High-pressure Raman spectroscopic studies on orthophosphates Ba3(PO4)2 and Sr3(PO4)2

By using diamond anvil cell (DAC), high-pressure Raman spectroscopic studies of orthophosphates Ba₃(PO₄)₂ and Sr₃(PO₄)₂ were carried out up to 30.7 and 30.1 GPa, respectively. No pressure-induced phase transition was found in the studies. A methanol:ethanol:water (16:3:1) mixture was used as pressure medium in DAC, which is expected to exhibit nearly hydrostatic behavior up to about 14.4 GPa at room temperature. The behaviors of the phosphate modes in Ba₃(PO₄)₂ and Sr₃(PO₄)₂ below 14.4 GPa were quantitatively analyzed. The Raman shift of all modes increased linearly and continuously with pressure in Ba₃(PO₄)₂ and Sr₃(PO₄)₂. The pressure coefficients of the phosphate modes in Ba₃(PO₄)₂ range from 2.8179 to 3.4186 cm⁻¹ GPa⁻¹ for ν₃, 2.9609 cm⁻¹ GPa⁻¹ for ν₁, from 0.9855 to 1.8085 cm⁻¹ GPa⁻¹ for ν₄, and 1.4330 cm⁻¹ GPa⁻¹ for ν₂, and the pressure coefficients of the phosphate modes in Sr₃(PO₄)₂ range from 3.4247 to 4.3765 cm⁻¹ GPa⁻¹ for ν₃, 3.7808 cm⁻¹ GPa⁻¹ for ν₁, from 1.1005 to 1.9244 cm⁻¹ GPa⁻¹ for ν₄, and 1.5647 cm⁻¹ GPa⁻¹ for ν₂.     

正磷酸盐晶体Ba3(PO4)2和Sr3(PO4)2高温拉曼光谱研究

测量了碱土金属正磷酸盐Ba₃(PO₄)₂和Sr₃(PO₄)₂常温及高温拉曼光谱, 对拉曼振动模式进行指认, 并分析了晶体拉曼振动光谱及晶体结构在高温下的变化. 在温度升高的过程中, 拉曼振动频率向低频移动且振动峰宽度展宽, 晶体中的P-O平均键长随温度升高而变长, 但O-P-O的键角并未发生变化. 晶体在900 ℃以下无结构相变发生. 关键词： 3(PO₄)₂和Sr₃(PO₄)₂')" href="#">Ba₃(PO₄)₂和Sr₃(PO₄)₂ 高温拉曼光谱 振动模式 高温结构     

Laser-diode-pumped Passively Q-switched Nd:Sr5(PO4)3F Green Laser

By using a laser-diode as pump source, a Cr4+ :YAG crystal as saturable absorber for passive Q-switch and a KTP as intracavity frequency doubling crystal, we have realized the green Q-switched laser output at 0.5295 μm from a Nd: S-FAP crystal. Output green laser characteristics, such as average power, single pulse energy, pulse width, repetition rate for different small-signal transmission of Cr4+ :YAG and different pump power, were measured. Meanwhile, the coupling rate equations of intracavity frequency doubling with Cr4+ :YAG as passive Q-switch were given and the numerical solution of equations agreed with the experimental results.     

Recombination luminescence mechanisms in Ba3(PO4)2

The effect of hole self-trapping in Ba₃(PO₄)₂ at low temperatures has been studied. The TSL peak at 135 K is due to hole delocalization and diffusion by thermally activated hopping between perfect lattice sites, resulting in a composite uv band, corresponding to the tunneling recombination of holes with localized electrons.     

Laser characteristics of a new crystal Nd:Sr5(PO4)3F at 1.059 μm

The absorption spectrum of a new crystal Nd : Sr₅(PO₄)₃F or Nd : S-FAP, was measured, its two strong absorption peaks and broad effective absorption band showed that Nd : S-FAP can be appropriately pumped at 575 nm and 805.4 nm as well as with a xenon flashlamp. By using a tunable dye-laser (570.0~600.0 nm), a laser-diode (805 nm) and a xenon flash lamp as pump sources, respectively, the performance of a low threshold and high efficiency Nd:S-FAP laser at 1.059 (μm) (including pulse run, cw run, free-run and Q-switch run) has been demonstrated. The laser characteristics, such as the emission spectrum, the output energy, the output power, the pulse width, etc, were measured. In addition, the prospect of a Nd:S-FAP crystal for low-threshold high-efficiency miniature lasers is discussed.     

Nonplanar domain walls in ferroelastic Gd2(MoO4)3 and Pb3(PO4)2

A new stable, mobile zigzag-shaped domain wall configuration has been discovered in the Gd₂(MoO₄)₃ and Pb₃(PO₄)₂ structures. Previous work on these materials had not predicted this type of domain wall. The zigzag walls have mobilities 30–40 times that of planar walls in the same material. This increased mobility can be explained as a geometrical effect.     

