The experimental and theoretical investigation of vibration spectra in ferroelectric semiconductor SbSBrxI1−x crystals

The vapor grown SbSBr_xI_1−x (x=0.1; 0.5; 0.9) crystals with clear mirror surfaces have been used for infrared reflection measurements with Fourier spectrometer. The vibration frequencies along c(z)-axis have been derived from Kramers–Kroning and optical parameters fitting analysis of the experimental reflectivity spectra at T=300 K. The theoretical vibration spectra of SbSBr_xS_1−x (x=0.1; 0.5; 0.9) crystals in paraelectric phase (T=300 K) along c(z)-axis have been determined in quasiharmonic approximation by diagonalization of dynamical matrix. The theoretical vibration spectra of these crystals in a–b(x−y) plane have been determined in harmonic approximation. In this work we discuss the nature of anharmonism in SbSBr_xI_1−x crystals along the c(z)-axis.     

Effects on structure and superconductivity for La and Ca codoping in YBa2Cu3Oy cuprates

The nominal composition of Y_0.8Ca_0.2Ba_2−xLa_xCu₃O_y (YBLCO) cuprates with x≤0.50 has been synthesized by the standard solid state reaction technique. X-ray diffraction and the resistivity measurements are used to characterize the structure and the superconductivity of YBLCO cuprates. There is no structural phase transition in the whole doping range. The dependencies of the lattice constants and some other structural parameters on the content of La for the samples YBLCO with x≤0.20 are different than those for the samples with x≥0.25. The zero resistance temperature T_c0 increases with the increase of the content of La in YBLCO as x≤0.20, and decreases as x≥0.25. We compared these results with those of Nd-doped Y_0.8Ca_0.2Ba_2−zNd_zCu₃O_y cuprates. It seems that T_c0 is related to the structural parameters due to Ca and La codoping in YBLCO.     

Growth and properties of air-processed GdBa2Cu3O7−δ superconductors with fined Gd2BaCuO5 and Gd2Ba4CuFeOy additions

We have succeeded in synthesizing a powder form of Gd₂Ba₄CuFeO_y (Gd2411) in air. GdBa₂Cu₃O_7−δ (Gd123)/Gd₂BaCuO₅ (Gd211) precursor powders added with different amounts of Gd₂Ba₄CuFeO_y (x = 0, 0.002, 0.004, 0.02) in molar ratio to Gd123 have been fabricated successfully into the form of large, single grains by the top seeded melt growth (TSMG) process. The relation between the additions amounts of Gd2411/Gd211 and critical current density (J_C) was analyzed. We found Gd2411 particles stably exist in the Gd123 matrix without degradation of superconducting properties owing to the existence of the Fe magnetic ion. The trapped field was observed to increase significantly compared with the bulk without Gd2411 additions.     

Effects of RE2O3 (RE = Tm, Sc, Yb) addition on the superconducting properties of ErBa2Cu3Oy

We investigated the effects of added Tm₂O₃, Sc₂O₃, and Yb₂O₃ on the superconducting properties of sintered Er123 samples. Tm₂O₃ addition caused the least T_c degradation, exhibiting a T_c above 90 K even for 17 vol% addition. Samples with added Sc₂O₃ maintained a T_c at above 90 K up to an addition of 7.2 vol%, while Yb₂O₃-containing samples showed a monotonic decrease in T_c with increased vol% of added Yb₂O₃. Tm₂O₃-containing samples exhibited a slight increase in J_c(0.1 T)/J_c(0) and had constant J_c values even for 17 vol% addition. XRD and SEM results indicate that the Tm₂O₃ is very stable in the superconducting matrix.     

