Fine structure in the low temperature luminescence of Zn2SiO4:Mn and Mg4Ta2O9:Mn

The luminescence of powder samples of the well-known green-emitting Zn₂SiO₄:Mn and the red-emitting Mg₄Ta₂O₉:Mn phosphor shows a considerable fine structure at 4° K in appropriately prepared samples containing a sufficiently low Mn concentration. For (Zn_1-xMn_x)₂SiO₄ (0.0005?x?0.05) two sharp lines were found which are interpreted as due to zero phonon transitions between the ⁴T₁ and ⁶A₁ levels of Mn²⁺ ions on the two crystallographically different zinc sites. The remaining structure is ascribed to vibronic sidebands. The decay times of the luminescence bands associated with the two sites differ; they are 12 and 15 ms for the high and low energy bands respectively. The experimental results of Vlam are confirmed by our data. In addition some (Zn_1-yBe_y)₂SiO₄:Mn (0.025? y ?1) samples were investigated. In Mg₄Ta₂O₉:Mn two zero phonon lines could be identified, indicating that in this material Mn²⁺ is distributed over two inequivalent Mg sites. Most of the phonon replicas were found at intervals of 15 meV. Raman scattering experiments showed that this energy corresponds to one of the lattice vibrations. The decay time of this luminescence band is 1.0 ms.     

Internal modes and the local symmetry of PO4 tetrahedra in K(H1−xDx)2PO4 by Raman scattering

The v₃ and v₄ internal modes of PO^3?₄ tetrahedra are observable in KH₂PO₄ even above the transition temperature in the scattering geometry x(zz)y contrary to the selection rule of the site symmetry S₄ in the D_2d space group. Tominaga et al. discussed that the origin of this broken selection rule is due to the momentary site symmetry C₂ of these tetrahedra, and that the mechanism of the phase transition is of the order-disorder type of these distorted tetrahedra. Parallel studies compatible with their results have been carried out on mixed crystals K(H_1?xD_x)₂PO₄ and the same conclusion has been obtained as to the momentary site symmetry. These internal modes increase in intensity with deuteration, and the origin of this increase is discussed.     

Coulometric titration of copper in CuxMo6S8−y(0⩽y⩽0.4) with solid Cu-electrolyte Rb4Cu16I7Cl13

In order to determine the copper content x of copper Chevrel compound Cu_xMo₆S_8?y(0?y?0.4) as a function of copper activity a_Cu and sulfur deficit y, a solid state electrochemical cell, Cu/Rb₄Cu₁₆I₇Cl₁₃/Cu_xMo₆S_8?y/Pt, was constructed and coulometric titration studies were made at 400 K. For the evaluation of the coulometric titration data, measurements were made on the electronic conductivity of copper-ion conductor Rb₄Cu₁₆I₇Cl₁₃. Also, a brief investigation was made on the condition of formation of single phase Chevrel Cu_xMo₆S_8?y with varying x and y at 1000°C. The structural change of Cu_xMo₆S_8?y with a change in x and y was studied by the X-ray diffraction method. It was found that x for constant a_Cu decreases with increasing y. The maximum value x_max of x in Cu_xMo₆S_8?y in equilibrium with metallic copper was found to be expressed by $\text{x}{}_{\mathrm{<mtext>max</mtext>}}\text{=-(}\text{10}\text{3}\text{)y+5}$. In the region of y<0.3, x_max exceeded 4, contrary to a presupposition that x_max is less than 4. X-ray analysis revealed that most of the copper Chevrel compounds denoted by Cu_xMo₆S₈ so far were sulfur deficient ones with y?0.4. The importance of sulfur deficit on the properties of the copper Chevrel compound was emphasized.     

