Concentration-phase transitions in solid solutions Li x Na1 − x Ta0.1Nb0.9O3, Li0.12Na0.88Ta y Nb1 − y O3, and NaTa y Nb1 − y O3 and their manifestations in Raman spectra

Using the Raman-spectroscopy method, we have studied concentration-phase transitions in the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃, Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ (x = 0?0.16, y = 0–1). It has been revealed that, for the solid solutions Li _x Na_{1 ? x} Ta_0.1Nb_0.9O₃ and Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, the concentration-phase transition is a transition between the ferroelectric and antiferroelectric states. It is accompanied by the disappearance from the spectrum of a line that corresponds to stretching bridge vibrations of oxygen atoms along the polar axis, which is forbidden by selection rules in the centrosymmetric phase, and by splitting into two components of a line that corresponds to librational vibrations of oxygen octahedra as a whole, which can be caused by doubling of the unit cell in the antiferroelectric phase. Manifestation and variation of intensities of lines with frequencies 860–873 and 900–905 cm^?1 upon variation of the concentration of tantalum for solid solutions Li_0.12Na_0.88Ta _y Nb_{1 ? y} O₃, and NaTa _y Nb_{1 ? y} O₃ is caused by the formation of polar clusters in the medium, which is centrosymmetric in general due to disordering in the sublattice of niobium and tantalum.     

Reentrant Dipole Glass-Like Ordering in Weakly Concentrated KTaO3:Nb

Recently we reported that a very small admixture of Li^? dipole impurities into moderately concentrated KTaO₃:Nb leads to an unusual sequence of ferroelectric-type phase transitions with a reentrant glass phase formation at the lowest temperatures [1], Here, we present dielectric permittivity and Raman scattering study for nearly the same composition as used in Ref. [1], but without Li admixture, for KTa_0.982Nb_0.018,O₃ (KTN1.8). It is found that the presence of strong Li dipole defects is not an essential condition for the reentrant glass formation. Above T_c (27 K) KTN1.8 behaves as a conventional soft mode displacive type ferroelectric in paraelectric phase. However, below T_c a crossover to the order-disorder polar microregion dynamics and a state at which a reentrant glass phase coexists with long-range ordering occurs.     

Magnetic ordering and magnetoresistive effect in La1−x Srx(Mn1−y Mey)O3 perovskites (Me = Nb, Mg)

Perovskites of composition La_1?x Sr_x(Mn_1?x/2Nb _x/2)O₃ and La_0.49Sr_0.51(Mn_1?y Nb_y)O₃ have been synthesized and investigated. The substitution of nonmagnetic niobium ions for manganese was shown to lead to a transition from the metallic into the insulating state due to a decrease in the number of dissimilar (different-valence) manganese atoms in the lattice. In spite of the high resistivity, the niobium-containing perovskites exhibit a large magnetoresistive effect and ferromagnetic ordering. Small additions of Nb⁵⁺ to La_0.49Sr_0.51MnO₃ stimulate the transition from the antiferromagnetic into the ferromagnetic state, whereas the substitution of Mg²⁺ for Mn stabilizes the antiferromagnetic state. It is supposed that the ferromagnetism in the insulating perovskites at hand is due to the positive superexchange of the Mn³⁺-O-Mn³⁺ type, and the magnetoresistive effect owes to the intergranular transfer of spin-polarized charge carriers and the suppression of magnetic nonuniformities by an applied magnetic field near T _C.     