Scanning tunneling microscopy/spectroscopy on multi-layered cuprate superconductor Ba2Ca5Cu6O12 (O1−x Fx)2

Scanning tunneling microscopy/spectroscopy (STM/STS) measurements on multi-layered cuprate superconductor Ba₂Ca₅Cu₆O₁₂ (O_1−x F_x)₂ are carried out. STM topographies show randomly distributed bright spot structures with a typical spot size of 0.8 nm. These bright spots are occupied about 28% per one unit cell of c-plane, which is comparable to the regular amount of apical oxygen of 20% obtained from element analysis. Tunneling spectra simultaneously show both the small and the large gap structures. These gap sizes at 4.9 K are about Δ 15 meV and 90 meV, respectively. The small gap structure disappears at the temperature close to T_C, while the large gap persists up to 200 K. Therefore, these features correspond to the superconducting gap and pseudogap, respectively. These facts give evidence for some ordered state with large energy scale even in the superconducting state. For the superconducting gap, the ratio of 2Δ/K_BT_C = 4.9 is obtained with T_C = 70 K, which is determined from temperature dependence of the tunneling spectra.     

Defect chemical and statistical thermodynamic studies on oxygen nonstoichiometric Nd2 − xSrxNiO4 + δ

In order to elucidate how oxygen content changes in Nd_2 − xSr_xNiO_4 + δ (x = 0, 0.2, 0.4), defect chemical and statistical thermodynamic analyses were carried out. The relationship among δ, P(O₂), and T were analyzed by a defect equilibrium model. Since Nd_2 − xSr_xNiO_4 + δ shows metal like band conduction at high temperatures, chemical potential of hole is expressed by the integration of the Fermi-Dirac distribution function and the density of state. The nonstoichiometric variation of oxygen content in Nd_2 − xSr_xNiO_4 + δ can be explained by the defect equilibrium model with a regular solution approximation. Partial molar entropy and partial molar enthalpy of oxygen are calculated from the nonstoichiometric data and Gibbs–Helmholtz equation. The relationship among defect structure, defect equilibrium, and thermodynamic quantities is elucidated by the statistical thermodynamic model. Thermodynamic quantities are calculated by the statistical thermodynamic model with the results of defect chemical analysis and compared with those obtained from experimental results. Thermodynamic quantities calculated by the statistical thermodynamic model can explain rough tendency of those obtained from the δ–T–P(O₂) relationship.     

Reduced anti-ferromagnetism promoted by Zn 3d substitution at CuO2 planar sites of Cu0.5Tl0.5Ba2Ca3Cu4O12−δ superconductors

The role of charge carriers in ZnO₂/CuO₂ planes of Cu_0.5Tl_0.5Ba₂Ca₃Cu_4−yZn_yO_12−δ material in bringing about superconductivity has been explained. Due to suppression of anti-ferromagnetic order with Zn 3d¹⁰ (S=0) substitution at Cu 3d⁹ sites in the inner CuO₂ planes of Cu_0.5Tl_0.5Ba₂Ca₃Cu₄O_12−δ superconductor, the distribution of charge carriers becomes homogeneous and optimum, which is evident from the enhanced superconductivity parameters. The decreased c-axis length with the increase of Zn doping improves interlayer coupling and hence the three dimensional (3D) conductivity in the unit cell is enhanced. Also the softening of phonon modes with the increased Zn doping indicates that the electron–phonon interaction has an essential role in the mechanism of high-T_c superconductivity in these compounds.     

Structural studies and T c dependence in La2−x Dy x Ca y Ba2Cu4+y O z type mixed oxide superconductors

A new series of mixed oxide superconductors with the stoichiometric composition La_2−x Dy _x Ca _y Ba₂Cu_4+y O _z (x=0.0 − 0.5, y=2x) has been studied for structural and superconductiong properties. Our earlier studies on La_2−x (Y/Er) _x Ca _y Ba₂Cu_4+y O _z series, show a strong dependence of T _c on hole concentration (p _sh). In the present work, the results of the analysis of the neutron diffraction measurements at room temprerature on x=0.3 and 0.5 samples are reported. It is interesting to know that Ca substitutes for both La and Ba site with concomitant displacement of La onto Ba site. Superconductivity studies show that maximum T _c is obtained for x=0.5, y=1.0 sample (T _c ∼ 75 K), for La_1.5Dy_0.5Ca₁Ba₂Cu₅O _z (La-2125).     

