Itinerant ferromagnetism to insulating spin glass in SrRu1−xCuxO3 (0 ≤ x ≤ 0.3)

The ferromagnetic metallic oxide, SrRuO₃ (T_C ∼ 165 K) undergoes structural, magnetic and metal-insulator transitions upon substitution of Cu at the Ru-site. For x = 0.2 in SrRu_1−xCu_xO₃, the structure becomes a tetragonal with the space group I4/mcm and there is a signature of both ferromagnetic (T_C = 65 K) and antiferromagnetic (T_N = 32 K) ordering due to possible magnetic phase separation. The antiferromagnetism arises due to short range ordering of Cu- and Ru-moments. Jahn-Teller distortion of (Ru,Cu)-O₆ octahedra indicates that the copper ions are in 2+ oxidation state with ⁶t2g³eg electronic configuration. For x ≥ 0.1, narrowing of Ru-4d bandwidth by the substitution of Cu ions results in semiconducting behavior. For x = 0.3, the ac and dc susceptibility measurements indicate a spin glass behavior. The origin of spin glass behavior has been attributed to competing ferromagnetic and antiferromagnetic interactions.     

Synthesis of perovskite-type (La1−xCax)FeO3 (0 ≤ x ≤ 0.2) at low temperature

Gel formation was realized by adding citric acid to a solution of La(NO₃)₃·5H₂O, Ca(NO₃)₂·4H₂O, and Fe(NO₃)₂·9H₂O. Perovskite-type (La_1−xCa_x)FeO₃ (0 ≤ x ≤ 0.2) was synthesized by firing the gel at 500 °C in air for 1 h. The crystallite size (D_1 2 1) decreased with increasing x, while the specific surface area was 6.8-9.4 m²/g and independent of x. The XPS measurement of the (La_1−xCa_x)FeO₃ surface indicated that the Ca²⁺ ion content increased with increasing x, while the Fe ion content was independent of x. Catalytic activity for CO oxidation increased with increasing x.     

Oxide-ion conductivity in CuxCe1−xO2−δ (0 ≤ x ≤ 0.10)

Up to 10 at.% of copper readily substitutes for cerium in ceria. It is found that at oxygen partial pressures between 0.21 atm and 10⁻⁵ atm, Cu_xCe_1−xO_2−δ (0 ≤ x ≤ 0.10) solid solution behave as an oxide-ion electrolyte. Interestingly, Cu_0.10Ce_0.90O_2−δ exhibits the oxide-ion conductivity of ca. 10⁻⁴ Ω⁻¹ cm⁻¹ at 600 °C at an oxygen partial pressure of 10⁻⁵ atm.     

Eu-Mössbauer spectroscopic and X-ray diffraction study on EuyM1−yO2−x (0 ≤ y ≤ 1.0) (M = Th, U)

¹⁵¹Eu-Mössbauer spectroscopic and powder X-ray diffraction (XRD) study has been performed for the Eu_yM_1−yO_2−x (M = Th and U) systems over the entire composition range of 0 ≤ y ≤ 1.0. The XRD results of the Eu-Th system showed that a very wide defect-fluorite (DF) type phase in which oxygen vacancies (V_O) are disordered (x = y/2) is formed for 0 ≤ y < 0.5 and that two-phase regions sandwitching a narrow C-type (C) single phase around y ≈ 0.8 appear for 0.5 < y < 0.8 (DF + C) and 0.82 < y < 1.0 (C + B-type (monoclinic) Eu₂O₃). The Mössbauer results show that the isomer shifts (ISs) of Eu³⁺ in this system smoothly increase with Eu composition, y. The decrease of average coordination number (CN) of O²⁻ around Eu³⁺ with increasing y (CN = 8 − 2y) (x = y/2) results in the decrease of the average EuO bond length, which is due to the decrease of repulsion force between O²⁻ anions. This result confirms that the IS of Eu³⁺ correlates well with the average EuO bond length in oxide systems. For the Eu-U system, the lattice parameter, a₀, of the system decreases almost linearly with y, in accordance with the calculated a₀ versus y curve for the oxygen-stoichiometric (i.e. x = 0) fluorite-type dioxide (CN = 8). The ISs of Eu³⁺ in this composition range remain almost constant around 0.5 mm/s, which is comparable to those of pyrochlore oxides (Eu₂Zr₂O₇ and Eu₂Hf₂O₇ (y = 0.5)) with O²⁻-eight-fold coordinated Eu³⁺(CN = 8).     

