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     

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.     

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.     

Inelastic neutron scattering study of the ferroelastic phase transition of lead phosphate (PO4)2Pb3

A soft phonon mode is observed above 395°C at zone boundary points of the high temperature β phase. A quasi-elastic scattering exists above the ferroelastic transition at 180°C and progressively vanishes when the temperature is raised. A cross over from 3d to 2d regime is observed in the same temperature range.     

Proprietes optiques de la phase Na3La1−x−yCexTby(PO4)2

Dans la phase Na₃La_1?x?yCe_xTb_y(PO₄)₂, le terbium présente une émission très intense sous excitation U.V. en raison d'un transfert efficace de l'excitation du cérium au terbium, le recouvrement des spectres d'émission de Ce³⁺ et d'excitation de Tb³⁺ étant particulièrement bon. L'ordre cationique éloigne les ions activateurs les uns des autres, de sorte que le rendement quantique de l'émission reste élevé aux fortes concentrations en terbium.     

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.     

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.     

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.     

Blue and red long lasting phosphorescence (LLP) in β-Zn3(PO4)2:Mn,Zr

Multi-color long lasting phosphorescent (LLP) phenomenon in β-Zn₃(PO₄)₂:Mn²⁺,Zr⁴⁺ was systematically investigated. It is found that the red (λ_Em=616 nm) LLP performance of Mn²⁺ such as brightness and duration is largely improved, and that the blue (λ_Em=475 nm) LLP of Zr⁴⁺ with lower intensity appears when Zr⁴⁺ ions are co-doped into the matrix. The fluorescence, phosphorescence and thermoluminescence (TL) spectra show that Mn²⁺ ion is solely expected as a luminescent center, while Zr⁴⁺ ion not only acts as a luminescent center, but also induces an electron trap (Trap_Zr) associated with a TL peak at 344 K. The trap depth for Trap_Zr is 0.25 eV, while that for the intrinsic trap is 0.38 eV, associated with a dominant peak at 385 K for Zn₃(PO₄)₂:Mn²⁺. The Zr⁴⁺-induced trap with suitable depth is responsible for the improvement of the red LLP of Mn²⁺ ion and the appearance of the blue LLP of Zr⁴⁺ ion. The LLP mechanism is also investigated.     

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

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Oxygen vacancy in LiTiPO5 and LiTi2(PO4)3: A first-principles study

The structures of LiTiPO₅ and LiTi₂(PO₄)₃, as well as the possibility of oxygen vacancies formation in the systems are studied by first-principles calculations. It is found that oxygen vacancies can be formed in LiTiPO₅ and LiTi₂(PO₄)₃ under oxygen poor condition. The formation of oxygen vacancies introduce a defect band within their band gaps, which is expected to improve the electronic conductivity of LiTiPO₅ and LiTi₂(PO₄)₃ significantly. Meanwhile, a great concentration of oxygen vacancies may increase the discharge voltage of LiTiPO₅ and LiTi₂(PO₄)₃.     

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.     

Magnetic phase transition in (Mn0.95Ni0.05)3B4

It was found that the metallic compound (Mn_0.95Ni_0.05)₃B₄ was ferromagnetic below 195 K and antiferromagnetic between 195 and 354 K. The transition temperature from ferromagnetic to antiferromagnetic increases with increasing external magnetic field. On the other hand, the transition temperature from antiferromagnetic to paramagnetic decreases with increasing magnetic field. It is expected that the present results might be explained by the theoretical results on the coexistence of ferro- and antiferromagnetism in the itinerant electron system reported by Moriya and Usami.     

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.     

Phase transition and analysis of AC conductivity data of the (Cs)0.26(Rb)0.74H(SO4)0.89(SeO4)0.11 compound

The X-ray diffraction, vibrational and impedance spectroscopy studies of (Cs)_0.26(Rb)_0.74H(SO₄)_0.89(SeO₄)_0.11 (CsRbHSSe) new solid solution are presented. The title compound undergo a superionic phase transition (SPT) at This transition was confirmed by an abrupt increase of conductivity. The bulk impedance parameters of CsRbHSSe, RbH(SO₄)_0.81(SeO₄)_0.19 (RbHSSe) and CsH(SO₄)_0.76(SeO₄)_0.24 (CsHSSe) were determined from an analysis of AC conductivity data measured in a wide temperature range. The charge carriers concentration in the samples investigated has been evaluated using the Almond-West formalism and shown to be independent of temperature.     

Raman and FTIR studies of the structural aspects of Nasicon-type crystals; AFeTi(PO4)3 [A=Ca, Cd]

Raman and FTIR spectra of CaFeTi(PO₄)₃ and CdFeTi(PO₄)₃ are recorded and analyzed. The observed bands are assigned in terms of vibrations of TiO₆ octahedra and PO₄ tetrahedra. The symmetry of TiO₆ octrahedra and PO₄ tetrahedra is lowered from their free ion symmetry. The presence of Fe³⁺ ion disrupts the Ti-O-P-O-Ti chain and leads to the distortion of TiO₆ octrahedra and PO₄ tetrahedra. The PO₄³⁻ tetrahedra in both crystals are linearly distorted. The covalency bonding factor of PO₄³⁻ polyanion of both the crystals are calculated from the Raman spectra and compared to that of other Nasicon-type systems. The numerical values of covalency bonding factor indicates that there is a reduction in redox energy and cell voltage and is attributed to strong covalency of PO₄³⁻ polyanionin.     

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.     

Phase transition in (NH4)3FeF6

By use of Mössbauer spectroscopy we have found that the transition from tetragonal to cubic structure in (NH₄)₃FeF₆ takes place at 263 K. The phase transition exhibits a hysteresis of 0.5 K. The experimental data indicate that the tetragonal deformation found at low temperatures diminishes gradually as the transition temperature is approached. The spectra are influenced by electronic relaxation.     

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.