Electron Paramagnetic Resonance,Optical Spectra and DC Conductivity Studies of Vanadyl Doped Bi2O3 · BaO · B2O3 Glasses

Glasses with composition xBi₂O₃ ·(0.30 - x)BaO · 0.70B₂O₃ have been prepared in the range (0.00 ≤ x ≤ 0.15) containing 2.0 mol% of V₂O₅. Electron paramagnetic resonance (EPR), optical transmission and absorption spectra and DC conductivity of these glasses have been studied. The spin Hamiltonian parameters (SHP) of VO²⁺ ions, dipolar hyperfine coupling parameter P, Fermi contact interaction parameter K, and molecular orbital coefficients (α² and γ²) have been calculated. The SHP arc related with the theoretical optical basicity. A_th. The position of the absorption edge and the values of the optical band gap have also been reported. The effect of addition of Bi₂O₃ on the DC conductivity has also been studied.     

Effect of Fe3+-doped Ca12Al14O33 cement on optical and thermal properties

This study aims to investigate the effect Fe ions doped into Ca₁₂Al₁₄O₃₃ (C12A7, 12CaO-7Al₂O₃) cement compound on its thermal and optical properties. Polycrystalline samples of Ca₁₂Al_14?xFe_xO₃₃ (where x?=?0.0, 0.5, and 1.0) were prepared via a solid state reaction in an oxygen atmosphere. The lattice constant of Ca₁₂Al₁₄O₃₃ determined using an XRD technique was in excellent agreement with first-principles calculations. With increasing Fe concentrations, the lattice constants were found to have increased. Additionally, the optical gaps of Ca₁₂Al_14?xFe_xO₃₃, (x?=?0, 0.25, 0.5, and 1.0) were 3.9?eV, 3.77?eV, 3.75?eV and 3.63?eV, respectively. It was clearly seen that the optical gap decreased with increasing Fe concentrations. As revealing by first-principles calculations, the optical gap was directly related to the electronic transition from the occupied electronic state of extra-framework O^2? ions (as free O^2? ions inside nano-cage) to the conduction band. Moreover, we also found that the thermal conductivity Ca₁₂Al_14?xFe_xO₃₃ was reduced when the larger atomic mass and atomic radii Fe was substituted into Al sites. Hence, this indicated that Fe³⁺-substitution into Al³⁺ sites of Ca₁₂Al₁₄O₃₃ cement directly affected both its optical gap and thermal conductivity.     

The study of thermal expansion properties in solid solutions Ln2−xCrxMo3O12 (Ln=Ho and Lu) by high temperature X-ray diffraction

A systematic study of the formation, crystal structures and thermal expansion properties of solid solutions Ln_2?xCr_xMo₃O₁₂ (Ln=Ho and Lu) has been performed. Rietveld refinement results indicate that compounds Ho_2?xCr_xMo₃O₁₂ with 0≤x≤0.2 and Lu_2?xCr_xMo₃O₁₂ with 0≤x≤0.5 have orthorhombic structures and show negative thermal expansion in the temperature range of 200–800 °C. Compounds Ln_2?xCr_xMo₃O₁₂ with 1.7≤x≤2.0 have monoclinic structures and show strong positive thermal expansion in the temperature range of 25–300 °C. While compounds Ln_2?xCr_xMo₃O₁₂ with 1.7≤x≤2.0 adopt orthorhombic structures and show very low positive thermal expansion from 500 to 800 °C. Though the crystal structure plays the key rule in determining the thermal expansion properties, chemical composition and temperature also show important effect on the thermal expansion properties of these compounds.     

