VUV spectroscopy of complex fluoride systems Na0.4(Y1−xREx)0.6F2.2 (RE3+ = Nd3+, Tm3+)

Emission and excitation spectra as well as luminescence decay kinetics of complex non-stoichiometric fluoride crystals Na_0.4(Y_1−xNd_x)_0.6F_2.2 (x = 0.005, 0.05, 0.2, 1) and Na_0.4(Y_1−xTm_x)_0.6F_2.2 (x = 0.0005, 0.01, 0.05, 0.1) have been studied in the VUV spectral range at liquid-helium (T ∼ 10 K) temperatures. It has been shown that these crystals show intense broad-band VUV luminescence due to the interconfiguration 5d-4f transitions in Nd³⁺ and Tm³⁺ ions. Remarkable concentration quenching is observed for Nd³⁺ 5d-4f luminescence whereas fast (spin-allowed) 5d-4f luminescence of Tm³⁺ shows no concentration quenching for the studied doping level up to 10%. The spin-allowed 5d-4f luminescence of Tm³⁺ in these crystals was found to be rather weak compared to spin-forbidden 5d-4f luminescence because of efficient nonradiative relaxation from higher-energy 5d states of Tm³⁺ to the lowest-energy 5d level responsible for spin-forbidden 5d-4f luminescence. The studied fluoride systems can be considered as promising active media for the development of VUV solid state lasers with optical pumping.     

Synthesis,structural characterization and photophysical properties of highly photoluminescent crystals of Eu(III), Tb(III) and Dy(III) with 2,5-thiophenedicarboxylate

Lanthanide compounds of general formula [Ln₂(2,5-tdc)₃(dmf)₂(H₂O)₂]·2dmf·H₂O (Ln = Eu(III) (1), Tb(III) (2), Gd(III) (3) and Dy(III) (4), dmf = N,N′-dimethylformamide and 2,5-tdc²⁻ = 2,5-thiophedicarboxylate anion) were synthesized and characterized by elemental analysis, X-ray powder diffraction patterns, thermogravimetric analysis and infrared spectroscopy. Phosphorescence data of Gd(III) complex showed that the triplet states (T₁) of 2,5-tdc²⁻ ligand have higher energy than the main emitting states of Eu(III), Tb(III) and Dy(III), indicating that 2,5-tdc²⁻ ligand can act as intramolecular energy donor for these metal ions. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal energy transfer. The high value of experimental intensity parameter Ω₂ for the Eu(III) complex indicate that the europium ion is in a highly polarizable chemical environment. The emission quantum efficiency (η) of the ⁵D₀ emitting level of Eu(III) was also determined. The complexes act as possible light conversion molecular devices (LCMDs).     

First observation of the reversible O3 ↔ P2 phase transition: Crystal structure of the quenched high-temperature phase Na0.74Ni0.58Sb0.42O2

According to thermal expansion data, O3-type phase Na_xNi_(1+x)/3Sb_(2−x)/3O₂ (x ≈ 0.8) undergoes at ca. 1270 K a reversible transition to a less dense form. The high-temperature phase quenched to liquid nitrogen belongs to P2 type, space group P6₃/mmc (no. 194), a = 3.0123 Å(2), c = 11.2264 Å(7) for x ≈ 0.74 at 298 K. The stabilisation of P2 versus O3-type structure at high temperatures seems to be due to alkali distribution over greater number of sites thus increasing entropy and decreasing Na⁺–Na⁺ repulsion.     

Giant magnetoimpedance in nanocrystalline Fe90.3−xZr7B2.7Cux (0.5 ≤ x ≤ 1.5) as-spun ribbons

The nanocrystalline ribbons Fe_90.3−xZr₇B_2.7Cu_x with low Cu contents can be directly obtained through melt-spinning technique with an appropriate low quenching speed such as 22 m/s. Sizes of bcc-Fe grains precipitated in Fe_90.3−xZr₇B_2.7Cu_x as-spun ribbons were 17 nm for x = 0.75, 15 nm for x = 1 and 12 nm for x = 1.25. The addition of Cu reduces grain size of bcc-Fe in as-spun nanocrystalline Fe_90.3−xZr₇B_2.7Cu_x ribbons. Among the investigated samples (0.5 ≤ x ≤ 1.5), the largest magnetoimpedance can be obtained in the nanocrystalline Fe_80.3Zr₇B_2.7Cu₁ as-spun ribbon with x = 1. The value of magnetoimpedance (Z(H) − Z(0)) / Z(0) under H = 90 Oe for Fe_80.3Zr₇B_2.7Cu₁ as-spun ribbon reaches − 28.2% at a frequency of 1 MHz.     

