Structural and electrical properties of crystalline (1−x)Ta2O5−xTiO2 thin films fabricated by metalorganic decomposition

Polycrystalline (1−x)Ta₂O₅−xTiO₂ thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO₂ layer was formed at the (1−x)Ta₂O₅−xTiO₂/Si interface. Thin films with 0.92Ta₂O₅–0.08TiO₂ composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×10¹¹ cm⁻² eV⁻¹, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm² was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10⁻⁹ A/cm² up to an applied electric field of 6 MV/cm.     

Densification and conductivity enhancement of Na4Zr2Si3O12-based solid electrolytes using TiO2 as a sintering aid

Densification of Na₄Zr₂Si₃O₁₂ (NZS) solid electrolytes was performed by dispersing TiO₂ (0.8–5.9 wt. %, corresponding to 5–30 mol %) in NZS powders prior to sintering at 1200°C. Increases in pellet density, from ca. 65 to 94% of the theoretical (X-ray density) value, and in electrical conductivity from 10⁻⁷ to 10⁻⁶ S/cm at 50°C were observed for small additions of TiO₂, which acts as a sintering aid. AC impedance spectroscopy reveals that the enhancement is not a bulk effect but instead is associated with a reduction in inter-granular constriction resistances within porous NZS ceramics. The presence of adsorbed water species in NZS powders prepared via a sol-gel route is found to have a dramatic effect on the conductivity enhancement.     

Nax/2Bi1−x/2MoxV1−xO4 and Bi1−x/3MoxV1−xO4 New Scheelite-related phases

New Scheelite-related solid solutions of the compositions Na_x/2Bi_1−x/2Mo_xV_1−xO₄ (0≤x≤1) and Bi_1−x/3 Mo_xV_1−xO₄(0≤x≤0.2) have been synthesised by the substitution of Na and Mo at the A and B sites respectively of the ABO₄ type ferroelastic BiVO₄. The phases were characterised using chemical analysis, powder X-ray diffraction, scanning electron microscopy, EDAX, and Raman spectroscopy. While almost a continuous solid solution is obtained for the series Na_x/2Bi_1−x/2Mo_xV_1−xO₄, the absence of Na at the A-site results only in a narrow stability region for the other series, Bi_1−x/3 Mo_xV_1−xO₄ where 0≤x≤0.2. Raman spectra of selected samples at room temperature also suggest that vanadium and molybdenum atoms are disordered at the tetrahedral sites.     

Investigation of 1.3 μm emission in Nd-doped bismuth-based oxide glasses

Nd₂O₃-doped 43Bi₂O₃–xB₂O₃–(57−x)SiO₂–1.0Nd₂O₃ (x=57, 47, 39, 28.5, 19.5, 10, 0 mol%) bismuth glasses were prepared by the conventional melt-quenching method, and the Nd³⁺: ⁴F_3/2→⁴I_13/2 fluorescence properties had been studied in an oxide system Bi₂O₃–B₂O₃–SiO₂. The Judd–Ofelt analysis for Nd³⁺ ions in bismuth boron silicate glasses was also performed on the basis of absorption spectrum, and the transition probabilities, excited-state lifetimes, the fluorescence branching ratios, quantum efficiency and the stimulated emission cross-sections of ⁴F_3/2→⁴I_13/2 transition were calculated and discussed. The stimulated emission cross-sections of 1.3 μm were quite large due to a large refractive index of the host. Although the effective bandwidths decreased with increasing SiO₂ content, quantum efficiencies and stimulated emission cross-sections enhanced largely with increasing SiO₂ content.     

Dy,Co共掺杂对BiFeO3陶瓷磁特性和磁相变温度Tc的影响

采用快速液相烧结法制备BiFeO₃和Bi_0.95Dy_0.05Fe_1-xCo_xO₃ (x=0, 0.05, 0.1, 0.15)陶瓷样品. 实验结果表明: 所有样品的主衍射峰与纯相BiFeO₃相符合且具有良好的晶体结构, 随着Co³⁺掺杂量的增大, Bi_0.95Dy_0.05Fe_1-xCo_xO₃样品的主 衍射峰由双峰(104)与(110)逐渐重叠为单峰(110), 当掺杂量x>0.05时, 样品呈现正方晶系结构; SEM形貌分析可知: Dy³⁺, Co³⁺共掺杂使BiFeO₃晶粒尺度由原来的3—5 μ减小到约1 μ. 室温下, BiFeO₃样品表现出较弱的铁磁性, 随着Dy³⁺和Co³⁺掺杂, BiFeO₃样品的铁磁性显著提高. 在外加磁场为30 kOe的作用下, Bi_0.95Dy_0.05Fe_1-xCo_xO₃ (x=0.05, 0.1, 0.15)的M_r分别为0.43, 0.489, 0.973 emu/g; M_S分别为0.77, 1.65, 3.08 emu/g. BiFeO₃和Bi_0.95Dy_0.05Fe_1-xCo_xO₃样品磁矩M随着温度T的升高而逐渐减小, Dy掺杂使BiFeO₃样品的T_N由644 K升高到648 K, 而T_C基本没有变化. Dy和Co共掺杂导致BiFeO₃样品磁相变温度T_C由870 K降低到780 K, 其T_C变化主要取决于Fe-O-Fe反铁磁超交换作用的强弱和磁结构的相对稳定性. 关键词： 铁磁电材料 磁滞回线 磁相变温度     