Phase stratification in the Nd1 − x BaxCoO3 − δ (0.3 ≤ x ≤ 0.54) system

Slowly cooled Nd_{1 ? x} Ba_xCoO_{3 ? δ} samples were two-phase in the concentration interval 0.3 ≤ x ≤ 0.46. One of the phases had O-orthorhombic lattice distortions (Pbnm) characteristic of ferromagnetic samples with x ≤ 0.3, and the other phase had tetragonal distortions (P4/mmm) characteristic of samples with x ≥ 0.46. Tetragonal distortions were caused by ordering of Nd³⁺ and Ba²⁺ ions. Samples with ordered neodymium and barium ions (Nd_{1 ? y} Ba_{1 + y} Co₂O_{6 ? γ} at ?0.08 ≤ y ≤ 0.08) experienced metal-dielectric and orientation magnetic phase transitions.     

Influence of calcium substitution on the phase transition and ionic conductivity in BICAVOX oxide ion conductor

Samples of Bi₄Ca _x V_{2? x} O_{11?(3 x /2)?δ} in the composition range 0.07 ≤ x ≤ 0.30 were prepared by conventional solid state reactions. The stability of different phases as a function of composition was analysed by X-ray powder diffraction, FT-IR spectra, differential thermal analysis and AC impedance spectroscopy. For the compositions x ≤ 0.10, monoclinic α-phase structure is retained at room temperature. For x = 0.13, orthorhombic β-phase is observed, whereas for x ≥ 0.17, high O^2?conducting tetragonal γ-phase is stabilised. However, the highest ionic conductivity σ_300°C = 3.27 × 10^?4 S cm^?1 was observed for x = 0.17. This higher value of conductivity of the substituted compound as compared to the parent compound can be attributed to the increased oxygen ion vacancies generated as a result of cation doping. AC impedance spectroscopy reveals the fact that this ionic conductivity is mainly due to the grain contribution.     

57Fe Mössbauer spectroscopy studies of Sr2Fe1−x Cr x Mo1−x W x O6 double perovskite compounds

Polycrystalline double perovskites Sr₂Fe_1?x Cr _x Mo_1?x W _x O₆ with x = 0, 0.05, 0.10, 0.15, 0.20, and 0.30 have been prepared by sold state reactions. A continuous decrease of the tetragonal unit cell parameters α and c with increasing x values is observed. The highest Curie temperature T _C = 426 K is recorded for the x = 0.10 compound. ⁵⁷Fe Mössbauer spectroscopy measurements indicate a non-integral electronic configuration of ～3d^5.3 for the Fe ions at the ordered double perovskite structure for x ≤ 0.20, which reaches ～3d^5.4 for x = 0.30. Fe–Mo/W anti-site and anti-phase boundary defects are observed in all samples in equal concentrations of around 3% of the total number of Fe ions in their structure.     

Spin state and magnetic interaction of cobalt ions in niobium-doped cobaltites

The magnetic properties and electrical conductivity of La_1?x Sr_xCo_1?x/2Nb _x/2O₃ solid solutions with trivalent cobalt ions are studied. These solid solutions are found to be spin glasses with T _f ～ 25 K. The ferromagnetic component is most pronounced in the composition with x = 0.15. The electrical conductivity decreases with increasing strontium content. The results obtained are interpreted within a model according to which cobalt ions located in the vicinity of strontium ions reside in an intermediate-spin state and the Co³⁺-O-Co³⁺ super-exchange interaction is ferromagnetic because of the local dynamic orbital correlations.     

Emission characteristics of Dy3+ ions in lead antimony borate glasses

Glasses with the composition 30PbO–25Sb₂O₃–(45?x)B₂O₃–xDy₂O₃ for x=0 to 1 were prepared in steps of 0.2 by the melt-quenching method. Various physical parameters, viz., density, molar volume, and oxygen packing density, were evaluated. Optical absorption and luminescence spectra of all the glasses were recorded at room temperature. From the observed absorption edges optical band gap, the Urbach energies are calculated; the optical band gap is found to decrease with the concentration of Dy₂O₃. The Judd–Ofelt theory was applied to characterize the absorption and luminescence spectra of Dy³⁺ ions in these glasses. Following the luminescence spectra, various radiative properties, like transition probability A, branching ratio β and the radiative life time τ for different emission levels of Dy³⁺ ions, have been evaluated. The radiative lifetime for the ⁴F_9/2 multiplet has also been evaluated from the recorded life time decay curves, and the quantum efficiencies were estimated for all the glasses. The quantum efficiency is found to increase with the concentration of Dy₂O₃.     