Diode-laser pumped 1.328 μm Nd:Sr5(PO4)3F miniature laser

Nd:Sr₅(PO₄)₃F, known as Nd:S-FAP, is a new material for efficient and miniature diode-laser pumped solid-state lasers. By using a laser-diode pump operating at 805.4 nm, Nd:S-FAP has been successfully lased at 1.328 μm. A slope efficiency of 33.5% and a laser threshold of 18.5 mW have been measured. The theoretical formulas for threshold power and slope efficiency were given and the theoretical estimation agreed with the experimental result.     

Low voltage electron induced cathodoluminescence degradation and surface characterization of Sr3(PO4)2:Tb phosphor

Tb³⁺-doped Sr₃(PO₄)₂ phosphor was prepared by a sol-gel combustion method. A trigonal structure having Sr and O atoms occupying two different lattice sites were obtained. Scanning Auger nanoprobe was used to analyze the morphology of the particles. Photoluminescence (PL) and cathodoluminescence (CL) properties of Sr₃(PO₄)₂:Tb powder phosphors were evaluated and compared. In addition, the CL intensity degradation of Sr₃(PO₄)₂:Tb was evaluated when the powders were irradiated with a beam of electrons in a vacuum chamber maintained at an O₂ pressure of 1 × 10⁻⁶ Torr or a background pressure of 1 × 10⁻⁸ Torr O₂. The surface chemical composition of the degraded powders, analyzed by X-ray photoelectron spectroscopy (XPS), suggests that new compounds (metal oxides) of strontium and phosphorous were formed on the surface. It is most likely that these compounds contributed to the CL intensity degradation of the Sr₃(PO₄)₂:Tb phosphors. The CL properties and possible mechanism by which the new metal oxides were formed on the surface due to a prolonged electron beam irradiation are discussed.     

Raman spectrum of α and β-Pb3(PO4)2

The Raman spectrum of Pb₃(PO₄)₂ exhibits a progressive modification from the α to the β phase spectrum. No discontinuities are observed at the transition point.One soft mode of A_g type due to a translation mode parallel to the binary axis appears in the α phase.A strong broadening of the Rayleigh line is also observed above and below the transition point.     

Laser Diode－end－pumped Laser Performance of Nd－doped Sr＿5（PO＿4）＿3F at 1059 and 1328 nm

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Structure and electrical conductivity of a novel inorganic solid electrolyte: Na14.5[Al(PO4)2F2]2.5[Ti(PO4)2F2]0.5 (NATP)

A novel inorganic solid electrolyte with a layered framework structure stable up to 1043 K, Na_14.5[Al(PO₄)₂F₂]_2.5[Ti(PO₄)₂F₂]_0.5 (NATP), has been hydrothermally prepared and characterized by single-crystal and powder X-ray diffraction techniques, X-ray fluorescence (XRF) analysis, IR spectroscopic measurement, thermogravimetric and differential thermal analysis (TGA and DTA). NATP crystallizes in the acentric hexagonal space group P3 with a=10.448(2), b=10.448(2), , Z=1, containing a large number of Na⁺ cations in the interlamellar space and the cavities of its framework. There are six different crystallographic Na⁺ cationic sites, in which 8% Na(5) and 12% Na(6) sites are vacant. Electrical conductivity measurements show that Na⁺ cations exhibit a high mobility with two domains for the electrical conductivity versus temperature.     

Structural and luminescence characterization of synthetic Cr-doped Ni3(PO4)2

Ni_3–xCr_2x/3(PO₄)₂ (x=0 and 0.02) microcrystalline powders were obtained as single phases via a modified sol–gel Pechini-type in situ polymerizable complex method. The samples were characterized using scanning electron microscopy, X-ray diffraction, cathodoluminescence (CL), and thermoluminescence (TL) techniques. We found that Cr³⁺ doping modified the average particle and distribution. The mean particle size was 0.441 μm for Ni₃(PO₄)₂ and 0.267 μm for Ni_2.98Cr_0.013(PO₄)₂. The results also reveal that Cr³⁺ doping notably enhanced the CL and TL UV-blue emission.     

Lattice site dependent cathodoluminescence behavior and surface chemical changes in a Sr5(PO4)3F host

Eu activated Sr₅(PO₄)₃F phosphor powders have been subjected to the electron bombardment at 2 keV (10 μA) at an oxygen pressure of 1×10⁻⁶ Torr. The synthesized Sr₅(PO₄)₃F phosphor was identical to the hexagonal apatite structure, with the Sr present at two different sites C_s (S1) and C₃ (S2) in the Sr₅(PO₄)₃F host, as inferred from the crystallographic study. Cathodoluminescence (CL) and Auger electron spectroscopy of the phosphor excited by the same electron beam were used to monitor changes in the surface state during prolonged electron bombardment. A direct correlation between the surface reactions and the degradation of the CL brightness was observed. Both C and F were depleted from the surface during electron bombardment. The postulated mechanism for the electron stimulated chemical reactions on the phosphor surface is electron beam dissociation of molecular species to atomic species, which subsequently react with C to form volatile compounds CO₂, CH₄, etc. and with Sr₅(PO₄)₃F to form a non luminescence layer of metal oxides of Sr and P.     