La and Co substituted M-type barium ferrites processed by sol–gel combustion synthesis

The flake-like Ba_1−xLa_xCo_xFe_12−xO₁₉ (x = 0.0–0.4) were synthesized using sol–gel combustion synthesis process followed by the thermal insulation process and heating treatment. The synthesis process was investigated and the structure details, morphology, and magnetic properties were evaluated. TG/DTA was used to investigate the formation mechanism and to identify the thermal insulation temperature at 400 °C followed by the heat treatment temperature at 1200 °C. XRD patterns demonstrated that the unit cell volume and particle size decreased with the increase of the substitution content. The typical particles size was in the range of 1–2 μm in the planar dimension whilst the thickness was in the range of 200–500 nm. It was found from the VSM graphs that the saturation magnetizations M_s reached a maximum of 68.15 emu g⁻¹ at x = 0.3 and then decreases to 64.72 emu g⁻¹ at x = 0.3 whilst the coercivity H_c sustained decreases from 2190.70 to 1181.07 Oe g⁻¹ with substitution content increased from 0 to 0.4.     

(C2N2H10)[FexV1−x(HPO3)F3] (x = 0.44, 0.72): Two new organically templated phosphites: Solvothermal synthesis and structural,thermal, spectroscopic and magnetic studies

(C₂N₂H₁₀)[Fe_xV_1−x(HPO₃)F₃] (x = 0.44, 0.72) have been synthesized using mild solvothermal conditions under autogenous pressure and the ethylenediamine molecule as templating agent. The crystal structures have been determined from X-ray single-crystal diffraction data. The compounds crystallize in the orthorhombic P2₁2₁2₁ space group with Z = 4 and unit-cell parameters a = 12.8494(9), b = 9.5430(6), c = 6.4372(5) Å, and a = 12.8578(1), b = 9.5342(1), c = 6.4370(7) Å for (C₂N₂H₁₀)[Fe_0.44V_0.56(HPO₃)F₃] and (C₂N₂H₁₀)[Fe_0.72V_0.28(HPO₃)F₃], (1) and (2), respectively. These isostructural compounds exhibit a monodimensional crystal structure formed by pillared double anionic chains with the formula [M(HPO₃)F₃]²⁻, extended along the [0 0 1] direction. These doubled ionic chains are the result of the linking of two simple chains in which there are alternating octahedral [MO₃F₃] and tetrahedral groups [HPO₃]. The ethylendiammonium cations are placed in the space delimited by three different chains. The metallic ions are interconnected by the pseudo-pyramidal (HPO₃)²⁻ phosphite oxoanions, adopting a slightly distorted octahedral geometry. The IR spectra show bands corresponding to the phosphite oxoanion and the ethylendiamonium cation at 2400 and 1600 cm⁻¹, respectively. The thermogravimetric analyses show that these phases are stable up to ca. 280 °C, at higher temperatures, the decomposition of the crystal structure begins by calcination of the organic cation and the elimination of the fluoride anions. The diffuse reflectance spectra show bands of the V³⁺ ion (d²) in octahedral symmetry. The values of the Dq (1540, 1540 cm⁻¹), and Racah parameters, B (560, 535 cm⁻¹) and C (3055, 3140 cm⁻¹) for (1) and (2), respectively, correspond with those usually found for octahedrically coordinated V(III) compounds. Magnetic measurements, performed on a powered sample from 5.0 to 300 K at 1000 G, in the ZFC and FC modes, indicate the existence of antiferromagnetic interactions.     

Microwave-induced combustion synthesis and electrical conductivity of Ce1−xGdxO2−1/2x ceramics

Ce_1−xGd_xO_2−1/2x nanopowder were successfully synthesized by microwave-induced combustion process. For the preparation, cerium nitrate, gadolinium nitrate hexahydrate, and urea were used for the microwave-induced combustion process. The process took only 30 min to obtain Ce_1−xGd_xO_2−1/2x powders. The exo-endo temperature, phase identification, and morphology of resultant powders were investigated by TG/DTA, XRD, and SEM. The as-received Ce_1−xGd_xO_2−1/2x powders showed that the average particle size ranged from 18 to 50 nm, crystallite dimension varied from 11 to 20 nm, and the specific surface area was distribution from 16 to 46 m²/g. As for Ce_1−xGd_xO_2−1/2x ceramics sintered at 1450 °C for 3 h, the bulk density of Ce_1−xGd_xO_2−1/2x ceramics were over 91% of the theoretical density, the maximum electrical conductivity, σ_700 °C = 0.017 S/cm with minimum activation energy, E_a = 0.869 eV was found at Ce_0.80Gd_0.20O_1.90 ceramic.     