Low-temperature phase transformations in weakly doped quantum paraelectrics: novel features and quantum reentrant dipolar glass state in KTa0.982Nb0.018O3

An unusual sequence of phase transitions (PT) and reentrant dipole glass-like phase formation at low temperatures was found recently in KTaO₃ weakly doped with Li and Nb (K_0.9986Li_0.0014Ta_0.976Nb_0.024O₃) [Phys. Rev. B 63 (2001) 172]. We report on detailed low frequency (100 Hz-1 MHz) permittivity and Raman light scattering studies of similar composition, but without Li admixture, KTa_1−xNb_xO₃ with x=0.018 (KTN1.8). The aim of the study is to answer the question if the reentrant dipole glass-like phase exists in KTN1.8 and what is the microscopic origin of this phase. A detailed study of the sharp low-temperature PT observed at T_C∼27 K revealed properties inherent to the reentrant glass-type state at lower temperatures. The substitution of Nb for Ta influences the TO₁ soft lattice mode and leads to PT with the long-range ferroelectric ordering. A crossover to an order-disorder polar microregion dynamics with a non-standard ε′(T) behaviour and dipole glass-like formation were found below T_C (at ∼15 K), which is attributed to the randomness of the Nb distribution. A crossover to the long-range order was found under a dc bias field.     

Investigating ionic mobility in solid solutions of Li x Na1 − x Ta y Nb1 − y O3 via Raman spectroscopy

The ionic mobility in Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions (SSes) is investigated by means of Raman spectroscopy. The average lifetime of an Li⁺ ion in the equilibrium position and the magnitude of the potential barrier are estimated from the temperature dependence of the line width corresponding to the vibrations of Li⁺ cations.     

Optical properties of Li1−xNb1−xEu2xO3 solid solutions

Abstract

The effects of europium substitution on crystalline solubility, structural changes and optical properties of LiNbO₃ is reported. Li_1?xNb_1?xEu_2xO₃ solid solutions exist over a very limited range of europium concentrations (x ≤ 0.01). The solid solutions were characterized by X-ray powder diffraction and density measurements. Within the range of compositions of the solid solutions, the optical properties (emission and excitation spectra) of the Eu³⁺ ions have been characterized. The obtained optical data indicate that two equally abundant europium luminescent species exist in the stoichiometric speciments; these correspond to the Eu³⁺ ions occupying the Li⁺ and Nb⁵⁺ sites, in agreement with the replacement mechanism which is inferred from density measurements. Other Eu³⁺ luminescent species which appear to be closely related with lithium deficiency were found to exist in nonstoichiometric samples, in addition to those which are present in the stoichiometric materials.     

Concentration phase transitions in Li x Na1 − x Ta y Nb1 − y O3 solid solutions

The ferroelectric-antiferroelectric concentration phase transitions in solid solutions of Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃, which are promising environmentally friendly (lead-free) ferropiezoelectric materials, are studied by means of Raman spectroscopy.     

Study of the ferrodistorsive orbital ordering in NaNiO2 by neutron diffraction and submillimeter wave ESR

NaNiO₂ has been studied by neutron-powder diffraction, magnetic susceptibility and submillimeter wave ESR. The monoclinic structure at room temperature is characterised by a ferrodistorsive orbital ordering due to the Jahn-Teller (JT) effect of the Ni³⁺ ions in the low spin state. NaNiO₂ undergoes a structural transition at around 480 K, above which the orbital ordering disappears. The high temperature phase is rhombohedral with the layered -NaFeO₂ structure ( space group). The magnetic susceptibility exhibits hysteresis and we observe a change of the Curie-Weiss law parameters above the JT transition. The anisotropy of the g-factor at 200 K can be attributed to the JT effect which favours the orbital occupation. Finally, the interplay between the magnetic and structural properties of NaNiO₂ and Li_1-xNi_1+xO₂ is discussed. Received 29 May 2000     