Influence of SnO2 addition on the thermoelectric properties of Zn1 − xSnxO (0.01 ≤ x ≤ 0.05)

The grain size and the density of the Zn_1 − xSn_xO (0 ≤ x ≤ 0.05) samples decreased with increasing SnO₂ content. The addition of a small amount of SnO₂ (x ≤ 0.01) to ZnO led to an increase in both the electrical conductivity and the absolute value of the Seebeck coefficient, resulting in a significant increase in the power factor. The thermoelectric power factor was maximized to a value of 1.25 × 10⁻³ Wm⁻¹ K⁻² at 1073 K for the Zn_0.99Sn_0.01O sample.     

Synthesis of spherical nanostructured LiMxMn2−xO4 (M = Ni, Co, and Ti; 0 ≤ x ≤ 0.2) via a single-step ultrasonic spray pyrolysis method and their high rate charge-discharge performances

LiM_xMn_2−xO₄ (M = Ni²⁺, Co³⁺, and Ti⁴⁺; 0 ≤ x ≤ 0.2) spinels were prepared via a single-step ultrasonic spray pyrolysis method. Comparative studies on powder properties and high rate charge-discharge electrochemical performances (from 1 to 15 C) were performed. XRD identified that pure spinel phase was obtained and M was successfully substituted for Mn in spinel lattice. SEM and TEM studies confirmed that powders had a feature of ‘spherical nanostructural’, that is, powders consisted of spherical secondary particles with the size of about 1 μm, which were developed from close-packed primary particles with several tens of nanometers. Substitutions enhanced density of second particles to different extents, depending on M and its content. Charge-discharge tests showed that as-prepared LiMn₂O₄ could deliver excellent rate performance (around 100 mAh/g at 10 C). Ni substitution contributed to improving electrochemical performances. In the voltage range of 4.95-3.5 V, the materials showed much better electrochemical performances than LiMn₂O₄ in terms of capacity, cycleability and rate capability.     

Synthesis, structural and magnetic studies of the CuCr1−xRhxO2 delafossite solid solution with 0 ≤ x ≤ 0.2

The CuCr_1−xRh_xO₂ series is investigated by X-ray diffraction, magnetization measurements and Raman spectroscopy on ceramic samples. It is found that a delafossite solid solution is maintained up to x = 0.2 in CuCr_1−xRh_xO₂. The small observed variation in cell parameters is consistent with the small difference between the ionic radii of Cr³⁺ and Rh³⁺. A significant broadening of X-ray reflections is observed and when analyzed using the Williamson-Hall relationship showed that the strain generated by Rh substitution is strongly anisotropic, affecting mainly (Cr,Rh)-O bonds in the ab plane. Room temperature Raman spectra displayed three main Raman active modes. All modes shift to lower frequency and undergo significant changes in intensity with increasing Rh content, showing the effect of Rh atoms on the M³⁺-O bond strength. The magnetic behavior of CuCr_1−xRh_xO₂ samples was investigated as a function of temperature and applied field. At high temperature paramagnetic behavior, and at low temperature, evidence for weak ferromagnetism, reinforced by a hysteresis loop at 4 K is observed. The magnetic behavior of CuCr_1−xRh_xO₂ is attributed to the disorder of Cr and Rh in octahedral sites resulting in short-range Cr-O-Cr and Cr-O-Rh interactions, which give rise to short-range weak ferromagnetism.     