Optical and electrical properties of flash-evaporated Pb1−xHgxSe films

Results of optical and electrical properties of flash-evaporated Pb_1−xHg_xSe films, in the composition range 0.07 ⩽ x ⩽ 0.93, show that the alloy films are formed by alloying of PbSe and HgSe. The optical band gaps of films grown on substrates at 25 and 100°C decrease linearly from 0.20 to 0.09 eV and from 0.15 to 0.065 eV, respectively, as the Hg concentration in the films is increased from 0.07 to 0.93. Activation energy values, as obtained from conductivity measurements, suggest that between 225 and 400 K the conduction results mainly from thermally-generated charge carriers, whereas at the lower temperatures (<225 K) impurity conduction dominates. Irreversible changes in the properties of the films are observed at > 400 K.     

Mössbauer and optical investigation of Co3−x Fe x O4 thin films grown by sol–gel process

Structural transformation and the related variation in magnetic and optical properties of Co_3?x Fe _x O₄ thin films grown by a sol–gel method have been investigated as the Fe composition varies up to x?=?2. The normal spinel phase is dominant below x?=?0.55 and the inverse spinel phase grows as x increases further. Conversion electron Mössbauer spectroscopy (CEMS) measurements indicate that the normal spinel phase have octahedral Fe³⁺ ions mostly while the inverse spinel phase contain octahedral Fe²⁺ and tetrahedral Fe³⁺ ions. For higher Fe composition (x?>?1.22), Co²⁺ ions are found to substitute the octahedral Fe²⁺ sites. The measured optical absorption spectra for the Co_3?x Fe _x O₄ films by spectroscopic ellipsometry support the CEMS interpretation.     

Magnetic and optical properties of spinel FexCo3−xO4 thin films

Magnetic and optical properties of Fe_xCo_3−xO₄ thin films grown by sol–gel method have been investigated as the Fe composition (x  ) increases from 0 to 2. X-ray diffraction measurements revealed that the normal- and inverse-spinel phases coexist for 0.76?x?0.93$0.76?x?0.93$. The normal-spinel phase is dominant below x=0.76$x=0.76$ while the inverse-spinel phase above x=0.93$x=0.93$. The lattice constant of the inverse-spinel phase is found to be larger than that of the normal-spinel phase. For both phases the lattice constant increases with increasing x. The Fe_xCo_3−xO₄ films containing the inverse-spinel phase exhibit net magnetization that increases with increasing x  . Conversion electron Mössbauer spectrum measured on the x=0.93$x=0.93$ sample showed that Fe²⁺ ions prefer the octahedral sites, indicating the formation of the inverse-spinel phase. Analysis on the measured optical absorption spectra for the samples by spectroscopic ellipsometry indicates a dominance of the normal-spinel phase for low x in which Fe³⁺ ions mostly occupy the octahedral sites. Observation of a crystal-field transition at 1.6 eV originating from tetrahedral Fe³⁺ ion confirms the existence of the inverse-spinel phase for high x.     

Mn<Superscript>2+</Superscript> 3<Emphasis Type="Italic">d</Emphasis> luminescence kinetics in Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>x</Subscript>Se

Intracenter luminescence (IL) of Mn²⁺ in Zn_1?xMn_xSe (x=0.07, 0.02) was studied under pulsed excitation by the neodymium laser second harmonic. At 4 K, the IL saturation originates from the nonlinearity of the system only at the instant of excitation, the IL decay kinetics after the exciting pulse termination depending only weakly on the pumping level. At 77 K, the decay kinetics in Zn_0.93Mn_0.07Se depends substantially on the pumping level, because the migration of intracenter excitation over the manganese ions initiates up-conversion, which is a slow nonlinear process. As shown by IL decay measurements in Zn_0.98Mn_0.02Se (x=0.02), excitation migration over the Mn²⁺ ions is insignificant even at a high temperature and under strong optical pumping.     