Enhanced luminescence from spontaneously ordered Gd2O3:Eu based nanostructures

Nanostructured Gd₂O₃:Eu³⁺ and Li⁺ doped Gd₂O₃:Eu³⁺ thin films were prepared by pulsed laser ablation technique. The effects of annealing and Li⁺ doping on the structural, morphological, optical and luminescent properties are discussed. X-ray diffraction and Micro-Raman investigations indicate a phase transformation from amorphous to nanocrystalline phase and an early crystallization was observed in Li⁺ doped Gd₂O₃:Eu³⁺ thin films on annealing. AFM images of Li⁺ doped Gd₂O₃:Eu³⁺ films annealed at different temperatures especially at 973 K show a spontaneous ordering of the nanocrystals distributed uniformly all over the surface, with a hillocks (or tips) like self-assembly of nanoparticles driven by thermodynamic and kinetic considerations. Enhanced photoemission from locations corresponding to the tips suggest their use in high resolution display devices. An investigation on the photoluminescence of Gd_2−xEu_xO₃ (x=0.10) and Gd_2−x−yEu_xLi_yO₃ (x=0.10, y=0.08) thin films annealed at 973 K reveals that the enhancement in luminescence intensity of about 3.04 times on Li⁺ doping is solely due to the increase in oxygen vacancies and the flux effect of Li⁺ ions. The observed decrease in the values of asymmetric ratio from the luminescence spectra of Li⁺ doped Gd₂O₃:Eu³⁺ films at high temperature region is discussed in terms of increased EuO bond length as a result of Li⁺ doping.     

Improving magnetocaloric properties of Fe68–xCrxTb5B23Nb4 (x = 0, 2, 4, 6 and 8) metallic glasses having high glass-forming ability with tunable Curie temperature

Abstract

The impacts of adding Cr on the Curie temperature (T_C), glass-forming ability (GFA), and magnetocaloric effect were studied in Fe_68?xCr_xTb₅B₂₃Nb₄ (x = 0, 2, 4, 6 and 8) metallic glasses prepared by suction casting. GFA depends on Cr content in the composition. For Fe_68?xCr_xTb₅B₂₃Nb₄ bulk metallic glasses (BMGs), with critical diameters up to ~3 mm can be produced by suction casting and maximum value of GFA was found for x = 6. By exchanging Cr with Fe partially, T_C could effectively be adjusted in a quite broad temperature interval from 487 K for x = 0 to 267 K for x = 8, whereas maximum magnetic entropy change decreased from 1.16 to 0.53 Jkg^?1 K^?1 and refrigeration capacity (RC) changed from 116 to 45.05 J/kg under a low field change of 2 T. Though T_C is shifted to room temperature, maximum magnetic entropy change and RC decreased almost half of the base alloy. To enhance these properties (Fe_0.62Cr_0.06Tb_0.05B_0.23Nb_0.04)_100?yCu_y (y = 0.75, 1), metallic glasses are prepared. By the help of small addition of Cu, magnetocaloric properties can be effectively increased without changing the T_C. These findings show that the successful synthesis of the Fe-based Fe₆₂Cr₆Tb₅B₂₃Nb₄ and (Fe_0.62Cr_0.06Tb_0.05B_0.23Nb_0.04)_100?yCu_y (y = 0.75, 1) BMGs near room temperature, could be considered as promising candidates as magnetic refrigerant materials.     

Synthesis and dielectric properties of modified potassium sodium niobate solid solutions

In the present work processing microstructure and dielectric properties of lead free KNN based ceramics have been studied. Compositions with a stoichiometric formula (1 ? x)(K_0.5Na_0.5)Nb_{1 ? y} Sb _y O₃-xBaTiO₃ (x = 0.01, 0.02, 0.04; y = 0.04, 0.07) were produced by solid state sintering method. The addition of manganese oxide MnO₂ after synthesis promoted the sintering and densification of ceramic samples. The influence of BaTiO₃ on the microstructure, density and electrical properties was investigated. X-ray diffraction analysis confirmed that obtained samples had a pure perovskite structure with no traces of secondary phase. Phase transition peak at T _c is broad indicating the diffuse phase transition.     