Luminescent spectral characteristics of EuxLa1 - xTa7O19 polycrystals

Eu_xLa_{1 - x}Ta₇O₁₉ geptatantalates have been synthesized (x = 0.005-10). The luminescence and excitation spectra of these geptatantalates have been investigated at 77 and 300 K. It is supposed that the Eu³⁺ luminescence spectrum for all x may be interpreted within one type optical center with D_2d symmetry. The energy level diagram of the luminescence center has been worked out. It has been found that there is concentration dependence quenching of an europium luminescence. The reasons for this are discussed.     

Non affinity of Fe2+ for B sites in iron thiochromites and compared band structures of oxides and sulfides spinels

Departure from stoichiometry in vapor grown FeCr₂S₄ was studied using Mössbauer spectroscopy. The paramagnetic Mössbauer spectra give evidence of two singlets and two doublets which correspond respectively to A site Fe²⁺ ? Fe³⁺, Fe^II in T_d symmetry and in symmetry lower than T_d. The following ionic distribution has been deduced:

$\text{(Fe}{}^{\mathrm{2+}}{}_{\mathrm{1?y}}\text{Fe}{}^{\mathrm{3+}}{}_{\mathrm{y}}\text{)|Cr}{}^{\mathrm{3+}}{}_{\mathrm{2?x}}\text{□}{}_{\mathrm{x}}\text{|S}{}_{\mathrm{4?z}}\text{□}{}_{\mathrm{z}}$

Compounds in the system Fe_1+xCr_2?xS₄ have been studied for 0 ? x ? 0.1. The spectra are solved assuming Fe^II in A site with T_d symmetry, A site Fe^II with lower symmetry and B site Fe³⁺. No Fe²⁺ appears in B site. These features are discussed in terms of schematic band structures implying single electron narrow bands. The non-affinity of Fe²⁺ for B sites of iron thiochromites is discussed in relation with B site Cr²⁺ level.     

A combinatorial approach to the discovery and optimization of YCa4O(BO3)3-based luminescent materials

Thin films of YCa₄O(BO₃)₃ (YCOB)-based new luminescent materials were explored by the combinatorial pulsed laser deposition (PLD) method which enabled us to fabricate continuous composition spread film libraries. Strong red and green luminescence were found in the Y_1−xEu_xCOB (0 ≤ x ≤ 1), (YEuCOB) and Y_1−yTb_yCOB (0 ≤ y ≤ 1) (YTbCOB) films, respectively. The film libraries were characterized by photoluminescence (PL), PL decay, an electron-probe microanalyzer and an electron diffraction analysis. The luminescent intensities in the amorphous film libraries strongly depended on the chemical composition of each rare-earth (RE) ion. The optimum concentration of rare-earth ions in YEuCOB and YTbCOB were experimentally determined to be Eu = 7.5% and Tb = 20-30%, respectively.     

Neutron inelastic scattering from mixed salts [(NH4)xK1−x]2SO4

Neutron inelastic scattering measurements have been performed on [(NH₄)_xK_1?x]₂SO₄. It is shown that NH₄⁺ preferentially occupies one of the two available inequivalent sites at smaller concentrations. NH₄⁺ at the other site seems to be necessary for the occurance of ferroelectricity in these compounds.     

Na+ ion conductivity and crystallographic cell characterization in the Hf-nasicon system Na1+xHf2SixP3−xO12

We have measured the effect of varying the mobile ion concentration on the sodium ion conductivity in the Hf-Nasicon system, Na_1+xHf₂Si_xP_3-xO₁₂, for 1.4 ? x ? 2.8. The conductivity is greatest for Na_3.2Hf₂Si_2.2 P_0.8O₁₂: σ_25°C = 2.3 × 10^?3 (ω cm)^?1, and σ_250°C = 1.7 × 10^?1 (ω cm)^?1. These values are approximately 50% greater and worse, respectively, than the values reported for the best Zr-Nasicon. We have characterized the variation of lattice parameters with composition and found the behavior to be similar to that of Zr-Nasicon. A small distortion from rhombohedral to monoclinic symmetry occurs for compositions 1.8 ? x ? 2.2.     