Free energy of (PO4)2Pb3 around the transition point

The structures of α and β(PO₄)₂Pb₃ show that there is a condensation of an Au type soft mode at the ferroelastic transition point (180°C). Since only the C₁₁ elastic constant has a strong discontinuity at the transition point, the interaction term in the free energy is ΔW₃=2b?₁₁Q². The calculated discontinuities of the spontaneous deformations are in good accordance with the experimental results.     

Synthesis and properties of a new copper(II)-hafnium phosphate Cu0.5Hf2(PO4)3

Phosphates of general formula M_0.5Hf₂(PO₄)₃ with M=Cd²⁺, Ca²⁺, Sr²⁺ and Cu²⁺ were prepared by coprecipitation and characterized by several physical techniques. The compounds containing Cd²⁺, Ca²⁺, Sr²⁺ belong to the Nasicon-type structure, whereas Cu_0.5Hf₂(PO₄)₃ exhibited substantially different DRX patterns. Combined temperature programmed reduction (TPR) and temperature-programmed oxidation (TPO) showed that the copper in Cu_0.5Hf₂(PO₄)₃ was distributed between two energetically different sites in proportions respectively equal to 40 and 60%. Electron Paramagnetic Resonance (EPR) investigations confirmed the TPR/TPO results and revealed that the two sites hosting the Cu²⁺ ions are of orthorhombic symmetry. Moreover, the Cu²⁺ ions might be reduced by hydrogen to Cu⁺. These results were also supported by the UV–visible studies that showed the disappearance, under reducing conditions, of the band corresponding to crystal field transitions of Cu²⁺ ions and the emergence of a new peak attributed to the transitions between (3d)¹⁰ and (3d)⁹(4s)¹ Cu⁺ levels. At the same time, IR spectroscopy confirmed that protons entered the open lattice framework of the material and gave rise to a new protonated phase containing monovalent copper Cu_0.5^IH_0.5Hf₂(PO₄)₃. This redox process was proven to be reversible without any subsequent change in the network of the phosphate.     

Synthesis and luminescence properties of Tb:NaGd(WO4)2 novel green phosphors

Tb³⁺:NaGd(WO₄)₂ (Tb:NGW) phosphors with different Tb³⁺ concentrations have been synthesized by a mild hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence excitation and emission spectra and decay curve were used to characterize the Tb:NGW phosphors. XRD analysis confirmed the formation of NGW with scheelite structure. SEM study showed that the obtained Tb:NGW phosphors appeared to be nearly spherical and their sizes ranged from 1 to 1.5 μm. The excitation spectra of these systems showed an intense broad band with maximum at 270 nm related to the O→W ligand-to-metal charge-transfer state. Photoluminescence spectra indicated the phosphors emitted strong green light centered at 545 nm under UV light excitation. Analysis of the photoluminescence spectra with different Tb³⁺ concentrations revealed that the optimum dopant concentration for Tb³⁺ is about 15 at% of Tb³⁺ ions in Tb:NGW phosphors.     

Crystal field parameters and energy level structure of the MnO4 tetroxo anion in Li3PO4, Ca2PO4Cl and Sr5(PO4)3Cl crystals

A comparative study concerning the electronic structure of the Mn⁵⁺ ion in the Li₃PO₄, Ca₂PO₄Cl, Sr₅(PO₄)₃Cl host lattices has been carried out in the framework of the exchange charge model. The crystal field parameters have been evaluated using the structural data as the only input information. The 10 K absorption spectra of the investigated compounds have been measured in order to verify the correspondence between experimental and calculated energy levels. A systematic trend of the crystal field splitting of the most intense transitions has been evidenced and discussed by considering the symmetry properties of the coordination polyhedra around Mn⁵⁺.     

Electron paramagnetic resonance of Mn IN (NH4)2Co2(SO4)3 and (NH4)2Ni2(SO4)3 single crystals

EPR studies are reported on single crystals of ammonium cobalt sulphate and ammonium nickel sulphate containing Mn²⁺ ions. In each case only one magnetic complex of Mn²⁺ ion is found. The resonance lines in the case of Mn²⁺ doped ammonium nickle sulphate are characterised by a strong angular dependence of line intensities. The resonance lines in both the cases are fitted to a spin-Hamiltonian corresponding to orthorhombic symmetry.     

准二维电荷密度波导体磷酸钨青铜(PO2)4(WO3)2 m(m=6)的磁电阻研究

对准二维电荷密度波导体磷酸钨青铜(PO₂)₄(WO₃)_2m(m=6)在2—300K温区内的磁电阻及在2K时的Δρ/ρ_０-B关系进行了 实验研究.利用电子磁击穿模型对其低温端的磁阻增强行为进行了分析解释,理论和实验相 符合,并估算出高温端第一个Peierls能隙的大小为3.0meV,电子在低温下的迁移率为0.0 42m²V^-1s^-1 关键词： 低维导体磁电阻 电荷密度波