Growth of the Zn1−xMnxO alloy by the MOCVD technique

Single-phase thin films of the diluted magnetic semiconductor Zn_1−xMn_xO have been grown by the MOCVD technique. Depositions have been done at T = 450 °C on fused silica and (0 0 0 1) sapphire substrates. Layers on silica exhibit polycrystalline structure with [0 0 1] preferential orientation while Zn_1−xMn_xO films are (0 0 0 1) epitaxially grown on c-sapphire with the epitaxy relation: 30° rotation of the Zn_1−xMn_xO [1 0 0] direction with respect to the [1 0 0] of the substrate. The manganese content varies in the (0–30%) range and is always higher in samples grown on sapphire substrates under the same conditions. Variations of a and c lattice parameters, assessed by X-ray diffraction, follow Vegard's law and attest to the incorporation of substitutional Mn²⁺ ions. Hall effect measurements show a decrease of the mobility with the incorporation of manganese in ZnO, and optical transmission results present the shift of the absorption edge towards higher energies.     

Microwave dielectric properties of Ba(Mg1/3Ta(2−2x)/3Wx/3Tix/3)O3 ceramics

The microwave dielectric properties of ceramics based on Ba(Mg_1/3Ta_(2−2x)/3W_x/3Ti_x/3)O₃ is investigated as a function of x. The densification as well as dielectric properties deteriorate with increase in the substitution levels of (Ti_1/3W_1/3)^3.33+ at (Ta_2/3)^3.33+ site in Ba(Mg_1/3Ta_2/3)O₃. The τ_f is approaching zero between x = 0.1 and 0.15 in Ba(Mg_1/3Ta_(2−2x)/3W_x/3Ti_x/3)O₃ where quality factor is reasonably good (Q_u × f = 80,000–90,000 GHz). The Ba(Mg_1/3Ta_(2−2x)/3W_x/3Ti_x/3)O₃ with x = 1.0 has ɛ_r = 15.4, τ_f = −25.1 ppm/°C, Q_u × f = 35,400 GHz.     

Luminescence properties of Sn2P2Se6 crystals

A large family of Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) semiconductor-ferroelectric crystals were obtained by the Bridgman technique. The photoluminescence properties of the Sn_2yPb_2(1−y)P₂S_6xSe_6(1−x) family crystals strongly depend on their chemical composition, excitation energy and temperature. The influence of the Pb → Sn and S → Se isovalent substitutions on the luminescence properties of a crystal with the Sn₂P₂Se₆ basic composition was investigated. A broad emission band observed in the Sn₂P₂Se₆ crystal with a maximum roughly at 600 nm (at T = 8.6 K) was assigned to a band-to-band electron-hole recombination, whereas broad emission bands, peaked near 785 nm (at T = 8.6 K) and 1025 nm (at T = 44 K) were assigned to an electron-hole recombination from defect levels localised within the bandgap. Possible types of recombination defect centres and specific mechanisms of luminescence in the Sn₂P₂Se₆ semiconductor-ferroelectric crystals were considered and discussed on the basis of the obtained results and the referenced data.     

Coupled substitutions in In2O3: New transparent conductors In2−xM2x/3Sbx/3O3 (M = Cu,Zn)

Two solid solutions In_2−xM_2x/3Sb_x/3O₃ (M = Cu, Zn) with the bixbyite structure have been synthesized in air at 1300 °C. The homogeneity range is larger for Zn (x = 0.42) than for Cu (x = 0.20) and the cationic distribution of the Cu/Sb and Zn/Sb couples is weakly ordered. These new oxides appear to be transparent conductors. Even fully deprived of tin, they have good potential properties. These oxides are either semiconductors with a small band gap (Cu/Sb) or semimetals (Zn/Sb) with σ = 3 × 10² (Ω cm)⁻¹ at room temperature. These materials are more efficient than bulk ITO prepared under the same experimental conditions, i.e. without reducing treatment (σ = 50 (Ω cm)⁻¹).     

Two-step growth of Cd0.96Zn0.04Te/Si(111) epilayers by HWE

High quality Cd_1−xZn_xTe, x = 0.04 epilayers are successfully grown directly on hydrogen-terminated Si(111) substrates by hot wall epitaxy method. Growth conditions are optimized in order to grow single crystal films with desired composition. It is found that surface morphology of the epilayers is dramatically affected by the growth temperature and the growth rate at the early stage of the crystal growth. Applying limited high substrate temperature of T_sub = 440 °C and low growth rate of 0.04 μm/h, the crystallinity is significantly improved and for the first time a pseudomorphic 2D growth is observed notwithstanding of the large lattice mismatch. Designing a suitable two-step growth process makes it possible that Cd_1−xZn_xTe/Si(111), x = 0.04 epilayers are fabricated with good surface morphology, which could be used as lattice matched substrates for MCT and MCZT epitaxy.     