Mössbauer study of Zn2+ and Sn4+ additives in Nickel ferrites

The Mössbauer study of Fe⁵⁷ in polycrystalline solid solutions of Ni_{1 + x ? y}Zn_ySn_xFe_{2 ? 2x}O₄ (y = 0.1, 0.3, 0.5 and x = 0.1 to 0.5 with x varying in steps of 0.1) has been made. The present work has been aimed at investigating the variation of isomer shift, nuclear magnetic field at Fe⁵⁷ nuclei and ionic distribution at tetrahedral and octahedral sites when the concentration of Zn²⁺ and Sn²⁺ ions is successively increased in nickel ferrites. The ionic distribution in samples having low tin concentration has been explained on the basis of Neel's molecular field model whereas the ionic distribution of samples having high tin and zinc concentration has been explained on the basis of formation of isolated superparamagnetic clusters at the octahedral site. It has been inferred that a larger substitution of zinc and tin ions enhances relaxation effects.     

Luminescence of Eu2+-activated Cs(Ca,Mg)F3 and Rb(Ca,Mg)F3

In the system CsCa_0.95?xMg_xEu_0.05F₃ a new phase has been found with x ≈ 0.7, which gives efficient blue luminescence. For RbCa_0.95?xMg_xEu_0.05F₃ efficient green luminescence is obtained at x ≈ 0.5.     

Energy transfer and luminescent properties of Ce, Cr co-doped Y3Al5O12

The phosphors in the system Y_3−xAl_5-yO₁₂:xCe³⁺,yCr³⁺ were synthesized by solid-state reactions and their photoluminescence properties were investigated. These phosphors have absorption in the visible light region and give luminescence in the far-red region (∼688 nm), which are suitable for the application in the device of luminescent solar concentrator (LSC). In these phosphors, Ce³⁺ located at Y³⁺ site can effectively transfer its absorbed energy to Cr³⁺ at Al³⁺ site.     

Magnetic ordering in EuxSr1−xSySe1−y

Specific heat and ac-susceptibility measurements are reported for Eu_xSr_1?xS_ySe_1?y samples. The critical concentrat ion for long-range magnetic ordering x_c increases with decreasing y, for y = 0.1, x_c = 1.0 holds. For samples with x < x_c a broad peak in the specific heat and a peak in the susceptibility at lower temperatures indicates a spin glass type of magnetic ordering.     

Electrochemical luminescence of Mg1−xCaxIn2O4:Er electrodes

Improvement for electrochemical luminescence (ECL) property of MgIn₂O₄ is attempted by partial exchange of Mg²⁺ ion in MgIn₂O₄ to Ca²⁺ ion. Mg_1−xCa_xIn₂O₄ solid solution was obtained in the region 0<x<0.4. Efficiency for ECL per unit current for Mg_1−xCa_xIn₂O₄:Er³⁺ increased with the increase in the ratio of Ca²⁺ ion, and showed a peak at x=0.25 and then decreased steeply. ECL efficiency for other rare-earth ion-(RE:Sm, Eu, Ho) doped Mg_1−xCa_xIn₂O₄ also increased comparing with those for MgIn₂O₄:RE. This Ca²⁺ addition effect on the ECL efficiency seems to be caused by the improvement of the efficiency for the impact activation.     

A study by E.S.R. of Mn2+ in potassium chromate

Divalent manganese ions are found in potassium chromate single crystals after heating at 600°C in the presence of iodine. These ions occupy three differently oriented sites with the same spin Hamiltonian parameters: g_z = 2·000, g_x = 2·008, g_y = 2·015; A_z = ?88·4 G, A_x = A_y = ?91 G; D = 190 and E = ?30 G.The authors suggest that Mn²⁺ occupies a substitutional (K⁺) position rather than an interstitial one. The influence of iodine is discussed.     