Crystal structure and electrical properties of new tungsten bronzes: BxWO3 (0.01 ≤ x ≤ 0.08)

Boron tungsten bronzes B_xWO₃ (0.01 ≤ x ≤ 0.08) were synthesized by hybrid microwave method from mixtures of WO₃ and amorphous boron powder. With the increase of boron content, the crystal structure of B_xWO₃ transforms from orthorhombic (x = 0.01) to tetragonal α (x = 0.048) and then to tetragonal β (0.07 ≤ x ≤ 0.08). The average size of crystallites is in the range of 1-10 μm. All samples show semiconducting behaviour in their temperature dependence of resistivity. The conduction behaviour above 80 K for samples with x = 0.01 and 0.08 can be explained using the variable-range hopping and thermally activated mechanism, respectively. Comparative experiments showed that boron bronze phases cannot be obtained by the microwave heating of pure WO₃ powder or a mixture of B₂O₃ and WO₃ under the same conditions.     

Electron paramagnetic resonance (EPR) of antiferromagnetic nanoparticles of La1−xSrxCrO3 (0.000 ≤ x ≤ 0.020) synthesized by combustion reaction

Nanocrystalline particles of La_1−xSr_xCrO₃ (0.000 ≤ x ≤ 0.020) compounds were synthesized in order to investigate the antiferromagnetic (AFM) to paramagnetic (PM) phase transition temperature, g-factor, line width and intensity by electron paramagnetic resonance (EPR). All samples were synthesized by combustion reaction method using strontium nitrate, lanthanum nitrate, chromium nitrate and urea as fuel without subsequent heat treatment. X-ray diffraction patterns of all systems showed broad peaks consistent with orthorhombic structure of LaCrO₃. The absence of extra reflections in the diffraction patterns of as-prepared materials ensures the phase purity. The average crystallite sizes determined from the prominent (1 1 2) peak of the diffraction using Scherrer's equation was independent of the addition of Sr²⁺ ions; being ca. 31–29 nm for x = 0.000 and 0.020, respectively. The EPR line width and intensity were found to be dependent on Sr²⁺ addition and temperature. However, the AFM–PM transition temperature was found to be independent of strontium concentration, being ca. 296 K. In the PM phase, g-factor was nearly temperature independent with increasing of x. The EPR results indicated that the addition of Sr²⁺ ions may induce creation of Cr³⁺–Cr⁴⁺ clusters.     

Synthesis and luminescence properties of color-tunable Ba1−ySryLa4−xTbx(WO4)7 (x = 0.02-1.2, y = 0-0.4) phosphors

Ba_1−ySr_yLa_4−xTb_x(WO₄)₇ (x = 0.02-1.2, y = 0-0.4) phosphors were prepared via a solid-state reaction and their photoluminescence properties were investigated. An analysis of the decay behavior indicates that the energy migration between Tb³⁺ ions is conspicuous in the ⁵D₃ → ⁷F₄ transition due to the cross-relaxation in BaLa₄(WO₄)₇. A partial substitution of Ba²⁺ by Sr²⁺ can not only enhance the emission intensity but also increase the solid solubility of Tb³⁺ in Ba_1−ySr_yLa_4−xTb_x(WO₄)₇. The emission intensity of the ⁵D₄ → ⁷F_J (J = 4, 5, 6) transitions can be enhanced by increasing Sr²⁺ and Tb³⁺ concentrations, with the optimal conditions being x = 1.2, y = 0.4 (Ba_0.6Sr_0.4La_2.8Tb_1.2(WO₄)₇). Under near-UV excitation at 379 nm, the CIE color coordinates of Ba_1−ySr_yLa_4−xTb_x(WO₄)₇ vary from blue (0.212, 0.181) at x = 0.04, y = 0, to green (0.245, 0.607) at x = 1.2, y = 0.4.     