The study of lithium fast ion conductors of Li3xLa0.67−xScyTi1−2yNbyO3 system

Perovskite-type lithium fast ion conductors of Li_3xLa_0.67−xSc_yTi_1−2yNb_yO₃ system were prepared by solid state reaction. X-Ray powder diffraction shows that perovskite solid solution form in the ranges of x=0.10, y≤0.10. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of the order of 10⁻⁴ S·cm⁻¹ and 10⁻⁵ S·cm⁻¹ at 25 °C respectively. The compositions have low bulk activation energies of about 17 kJ/mol in the temperature ranges of 298 – 523 K and total activation energies of about 37 kJ/mol in the temperature ranges of 298 – 523 K.     

Electrical conductivity and magnetic properties of La1 ? xCaxMn1 ? yFeyO3 ceramic samples (x = 0.67, y = 0, 0.05)

The temperature dependences of the magnetic susceptibility χ(T) and the electrical resistivity ρ(T) of ceramic samples of La_{1 − x} Ca _x MnO₃ with x = 0.67 (LCMO) and La_{1 − x} Ca _x Mn_{1 − y} Fe _y O₃ with x = 0.67 and y = 0.05 (LCMFO) are investigated in magnetic fields B = 50–10⁵ G and the temperature range T = 4.2–400 K. Both samples undergo a transition from the paramagnetic state to a state with charge (orbital) ordering (CO) at temperatures T _CO ≈ 272 K for LCMO and T _CO ≈ 222 K for LCMFO. The behavior of the paramagnetic phase in the temperature range 320–400 K for LCMO and 260–400 K for LCMFO is described by the Curie-Weiss law with effective Bohr magneton numbers p _eff = 4.83 μ_B (LCMO) and 4.77 μ_B (LCMFO), respectively. The disagreement between the observed positive Weiss temperatures (θ ≈ 175 K (LCMO) and θ ≈ 134 K (LCMFO)) and negative Weiss temperatures required for the antiferromagnetic ground state can be explained by the phase separation and transition to the charge-ordered state. The magnetic irreversibility for T < T _CO is accounted for by the existence of a mixture of the ferromagnetic and antiferromagnetic phases, as well as the cluster glass phase. At low temperatures, doping with iron enhances the frustration of the system, which manifests itself in a more regular behavior of the decay rate of the remanent magnetization with time. The temperature dependence of the electrical resistivity in the range of the charge-ordered phase conforms to the variable-range hopping model. The behavior of the electrical resistivity is governed by the complex structure of the density of localized states near the Fermi level, which includes a soft Coulomb gap Δ = 0.464 eV for LCMO and 0.446 eV for LCMFO. It is established that the ratio between the localization radii of charge carriers a for LCMFO and a _und for LCMO is a/a _und = 0.88. Original Russian Text ? V.S. Zakhvalinskiĭ, R. Laiho, T.S. Orlova, A.V. Khokhulin, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 1, pp. 61–68.     

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.     

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.     

Relationship between the crystal structure and the reentrant superconducting properties of (Sn1-xErx)Er4Rh6Sn18

Single crystals of (Sn_1-xEr_x)Er₄Rh₆Sn₁₈ are superconducting (T_c = 1.3K) for x 0, are reetrant superconducting (T_c = 1.24K and T_M = 0.34K) for x ～.30 and undergo a singel magnetic transition (T_M=0.68K) for x～.75. Since the occupancy of the [Sn(1)_1-xEr(1)_x]Er(2)₄ sublattice is responsible for the variation of the low-temperature properties, one can make predictions as to new reentrant superconductors in the MRh_xSn_y series (M=RE). This appears to be the first system of reentrant superconductors where stoichiometry within a sublattice controls both magnetic ordering and superconductivity.     