Raman scattering studies of the effects of a symmetry-breaking impurity on the ferroelectric phase transition in K1−xLixTa1−yNbyO3

Raman scattering and optical depolarization measurements on K_1?xLi_xTa_1?yNB_yO₃ with y ? 0.028 and x ? 0.06 show that lithium impurities destabilize the niobium-induced rhombohedral ferroelectric phase. With increasing x the phase transition is altered from a soft-mode dominated transition to a disorder-order transition into a tetragonal phase. The dependence of T_c on x disagrees with the predictions of classical mean-field theory.     

Intracenter luminescence of Mn2+ in Cd1−x MnxTe and Cd1−x−y MnxMgyTe under intense optical pumping

A comparative analysis of the kinetic properties of intracenter 3d luminescence of Mn²⁺ ions in the dilute magnetic superconductors Cd_1?x Mn_xTe and Cd_1?x?y Mn_xMg_yTe is carried out. The influence of relative concentrations of the cation components on the position of the intracenter luminescence peak indicates that the introduction of magnesium enhances crystal field fluctuations. As a result, the processes facilitating nonlinear quenching of luminescence are suppressed. The kinetics of 3d-luminescence quenching in Cd_1?x Mn_xTe are accelerated considerably upon elevation of optical excitation level due to the evolution of cooperative processes in the system of excited manganese ions.     

Neutron powder diffraction study on the structures of LaNi5−xAlxDy compounds

The structures of LaNi_5−xAl_xD_y (x=0.75,0.25,y=1.01, 1.10, 1.91 and 3.1) were systematically investigated by neutron and X-ray diffraction. D atoms are found to enter the 6m site of the α-phase but not the reported 12n site, while the 6m and 12n sites of the β-phase. In the case of LaNi_4.75Al_0.25D_y with lower Al content and symmetry, D atoms do not enter the α-phase but occupy the 4h site besides the 6m and 12n sites of the β-phase. The relationship between structures and properties is also discussed.     

Thermodynamics of type A1−xBxC1−yDy III–V quaternary solid solutions

An improved theory based on the pair approximation is given for the thermodynamic properties of type A_1?xB_xC_1?yD_yIII–V quaternary solid solutions. The theory takes into account the quasi-chemical nature of the nearest neighbor pair distribution, which has been neglected or inadequately treated in previous work. With a suitable thermodynamic treatment, a quasi-chemical equilibrium relation for the nearest neighbor pair distribution is derived. Numerical calculations using available thermodynamic data show that the distribution will deviate appreciably from random mixing values in the In_1?xGa_xP_1?yAs_y and Al_1?xGa_xAs_1?ySb_y systems due to a short-range clustering effect of nearest neighbor pairs with strong bond energy, whereas the deviation will be small in the Al_1?xGa_xP_1?yAS_y system. The expressions for the chemical potentials and the activity coefficients of the binary compound components are given. These are readily applicable to phase diagram calculations.     

Transport and magnetic properties of disordered LixVyO2 (x=0.8 and y=0.8)

The magnetic and electron transport properties of rhombohedral Li_xV_yO₂ (x=0.8 and y=0.8) are studied. The dc susceptibility of Li_xV_yO₂ can be well fitted to the modified Curie-Weiss law, which verified the paramagnetic ground state. The magnetic hysteresis and ac susceptibility also confirm this paramagnetism. The Li_xV_yO₂ exhibits semiconducting behavior, which is explained by thermal activated process at high temperature and variable-range hopping mechanism at low temperature. Anderson localization plays an important role in both the electron transport behavior and the magnetic behavior due to the site disorder between the Li⁺ ion and V⁴⁺ ion.     

Evidence by Raman scattering on In1−xGaxAsyP1−y of the two-mode behaviour of In1−xGaxP

We report the Raman scattering study of optical vibrations in indium rich In_1?xGa_xAs_yP_1?y epitaxial layers grown on InP. We evidence the splitting of the LO line of InP even for very small x and demonstrate it is due to the presence of gallium in the samples. These results lead us to ascribe to In_1?xGa_xP a somewhat modified two-mode behaviour and to In_1?xGa_xAs_yP_1?y a four-mode behaviour.