of the images reconstructed from these diffraction patterns were twice as high or more for gold-labeled samples, demonstrating that this enhancement method provides a promising approach for the high-resolution imaging of biomaterials and biological systems.

Cation distribution in co-doped ZnAl2O4 nanoparticles studied by X-ray photoelectron spectroscopy and 27Al solid-state NMR spectroscopy.

Co(x)Zn(1-x)Al(2)O(4) (x = 0.01-0.6) nanoparticles were synthesized by the citrate sol-gel method and were characterized by X-ray powder diffraction and transmission electron microscopy to identify the crystalline phase and determine the particle size. X-ray photoelectron spectroscopy and (27)Al solid-state NMR spectroscopy were used to study the distribution of the cations in the tetrahedral and octahedral sites in Co(x)Zn(1-x)Al(2)O(4) nanoparticles as a function of particle size and composition. The results show that all of the as-synthesized samples exhibit spinel-type single phase; the crystallite size of the samples is about 20-50 nm and increases with increasing annealing temperature and decreases with Co-enrichment. Zn(2+) ions are located in large proportions in the tetrahedral sites and in small proportions in the octahedral sites in Co(x)Zn(1-x)Al(2)O(4) nanoparticles. The fraction of octahedral Zn(2+) increases with increasing Co concentration and decreases with increasing particle size. Besides the tetrahedral and octahedral coordinations, the presence of the second octahedrally coordinated Al(3+) ions is observed in the nanoparticles. The change of the inversion parameter (2 times the fraction of Al(3+) ions in tetrahedral sites) with Co concentration and particle size is consistent with that of the Zn fraction in octahedral sites. Analysis of the absorption properties indicates that Co(2+) ions are located in the tetrahedral sites as well as in the octahedral sites in the nanoparticles. The inversion degree of Co(2+) decreases with increasing particle size.