Temperature dependence of the indirect band gap, steepness parameter and related optical constants of [Kx(NH4)1−x]2ZnCl4 mixed crystals

Optical transmittance measurements near the absorption edge of [K_x(NH₄)_1−x]₂ZnCl₄ mixed crystals, where x=0.00, 0.232, 0.522, 0.644, 0.859 and 1.00, are reported over 276–350 K range. Analysis reveals that the type of transition is the indirect allowed one. The absorption edge shifted towards lower energy with increasing temperature. It is shown that [K_x(NH₄)_1−x]₂ZnCl₄ mixed crystals with x0.644 reveal a phase transition at 319 K, this phase disappeared at high concentrations of K⁺ ions. The steepness parameter is given, its value is used to estimate the temperature dependence of the indirect energy gap. In the region of the absorption edge, the absorption coefficient obeys Urbach's rule. Urbach parameters are investigated as a function of temperature.     

Structure, ferroelectric and piezoelectric properties of (Bi1−x−yNa0.925−x−yLi0.075)0.5BaxSryTiO3 lead-free piezoelectric ceramics

Lead-free multi-component ceramics (Bi_1−x−yNa_{0.925−x−y}Li_0.075)_0.5Ba_xSr_yTiO₃ have been prepared by an ordinary sintering technique and their structure and electrical properties have been studied. All the ceramics can be well-sintered at 1100 °C. X-ray diffraction patterns shows that Li⁺, Ba²⁺ and Sr²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) is formed at 0.04 < x < 0.08. As compared to pure Bi_0.5Na_0.5TiO₃ ceramic, the coercive field E_C of the ceramics decreases greatly and the remanent polarization P_r of the ceramics increases significantly after the formation of the multi-component solid solution. Due to the MPB, lower E_C and higher P_r, the piezoelectricity of the ceramics is greatly improved. For the ceramics with the compositions near the MPB (x = 0.04–0.08 and y = 0.02–0.04), piezoelectric coefficient d₃₃ = 133–193 pC/N and planar electromechanical coupling factor k_P = 16.2–32.1%. The depolarization temperature T_d reaches a minimum value near the MPB. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both the polar and non-polar regions at temperatures near/above T_d.     

Effect of Ca doping on the superconducting properties of GdBaSrCu3O7−δ bulk samples

Gd_1−xCa_xBaSrCu₃O_7−δ samples (0  x  0.1) were prepared via solid-state reaction. Four-point probes method was used for resistance versus temperature measurements. Results show decrease in T_c by increasing x content. This variation is assumed to be irrelevant to the different phases or impurity effects since X-ray patterns show all samples are tetragonal single-phase. Ca doping decreases the oxygen content and lattice parameters of the samples. It is suggested that Ca prevents the dislocation of oxygen, and then disrupts the hole concentration of the system and antiferromagnetic correlation at CuO₂ planes. Subsequently, destroys the superconductivity of the samples.     

Conversion of egg shell membrane to inorganic porous CexZr1−xO2 fibrous network

The binary system CeO₂–ZrO₂ is thermally stable and has superior reduction–oxidation properties. It has been commonly used in the three-way catalytic converters for automobiles. In this work, an inorganic biomorphic porous Ce_xZr_1−xO₂ fibrous network was successfully synthesized by using the egg shell membrane (ESM) as templates, and its morphology was a perfect replica of the original ESM. The synthesis involved a simple infiltration and calcination process. A fresh ESM was peeled from a chicken egg shell. It was soaked in a Ce(NO₃)₃ and Zr(NO₃)₄ mixture before it was calcined at 700 °C in ambient environment. The fibers in the biomorphic network had diameter ranged from 1 to 4 μm, and they were composed of Ce_xZr_1−xO₂ nanocrystallites having an average grain size of 10 nm.     