Microwave dielectric ceramics in (Ca1− xBax)(Zn1 / 3Nb2 / 3)O3 system

(Ca_1−xBa_x)(Zn_1 / 3Nb_2 / 3)O₃ (x = 0–1.0) microwave dielectric ceramics were prepared and investigated. The Ba(Zn_1 / 3Nb_2 / 3)O₃-based solid solution was observed for x = 0.9, and the compositions with x = 0.1–0.7 resulted in the mixture of two phases. Dielectric constant ε_r and temperature coefficient of resonant frequency τ_f of the present ceramics varied anomalously and reached their maximum at x = 0.7–0.9, and these phenomena were originated from the partial substitution of small Ca²⁺ ions for larger Ba²⁺ at A-site. On the other hand, a good combination of microwave dielectric properties (ε_r = 36, Qf = 16,170 GHz, τ_f = − 12 ppm/°C) were obtained at x = 0.1, while the decreased Qf value was observed in other compositions.     

Low temperature synthesis of LnOF rare-earth oxyfluorides through reaction of the oxides with PTFE

A low temperature solid-state synthesis route, employing polytetrafluoroethylene (PTFE) and the rare-earth oxides, for the formation of the LnOF rare-earth oxyfluorides (Ln = Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er), is reported. With the exception of LaOF, which forms in a tetragonal variant, rhomobohedral LnOF is found to be the major product of the reaction. In the case of PrOF, a transition from the rhombohedral to the cubic fluorite phase is observed on heating in air to 500 °C. X-ray diffraction shows the expected lanthanide contraction in the lattice parameters and bond lengths. Magnetic susceptibility measurements show antiferromagnetic-like ordering in TbOF, T_m = 10 K, with a metamagnetic transition at a field μ₀H_t = 1.8 T at 2 K. An antiferromagnetic transition, T_N = 4 K, is observed in GdOF. Paramagnetic behavior is observed above 2 K in PrOF, NdOF, DyOF, HoOF and ErOF. The magnetic susceptibility of EuOF is characteristic of Van Vleck paramagnetism.     

Microstructure,luminescence and thermal stability properties of NaSrPO4:Tb3+ phosphors with various doping concentrations prepared using conventional solid-state sintering

This paper reports the microstructure, luminescence and thermal stability properties of the NaSr_1−xPO₄:xTb³⁺ powders (x = 0.008, 0.01, 0.02, 0.04 and 0.06) via the conventional solid-state sintering at 1200 °C for 5 h. The X-ray diffraction result verifies all diffraction peaks are pure phase of NaSrPO₄. The luminescence results show that the NaSrPO₄:xTb³⁺ powders mainly excited at 370 nm have a series of the emission-states, related to the typical 4f → 4f intra-configuration forbidden transitions of Tb³⁺, and a major emission peak of around 546 nm. The concentration quenching of the NaSr_1−xPO₄:xTb³⁺ phosphors is appeared at x = 0.02. The decay time values of the NaSr_1−xPO₄:xTb³⁺ phosphors for the ⁵D₄ state of the Tb³⁺ are around 3.30 ms to 3.60 ms. It is also found the chromaticity coordinate of NaSrPO₄:Tb³⁺ phosphor varies with the increase of the concentration of Tb³⁺ ions from blue to green. Moreover, the thermal stability of the NaSrPO₄:xTb³⁺ phosphors is slightly better than that of conventional YAG phosphors.     

Structural and electrochemical characterization of layered 0.3Li2MnO3·0.7LiMn0.35−x/3Ni0.5−x/3Co0.15−x/3CrxO2 cathode synthesized by spray drying

Cr doped 0.3Li₂MnO₃·0.7LiMn_0.35−x/3Ni_0.5−x/3Co_0.15−x/3Cr_xO₂ (x = 0, 0.02, 0.04, 0.06) as a cathode material for Li-ion battery has been successfully synthesized by spray drying and subsequent calcination. The effects of Cr dopant on the structural and electrochemical properties of this material have been investigated by XRD, SEM, EDS, charge–discharge measurements, Ac impedance spectroscopy as well as cyclic voltammetry. These results demonstrated that the element Cr distributed uniformly in these materials. With the Cr content increasing, lattice parameters a and c decrease and less Li ion locates in transition metal site. Among the synthesized Cr-doped materials, when x = 0.04, this material shows the best electrochemical properties. Between 2.5 and 4.8 V (vs. Li/Li⁺), the initial discharge capacities of the materials increased from 143 to 168 mA h g⁻¹ at a constant current density of 250 mA g⁻¹. After 50 cycles, the capacity retention of the materials raised from 83% to 93%.     