Sintering behavior, microstructure and microwave dielectric properties of Li2+xTiO3 (0 ≤ x ≤ 0.2)

Sintering behavior, microstructure and microwave dielectric properties of Li_2+xTiO₃ (0 ≤ x ≤ 0.2) ceramics have been studied by X-ray diffraction (XRD), scan electron microscopy (SEM), Raman spectra, dilatometery and microwave resonant measurement in this research. Homogeneous non-stoichiometric composition with rock salt structure existed for Li_2+xTiO₃ (0 ≤ x ≤ 0.2) ceramics. The sintering temperature was successfully reduced and highly densified sample could be obtained with appropriate excessive amount of lithium (x = 0.08). A transient reactive liquid phase sintering mechanism was proposed. The preferred orientation of grain growth and micro-cracks existed in the Li₂TiO₃ (x = 0) sample disappeared in the lithium excessive samples with x ≥ 0.08. The microwave dielectric properties varied significantly with the excessive amount of lithium. Optimized microwave dielectric properties were obtained for the x = 0.08 composition: ?_r = 24.6, Q × f = 66,000 GHz, and τ_f = 22.1 ppm/°C.     

Oxygen vacancy ordering in strontium doped rare earth cobaltate perovskites Ln1−xSrxCoO3−δ (Ln = La, Pr and Nd; x > 0.60)

A family of Sr-doped perovskite compounds Ln_1−xSr_xCoO_3−δ (Ln = La³⁺, Pr³⁺ and Nd³⁺; x > 0.60), were prepared by sol-gel chemistry and reaction at 1100 °C under 1 atm of oxygen. This structural family has been shown to be present only for rare earth ions larger than Sm³⁺ and an upper limit of Sr²⁺ solubility in these phases was found to exist between x = 0.90 and 0.95. X-ray diffraction shows oxygen-deficient, simple cubic (Pm-3m) perovskite crystal structures. The combination of electron and powder neutron diffraction reveals that oxygen vacancy ordering occurs, leading to a tetragonal (P4/mmm) superstructure and a doubling of the basic perovskite unit along the crystallographic c-axis. No additional Ln³⁺/Sr²⁺ cation ordering was observed.     

Synthesis and electrical properties of ordered perovskite oxide Cd3−x−yCuxAyTeO6 (A = Li, Na; 0.00 ≤ x, y ≤ 0.15)

Polycrystalline Cd_3−x−yCu_xA_yTeO₆ (A = Li, Na) samples were prepared by solid-state reaction, and their crystal structure and electrical properties were investigated. In Cd_3−xCu_xTeO₆ and Cd_3−yA_yTeO₆ (A = Li, Na), the maxim solubility of x and y was 0.15 and 0.15 for A = Li, 0.05 for A = Na, respectively. For co-substituted samples Cd_2.9−yCu_0.1Li_yTeO₆ and Cd_2.9−yCu_0.1Na_yTeO₆, the maxim solubility of x was the same as single substitution above-mentioned. The alkali-metal substituted samples Cd_3−yA_yTeO₆ (A = Li, Na) showed a negative Seebeck coefficient, which indicates that the major conduction carriers are electron. On the other hand, the co-substituted samples Cd_2.9−yCu_0.1A_yTeO₆ (A = Li, Na) represented a positive Seebeck coefficient, and major conduction carriers were hole through substitution by copper ions.     