Microstructure and electrical properties of Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3–LiNbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics of (1?x?y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yLiNbO₃ (BNT–BKT–LN-x/y) have been fabricated by a conventional solid-state reaction method, and their microstructure and electrical properties have been investigated. The results of X-ray diffraction (XRD) measurement show that K⁺, Li⁺ and Nb⁵⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a solid solution with a pure perovskite structure. The BKT and LN addition has no remarkable effect on the crystal structure. However, a significant change in grain size took place. Simultaneously, with increasing amount of LN, the temperature for a ferroelectric–antiferroelectric phase transition is clearly reduced. The temperature dependence of dielectric properties suggests that the ceramics have diffuse-type phase transition characteristics. The piezoelectric constant d₃₃ and the electromechanical coupling factor k_p of the ceramics attain maximum values of 195 pC/N and 0.336 at x=0.18 and y=0.01.     

Crystalline structural phase boundaries in (K,Na,Li)NbO 3 ceramics

Lead-free (K_xNa_1−x)_1−yLi_yNbO₃ ceramics (with x=0.50, y=0–0.08 and x=0.30–0.70, y=0.06, respectively) were synthesized using the conventional solid-state reaction technique. Compositional influences of K, Na and Li constituents on microstructures, crystalline structures, dielectric and piezoelectric properties were investigated. It has been known that microstructures change largely with the alkali constituents and that there exist three orthorhombic-tetragonal phase boundaries at room temperature. One occurs in (K_0.50Na_0.50)_1−yLi_yNbO₃ ceramics at y=0.05–0.06, which corresponds to the previously reported morphotropic phase boundary (MPB). The other two appear in (K_xNa_1−x)_0.94Li_0.06NbO₃ ceramics near x=0.40 and x=0.60, respectively. (K_0.50Na_0.50)_0.935Li_0.065NbO₃ and (K_0.45Na_0.55)_0.94Li_0.06NbO₃ ceramics show high piezoelectric properties with the d₃₃ values over 200 pC/N and the k_p values around 45% at room temperature. It is thought that the observed high piezoelectric properties are largely affected by the temperature-driven orthorhombic-tetragonal phase transition.     

Crystal and magnetic structure of CeVO<Subscript>3</Subscript>

The crystal structure and the magnetic ordering pattern of the electrically insulating perovskite CeVO₃ was investigated by high-resolution powder X-ray diffraction and single-crystal neutron diffraction. A structural phase transition from an orthorhombic to a monoclinic structure (with space groups Pbnm and P2₁/b, respectively) was observed upon cooling below T _s = 136 K. This transition is associated with a strong distortion of the VO₆-octahedra and can be attributed to orbital ordering. A magnetic ordering transition driven by exchange interactions between vanadium moments is observed at T _N = 124 K, and antiferromagnetic interactions between magnetic moments on vanadium and cerium ions induce a progressive magnetic polarization of the cerium sublattice at lower temperatures. The full magnetic structure is described by a superposition of the modes (C _x , F _y , −) and (F _x , C _y , −). The unit cell volume and the tilt angles of the VO₆-octahedra in the CeVO₃-crystal structure are anomalous compared to those of other members of the series RVO₃ (R = lanthanide atom), and the ordered magnetic moments on both vanadium and cerium sublattices at low temperatures are considerably smaller than the free-ion values of V³⁺ and Ce³⁺. Possible origins of this behavior are discussed.     

X-ray spectra and specific features of the structure of lithium-sodium cobaltite Li<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Na<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>CoO<Subscript>2</Subscript>

The electronic structure and specific features of the structure of nonstoichiometric cobaltite Li _x Na _y CoO₂ (x = 0.42, y = 0.36) have been studied comprehensively. The calculated multiplet for the lowspin state of the Co³⁺ ion agrees with the experimental spectra. It has been established using X-ray absorption spectra measured in the total photoelectric effect yield and total fluorescence yield modes that the Li _x Na _y CoO₂ cobaltite is stoichiometric with respect to the alkali metal near its surface and is defective inside. It has been demonstrated that the charge compensation in the case of an alkali metal deficit in LixNayCoO₂ is due to holes in O 2p states.