Superconductivity in the hole-doped oxy-arsenide RE1−xSrxFeAsO (RE = La, Pr)

Bulk superconductivity was observed in the FeAs-based RE_1−xSr_xFeAsO (RE = La, Pr) when the di-valence element Sr was substituted to the site of the tri-valence element La and Pr. The maximum superconducting transition temperatures T_c for the two systems are 26 K and 16.3 K, respectively. The doping dependence of the electrical properties and structure of these two systems were investigated systematically. A roughly monotonic increase of T_c and the lattice constants (a-axis and c-axis) with Sr concentration and a saturation behavior in the high doping levels were found. We confirmed that conduction in this type of materials is dominated by hole-like charge carriers by the Hall effect measurements. Also the resistive measurements revealed possible higher upper critical field in these systems comparing with the electron-doped ones.     

Effects of indium doping on the superconducting properties of YBa2Cu3Oy sintered compounds and thin films

We investigated the effects of indium doping on the superconducting properties of YBCO sintered samples and thin films. In₂O₃-doped YBCO and YBa₂Cu_3−xIn_xO_y sintered samples showed a gradual decrease in the critical temperature (T_c) with increasing indium content; however, a T_c value above 80 K was maintained even up to 30 vol.% addition and x = 0.4, respectively. Ba₃Cu₃In₄O₁₂ was detected by X-ray diffractometry and energy-dispersive X-ray spectroscopy as a reaction product for both sintered samples. The normalized J_c under a magnetic field of 0.1 T showed a maximum at x = 0.3. Indium-doped YBCO films prepared by pulsed laser deposition showed a similar dependence of T_c on indium content as the sintered samples.     

Effect of Y2O3 addition on the conductivity and elastic modulus of (CeO2)1 − x(YO1.5)x

The conductivity and elastic modulus of (CeO₂)_1 − x(YO_1.5)_x for x values of 0.10, 0.15, 0.20, 0.30, and 0.40 were investigated by experiments and molecular dynamics simulations. The calculated conductivity exhibited a maximum value at approximately 15 mol% Y₂O₃; this trend agreed with that of the experimental results. In order to clarify the reason for the occurrence of the maximum conductivity, the paths for the transfer of oxygen vacancies were counted. The numerical result revealed that as the content of Y₂O₃ dopant increases, the number of paths for the transfer of oxygen vacancies decreases, whereas the number of oxygen vacancies for conductivity increases. Thus, the trade-off between the increase in the number of vacancy sites and the decrease in the vacancy transfer was considered to be the reason for the maximum conductivity occurring at the Y₂O₃ dopant content of approximately 15 mol%. The calculated elastic modulus also exhibited a minimum value at approximately 20 mol% Y₂O₃, which also agreed with the experimental results. It was shown that the Y–O–Y bonding energy increased with the increasing content of Y₂O₃ dopant. Thus, the trade-off between the increase in the number of vacancy sites and that in the Y–O–Y bonding energy was considered to be the reason for the minimum elastic modulus occurring at the Y₂O₃ dopant content of approximately 20 mol%.     

Structures and luminescence properties of Yb3＋ in the double perovskites Ba2YB＇O6 （B＇=Ta5＋, Nb5＋） phosphors