Thermal stability and transport studies of (100 − 2x)TeO2-xAg2O-xWO3 (7.5 ≤ x ≤ 30) glass system

Differential scanning calorimetry (DSC), infrared (IR) and direct current (DC) conductivity studies have been carried out on (100 − 2x)TeO₂-xAg₂O-xWO₃ (7.5 ≤ x ≤ 30) glass system. The IR studies show that the structure of glass network consists of [TeO₄], [TeO₃]/[TeO₃₊₁], [WO₄] units. Thermal properties such as the glass transition (T_g), onset crystallization (T_o), thermal stability (ΔT), glass transition width (ΔT_g), heat capacities in the glassy and liquid state (C_pg and C_pl), heat capacity change (ΔC_p) and ratios C_pl/C_pg of the glass systems were calculated. The highest thermal stability (237 °C) obtained in 55TeO₂-22.5Ag₂O-22.5WO₃ glass suggests that this new glass may be a potentially useful candidate material host for rare earth doped optical fibers. The DC conductivity of glasses was measured in temperature region 27-260 °C, the activation energy (E_act) values varied from 1.393 to 0.272 eV and for the temperature interval 170-260 °C, the values of conductivity (σ) of glasses varied from 8.79 × 10⁻⁹ to 1.47 × 10⁻⁶ S cm⁻¹.     

Synthesis of (1 − x)Ca2/5Sm2/5TiO3-xLi1/2Nd1/2TiO3 ceramic powder via ethylenediaminetetraacetic acid precursor

(1 − x)Ca_2/5Sm_2/5TiO₃-xLi_1/2Nd_1/2TiO₃ (CSLNT) ceramic powder was prepared by a liquid mixing method using ethylenediaminetetraacetic acid (EDTA) as the chelating agent. TG, DTA, XRD and TEM characterized the precursors and derived oxide powders. When x = 0.3, perovskite CSLNT was synthesized at 1000 °C for 3 h in air. The CSLNT (x = 0.3) ceramics sintered at 1200 °C for 3 h show excellent microwave dielectric properties of ?_r = 99, Q_f = 6200 GHz and τ_f = 9 × 10⁻⁶ °C⁻¹.     

Synthesis, low-temperature sintering and the dielectric properties of the ZnO-(1 − x)TiO2-xSnO2 (x = 0.04-0.2)

ZnO-(1 − x)TiO₂-xSnO₂ (x = 0.04-0.2) ceramics were prepared by conventional mixed-oxide method combined with a chemical processing. Fine particle powders were prepared by chemical processing to activate the formation of compound and to improve the sinterability. One wt.% of V₂O₅ and B₂O₃ with the mole ratios of 3:1 were used to lower the sintering temperature of ceramics. The effect of Sn content on phase structure and dielectric properties were investigated. The results show that the substituting Sn for Ti accelerates the hexagonal phase transition to cubic phase, and an inverse spinel structure Zn₂(Ti_1−xSn_x)O₄ solid solution forms. The best dielectric properties obtained at x = 0.12. The ZnO-0.88TiO₂-0.12SnO₂ ceramics sintered at 900 °C exhibit a good dielectric property: ?_r = 29 and tan δ = 9.86 × 10⁻⁵. Due to their good dielectric properties, low firing characteristics, ZnO-(1 − x)TiO₂-xSnO₂ (x = 0.04-0.2) can serve as the promising microwave dielectric capacitor.     

Structural and optical properties of polycrystalline CdSexTe1−x (0 ≤ x ≤ 0.4) thin films

CdSe_xTe_1−x (0 ≤ x ≤ 0.4) ternary thin films have been deposited on quartz substrates at room temperature by a single source thermal evaporation. X-ray diffraction patterns and transmission electron microscope micrographs of these films showed that the films were of polycrystalline texture over the whole range studied and exhibit predominant cubic (zinc blende) structure with strong preferential orientation of the crystallites along (1 1 1) direction. Linear variation of the lattice constant with mole fraction x is observed obeying Vegard's law. The dependence of the optical constants, the refractive index n and extinction coefficient k, of the films on the mole fraction x was studied in the spectral range of 400-2500 nm. The normal dispersion of the refractive index of the films could be described using the Wemple-DiDomenco single-oscillator model. CdSe_xTe_1−x thin films of different composition have two direct and indirect transitions corresponding to energy gaps and . The variation in either or with x indicates that this system belongs to the amalgamation type. The variation follows a subquadratic dependence and the bowing parameters were found to be 0.36 and 0.48 eV for the direct, and indirect energy gaps, respectively. Direct linear variation of the ratio N/m^* with x is observed.     