Crystalline and magnetic structures of La1−x BixMnO3+δ manganites

The crystalline and magnetic structures and magnetic properties of La_1?x Bi_xMnO_3+δ (0.4 ≤ x ≤ 0.6, 0 ≤ δ ≤ 0.06) manganites have been studied. The solid solutions having the stoichiometric oxygen content are shown to be orbitally ordered A-type antiferromagnets. An increase in the oxygen content above the stoichiometric value is found to cause Mn⁴⁺ ions in the perovskite lattice, to remove the cooperative Jahn-Teller distortions, and to form a long-range ferromagnetic order. This order becomes broken as the concentration of the tetravalent manganese ions increases further. The tendency toward breaking the ferromagnetic order increases with the bismuth content. The magnetic properties are interpreted in terms of superexchange interactions on the assumption of local lattice distortions induced by anisotropy of the 6s ²(Bi³⁺)-2p ⁶(O^2?) chemical bonds.     

Investigation of gain characteristics in mixed crystals LiMeF4 (Me = Y,Lu, Yb) doped by Ce3+ ions

Differential gain spectra in the range 295–335 nm were measured in crystals of scheelite structure LiY_{1 ? x} Lu _x F₄ (x = 0–1), doped by Ce³⁺ ions. It is shown that variation of Lu³⁺ and Y³⁺ ions relative content in LiY_{1 ? x} Lu _x F₄ crystals allows to manipulate the spectral width of the amplification band. Cross-sections of excited-state absorption at the wavelengths of Ce³⁺ luminescence, probability ratios of formation and thermal destruction of color centers depending on the Y³⁺ ions content in LiY_{1 ? x} Lu _x F₄ crystals were estimated. Even better gain characteristics have been demonstrated by LiLuF₄:Ce³⁺, doped by Yb³⁺ ions. The highest optical gain coefficient with a wide amplification band among studied samples was observed in LiLuF₄:Ce³⁺ crystal, codoped by Yb³⁺ ions.     

Non-adiabatic polaron hopping conduction in CaMn1−xCrxO3 (0?x?0.3)

DC electrical conductivity (σ_dc) of electron-doped antiferromagnetic CaMn_1−xCr_xO₃ (0?x?0.3) has been discussed elaborately in the light of polaron hopping conduction. The increase in Cr doping concentration increases the conductivity and decreases the activation energy. Non-adiabatic polaron hopping conduction is observed in all the manganites at high temperatures. The analysis of σ_dc data shows that small polarons are formed at lower concentrations (?5%) of Cr doping and undoped samples. However, large polarons are materialized at higher doping (?10%) concentrations. This is consistent with the fact that doped Cr³⁺ has larger ionic size compared to that of Mn⁴⁺. Again, strong electron-phonon (e-ph) interaction is perceived in undoped and 5% Cr-doped samples but not in manganites with larger doping concentration. This also confirms the formation of larger polarons with the increase of x. Mott's variable range hopping (VRH) model can elucidate the dc conductivity at very low temperatures. It has been detected that single phonon-assisted hopping is responsible for the dc conduction in the Cr-doped CaMnO₃ manganites.     

Structural and optical properties of lithium borobismuthate glasses

Glasses with compositions 25Li₂O-(75−x)Bi₂O₃-x B₂O₃, with 0?x?30 mol%, have been prepared using the melt quenching technique. The density and the molar volume have been determined. IR spectroscopy is used as a structural probe of the nearest neighbor environment in the glass network. The optical transmittance and reflectance spectrum of the glasses have been recorded in the wavelength range 400-1100 nm. The values of the optical band gap E_g^opt for indirect transition and refractive index have been determined for 0?x?30 mol%. The average electronic polarizability of the oxide ion α_o²⁻ and the optical basicity have been estimated from the calculated values of the refractive indices. Variations in the different physical parameters such as the density, molar volume, optical band gap, refractive index, average electronic polarizability of the oxide ion and optical basicity with B₂O₃ content have been analyzed and discussed in terms of the changes in the glass structure.     