The Yb³⁺ doped Ba₂YB'O₆ (B'=Ta⁵⁺, Nb⁵⁺) were prepared by high temperature solid-state reaction method, their structures were determined by x-ray diffraction and refined by Rietveld method. The diffuse reflection absorption, excitation and emission spectra of Yb³⁺:Ba₂YB'O₆ (B'=,Ta⁵⁺, Nb⁵⁺) were measured at room temperature. Under the excitation of ultraviolet light, these phosphors exhibit broad charge transfer band emissions of TaO₆ or NbO₆ centre with large Stokes shift. The Yb³⁺ doped into these hosts are situated at Y³⁺ sites of cubic symmetry (O_h). The experimental energy levels of Yb³⁺ in Ba₂YTaO₆ and Ba₂YNbO₆ were determined by photoluminescence and diffuse reflection absorption spectra. Their wavefunctions and theoretical energy levels were obtained by diagonalising the Hamiltonian matrix. The experimental energy levels were fitted by Levenberg--Marquardt iteration algorithm to determine crystal field parameters. Then, the magnetic-pole transition line strengths of Yb³⁺:Ba₂YB'O₆(B'=Ta⁵⁺, Nb⁵⁺) from (²F_5/2)Γ₈^- to the low-energy states were calculated.     

Improvement of the superconducting properties of an infiltrated YBCO bulk superconductor by a BaCeO3 addition

Single grain YBa₂Cu₃O_7−x (Y123) bulk superconductors with Y₂BaCuO₅ (Y211) and various amounts of BaCeO₃ (5–45 wt.% by an increment of 10 wt.%) were fabricated by a seeded infiltration process. The addition of BaCeO₃ was found to be effective for a modification of the microstructure and an improvement of the superconducting properties. The refinement effect for Y211 particles within an entire superconducting YBa₂Cu₃O_7−x (Y123) matrix was achieved by BaCeO₃ additions. The critical current density (J_c) values were increased as the BaCeO₃ contents were increased (maximum J_c at 35 wt.% BaCeO₃ addition). The J_c improvement by BaCeO₃ additions might be due to the microstructure modifications associated with the finely distributed Y211 and BaCeO₃ particles. With the addition of BaCeO₃ the onset T_c values decreased slightly, indicating highly limited Ce substitution for Y site. It can be concluded that the BaCeO₃ addition has a beneficial effect on the morphology, the size and the distribution of the Y211 inclusions and the microstructure regarding pinning improvement.     

On the existence of a homologous series of BamCum+nOy oxides with the cubic structure of the BaCuO2 oxide

Phase relations have been studied in the BaO–CuO_x system in the range of 42.0–83.0 mol.% CuO at P(O₂) = 21 kPa (air) by visual polythermal analysis (VPA), powder X-ray diffraction (XRD), differential thermal analysis (DTA), thermogravimetric analysis (TGA), chemical analysis (CA), and electron diffraction (ED) with simultaneous elemental analysis (EA) in a transmission electron microscope (TEM). The existence of discrete crystallization fields of barium–copper oxides of cation compositions Ba₄Cu₅O_y, Ba₅Cu₆O_y, Ba₇Cu₈O_y, Ba₁₂Cu₁₃O_y, and Ba₂₄Cu₂₅O_y, which have the cubic structure of the BaCuO₂ oxide, is revealed in the studied region of the system. The oxides may be represented as members of a Ba_mCu_m+nO_y homologous series. The BaCuO₂ oxide does not exist in the subsolidus region and does not have its own crystallization field. The oxygen-deficient oxide BaCuO_1.78 of the cation composition (Ba:Cu) 1:1 with the BaCuO₂ cubic structure is found in melted samples of the 50.0 mol.% CuO composition quenched at 1020–1060 °С.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

The effect of PT on phases and electrical properties in Ba-Y-Cu-O system

Several new phases containing platinum in Y-Ba-Cu-O system are reported in this paper. When Ba-Y-Cu-O system containing platinum is sintered at 950°C, two hexagonal phases YBa₂(Pt, Cu)₃O_9-δ and Ba₄Pt_1+x Cu_2-x Cu_2-x O_9-δ (x = 0.1 – 0.9) are found, respectively. The super-K₂NiF₄ structure Ba _x Y_2-x (Cu, Pt)O₄ is obtained above 1000°C in the Y-Ba-Cu-O system containing platinum. Electrical properties of these phases are also reported.