Synthesis and characterization of a new p-phenylenediammonium dihydrogenmonophosphate [p-NH3C6H4NH3][H2PO4]2

Chemical preparation, crystal structure and NMR spectroscopy of a new organic cation p-phenylenediammonium monophosphate [p-NH₃C₆H₄NH₃][H₂PO₄]₂ are presented. This new compound crystallizes in the orthorhombic system, with the space group Pnma and the following parameters: a = 7.970 (2) Å; b = 22.770 (7) Å; c = 7.000 (7) Å, V = 1270.3 (11) Å³, Z = 4 and D_x = 1.590 g cm⁻³. The crystal structure has been determined and refined to R = 0.043 and R_(w) = 0.057 using 2623 independent reflections. The structural arrangement can be described as inorganic layers of (H₈P₄O₁₆)⁴⁻ units, parallel to (a, c) planes. The organic groups (p-H₃NC₆H₄NH₃)²⁺are anchored between the phosphoric layers to form a three-dimensional infinite network. This compound is also investigated by IR and solid-state ¹H, ¹³C and ³¹P MAS NMR spectroscopies. The ab initio method is used in the calculation of chemical shifts.     

Influence of manganese on magnetic and electronic properties of ZnCr2Se4

The Zn_1?xMn_xCr₂Se₄ crystals were prepared by chemical vapor transport in closed silica tubes using ZnSe and MnSe with CrCl₃ as the transport agent. Four crystals with different Mn content (x = 0.12, 0.13, 0.18 and 0.24) were studied by X-ray photoelectron spectroscopy (XPS) and magnetic measurements in order to determine influence of manganese on their magnetic and electronic properties. The XPS revealed no change of chemical shifts of Cr core lines indicating a Cr³⁺ (3d³) electronic configuration. Magnetization measurements revealed a systematic increase in saturation magnetic moments from 6.32 μ_B/mol for x = 0.12 to 7.63 μ_B/mol for x = 0.24, as well as effective paramagnetic Bohr magneton numbers from 4.87 μ_B/mol for x = 0.12 to 6.91 μ_B/mol for x = 0.24.     

Synthesis and properties of Ce1−xGdxO2−x/2 solid solution prepared by flame spray pyrolysis

Flame spray pyrolysis, which produces ultrafine particles, was applied to the synthesis of Ce_1−xGd_xO_2−x/2 solid solutions by substituting Gd from a mole fraction of 0–0.40. The solubility limit of Gd in the Ce_1−xGd_xO_2−x/2 solid solution produced by flame spray pyrolysis was between 0.25 and 0.30, which is consistent with the reported value. The as-prepared Ce_1−xGd_xO_2−x/2 particles had a square morphology and a nanometer range in the equivalent diameter. The small particle size made it possible to reduce the sintering temperature of the Ce_1−xGd_xO_2−x/2 solid solution from 1650 °C to 1400 °C for the ceria-based solid electrolytes produced by the solid state preparation. The maximum ionic conductivity was achieved when the mole fraction of Gd was 0.25. The mole fraction for the highest ionic conductivity was the same as the particles produced by hydrothermal synthesis. However, the ionic conductivity of the Ce_1−xGd_xO_2−x/2 prepared by the flame spray pyrolysis (1.01 × 10⁻² S/cm at 600 °C) was higher than that prepared by the hydrothermal synthesis (7.53 × 10⁻³ S/cm at 600 °C).     

Hydrothermal synthesis and 121Sb Mössbauer characterization of perovskite-type oxides: Ba2SbLnO6 (Ln = Pr,Nd, Sm,Eu)

A mild hydrothermal process to prepare Ba₂SbLnO₆ (Ln = Pr, Nd, Sm, Eu) perovskite-type oxides are presented. These perovskites were characterized on the basis of X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), inductively-coupled plasma spectra (ICP) techniques. Primary structure was confirmed using Rietveld method based on XRD data shows that the likely space groups of Ba₂SbLnO₆ are R-3 for Ln = Pr and Nd and F_m-3_m for Ln = Sm and Eu, respectively. The measurement of Mössbauer effect of the 37.2 keV γ transition of ¹²¹Sb indicates that the isomer shift of these perovskites falls in the region of the Sb⁵⁺ and reflects some hybridized-orbital behavior in Sb–O bonds.