Pechini sol-gel deposition and luminescent properties of SrLa1−xRExGa3O7 (RE = Eu, Tb) phosphor films

SrLa_1−xRE_xGa₃O₇ (RE = Eu³⁺, Tb³⁺) phosphor films were deposited on quartz glass substrates by a simple Pechini sol-gel method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy, field-emission scanning electron microscopy, photoluminescence spectra, and lifetimes were used to characterize the resulting films. The results of XRD indicated that the films began to crystallize at 700 °C and crystallized fully at 900 °C. The results of FT-IR spectra were in agreement with those of XRD. Uniform and crack-free films annealed at 900 °C were obtained with average grain size of 80 nm, root mean square roughness of 46 nm and thickness of 130 nm. The RE ions showed their characteristic emission in crystalline SrLa_1−xRE_xGa₃O₇ films, i.e., Eu³⁺⁵D₀-⁷F_J (J = 0, 1, 2, 3, 4), Tb³⁺⁵D₄-⁷F_J (J = 6, 5, 4, 3) emissions, respectively. The optimum concentrations (x) of Eu³⁺ and Tb³⁺ were determined to be 50, and 80 mol% in SrLa_1−xRE_xGa₃O₇ films, respectively.     

Influence of mixed alkali on the spectral properties of vanadyl ions doped xNa2O-(30 − x)K2O-60B2O3 glasses—an EPR and optical study

Electron paramagnetic resonance (EPR) and optical investigations have been performed in the mixed alkali borate xNa₂O-(30 − x)K₂O-60B₂O₃ (5 ≤ x ≤ 25) glasses doped with 10 mol% of vanadyl ions in order to look for the effect of ‘mixed alkalis’ on the spectral properties of the glasses. The observed EPR spectra have structures for x > 5 mol% which are characteristic of a hyperfine interaction arising from an unpaired electron with the ⁵¹V nucleus and it builds up in intensity as x increases. It is observed that the mixed alkali play a significant role in accommodating the vanadyl ions in these mixed alkali glasses and for x > 5 mol%, shows a well resolved hyperfine structure typical for isolated VO²⁺ ions. The spin-Hamiltonian parameters (g and A), the dipolar hyperfine coupling parameter (P) and Fermi contact interaction parameter (k) have been evaluated. It is observed that the spin-Hamiltonian parameters do not vary much with the change in composition. It is observed that with increase of x, an increase occurs in tetragonal distortion for VO²⁺. The number of spins (N) participating in resonance and the paramagnetic susceptibility (χ) have been calculated. It is observed that N and χ increase with x. The optical bandgap energies evaluated for these glasses slightly increase with x and reach a maximum around x = 20 and thereafter decrease showing the mixed alkali effect. Optical band gap energies obtained in the present work vary from 2.73 to 3.10 eV for both the direct and indirect transitions. The physical parameters of the glasses are also determined with respect to the composition.     

Synthesis, structural and magnetic properties of La1−xCdxFeO3 (0.0 ≤ x ≤ 0.3) orthoferrites

Nanocrystalline La_1−xCd_xFeO₃ (0.0 ≤ x ≤ 0.3) solid solutions have been synthesized by a single-step solution combustion method at a relatively low temperature of 400 °C. The combustion-synthesized solid solutions were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and magnetic measurements. The crystal structure examined by XRD indicates that the samples were single-phase, and crystallize in an orthorhombic (space group, Pbnm no. 62) structure. The parent and doped compounds showed canted antiferromagnetic behavior associated with an increase in magnetic moment with Cd doping. The changes in magnetic properties of the materials are correlated to the changes in structural features resulting from the Rietveld structural refinement of the materials.