Order–disorder transition and thermal conductivity of (Yb x Nd1− x )2Zr2O7 solid solutions

X-ray diffraction, transmission electron microscopy and a laser-flash method were used to investigate the order–disorder transition and thermal conductivity of (Yb _x Nd_{1? x} )₂Zr₂O₇ (0 ≤ x ≤ 1.00) solid solutions. The structures were found to be pyrochlore-type for 0 ≤ x ≤ 0.25, defect fluorite for 0.45 ≤ x ≤ 1.00 and a mixture of these at 0.30 ≤ x ≤ 0.40. The thermal conductivities of (Yb _x Nd_{1? x} )₂Zr₂O₇ first gradually decrease with increasing temperature, and then increase slightly above 800°C due to the increased radiation contribution. YbNdZr₂O₇ has the lowest thermal conductivity due to the reduced cation mean free path at the compositional combination of equal molar Yb³⁺ and Nd³⁺ cations.     

Dielectric properties of the Li0.07Na0.93Ta0.1Nb0.9O3 and Li0.07Na0.93Ta0.111Nb0.889O3 solid solutions

Dielectric properties of perovskite ferroelectric solid solutions Li_0.07Na_0.93Ta_0.1Nb_0.9O₃ and Li_0.07Na_0.93Ta_0.111Nb_0.889O₃ are studied over the 290?C700 K range of temperature within the frequency range of 25?C10⁶ Hz. A decrease of the Curie temperature (??75 K) compared with Li_0.07Na_0.93Ta_0.1Nb_0.9O₃ synthesized from mechanical mixture of pentoxides Ta₂O₅ and Nb₂O₅ is observed in Li_0.07Na_0.93Ta_0.111Nb_0.889O₃ synthesized from co-precipitated pentoxide Ta_2y Nb_{2(1 ? y)}O₅.     

119Sn and 57Fe M?ssbauer study of the local structure of perovskite-type ferrites CaFe2 ? x N x O5 ( N = Sc, Al) and manganite CaMn7O12

Anion-deficient substituted ferrites Ca₂Fe_{2 − x} N _x O₅ (N = Sc³⁺, Al³⁺) and mixed manganite CaMn₇O₁₂ have been investigated by ¹¹⁹Sn and ⁵⁷Fe probe M?ssbauer spectroscopy. The mechanism of charge compensation for heterovalent impurity Sn⁴⁺ ions in the structure of the ferrite Ca₂Fe₂O₅ has been established. The presence of nonequivalent crystallographic positions of manganese cations, caused by their charge ordering in the structure of the manganite CaMn₇O₁₂, is shown. Magnetic ordering of Mn³⁺ and Mn⁴⁺ cations in the octahedral sublattice of CaMn₇O₁₂ at T < T _M2 ≈ 90 K is established. Original Russian Text ? A.V. Sobolev, I.A. Presnyakov, K.V. Pokholok, V.S. Rusakov, T.V. Gubaidulina, A.V. Baranov, G. Demazeau, 2007, published in Izvestiya Rossiiskoi Akademii Nauk Seriya Fizicheskaya, 2007, Vol. 71, No. 9, pp. 1347–1354.     

Luminescence and vibration spectra of zinc manganese diphosphates

The synthesis conditions for new luminescent materials, zinc manganese diphosphates Zn_{2? x}Mn_xP₂O₇ · 5H₂O) (0 ≤ x ≤ 2.0), are considered. The photoluminescence and its excitation spectra, IR absorption, and Raman spectra of these materials are studied. The red luminescence band with a peak at about 700 nm is shown to be due to the radiative transitions in Mn²⁺ ions, which are set in an octahedral oxygen environment. The range of concentration quenching of Mn²⁺ ion radiation is determined. Correlation of the luminescent and vibration properties of these compounds is discussed.