Effect of Cu doping in MgB2 superconductor at various processing temperatures

The effects of Cu doping in MgB₂ superconductor has been studied at different processing temperatures. The polycrystalline samples of Mg_1−xCu_xB₂ with x = 0.05 were synthesized through the in-situ solid sate reaction method in argon atmosphere at different temperature range between 800–900 °C. The samples were characterized through X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and low temperature R–T measurement techniques for the phase verification, microstructure and superconducting transition temperature, respectively. The XRD patterns of Mg_1−xCu_xB₂ (x = 0.05) do not exhibit any impurity traces of MgB₄ or MgB₆ and they show the sharp transition in the samples prepared at 850 °C. The onset transition temperature of the prepared samples is around 39 K, which is almost the same as that for the pure MgB₂. This indicates that Cu doping in MgB₂ does not affect the transition temperature. The SEM micrograph of Mg_0.95Cu_0.05B₂ has shown that the sample is dense with grain size smaller than 1 μm.     

Ionic conduction and dielectric relaxation in Ag/Na ion-exchanged aluminosilicate glasses: mixed mobile ion effect and KWW relaxation

Ag⁺/Na⁺ ion-exchanged aluminosilicate glasses with uniform concentration profiles were prepared, and their electrical conductivities were investigated as functions of the ion-exchange ratio and the initial glass compositions. In the case of the ion-exchanged glasses of x20Ag₂O–(1−x)20Na₂O–10Al₂O₃–70SiO₂ in mol%, the conductivity, σ, and its activation energy, E_σ, showed a minimum and a maximum at the same ion-exchange ratio x=0.3, respectively, and the mixed mobile ion effect (MMIE) was observed. The fully ion-exchanged sample attained σ=3.5×10⁻⁵ S/cm at 200 °C, which was 1.5 orders of magnitude larger than that of initial glass. In the case of x25Ag₂O–(1−x)25Na₂O–25Al₂O₃–50SiO₂, the mixed mobile ion effect was also observed at x=0.5. The maximum conductivity of 2×10⁻⁴ S/cm at 200 °C was obtained in the fully ion-exchanged glass sample.

The electric relaxation analysis was also conducted on both systems, and Kohlrausch–Williams–Watts (KWW) fractional exponent β was obtained as a function of x. The decrease of β was observed near x≈0.3 in the former system, while that of the later system was independent of the ion-exchange ratio. Based on the structural analysis results, the observed behaviors were investigated from the point of view of the occupation of Ag⁺ ions on the non-bridging oxygen-site (NBO-site) and the charge compensation-site (CC-site) of AlO₄ tetrahedral unit.     

Preparation, characterization and oxide ion conductivity in U-substituted Bi4V2O11

A Bi₂V_{1 − x − y}U_xBi_yO_{5.5 + 0.5x − y} solid solution derived from Bi₄V₂O₁₁ has been prepared and characterized with x up to 0.125 for y = 0. Partial substitution of U⁶⁺ for V⁵⁺ in Bi₄V₂O₁₁ leads to the stabilization at room temperature of the high-oxide ion conducting γ-phase, in contrast with other M⁶⁺ dopants which stabilize the β-phase. The lower conductivity in U substituted system compared with BICUVOX.10 is attributed to its higher activation energy. Conductivity values and activation energies of the U substituted phases compare well with Bi₂UO₆.     

Enhanced luminescence from transparent Ni-doped MgO–Al2O3–SiO2 glass ceramics by Ga2O3 addition

Transparent Ni²⁺-doped MgO–Al₂O₃–SiO₂ glass ceramics without and with Ga₂O₃ were synthetized. The precipitation of spinel nanocrystals, which was identified as solid solutions in the glass ceramics, could be favored by Ga₂O₃ addition and their sizes were about 7.6 nm in diameter. The luminescent intensity of the Ni²⁺-doped glass ceramics was largely enhanced by Ga₂O₃ addition which could mainly be caused by increasing of Ni²⁺ in the octahedral sites and the reduction of the mean frequency of phonon density of states in the spinel nanocrystals of solid solutions. The full width at half maximum (FWHM) of emissions for the glass ceramics with different Ga₂O₃ content was all more than 200 nm. The emission lifetime increased with the Ga₂O₃ content and the longest lifetime is about 250 μs. The Ni²⁺-doped transparent glass ceramics with Ga₂O₃ addition have potential application as broadband optical amplifier and laser materials.     

Synthesis and characterization of the Aurivillius phases Bi2 − xPbxSr1 − xNdxNb2O9

The n = 2 Aurivillius phase Bi_{2 − x}Pb_xSr_{1 − x}Nd₂O₉ was successfully synthesized as a ceramic material over the whole range of simultaneous, charge compensated substitution x = 0–1.0. Structural investigations were performed by Rietveld refinement applying different space groups Fmmm and A2₁am, and additionally by X-ray absorption spectroscopy (EXAFS) on the Nd L_III-edge, confirming the accommodation of Nd on the atomic sites of Sr, which implies the substitution of Bi³⁺ by the isoelectronic Pb²⁺. The ferroelectric transition temperature T_c = 270 °C of the substituted powders with x = 0.4 and 1.0 is distinctly reduced compared to the unsubstituted sample with T_c = 450 °C. In temperature resolved powder X-ray diffraction patterns no structural phase transition could be detected.     

Effect of lead addition to Bi-based 2222 superconducting cuprates Bi2-xPbxSr2(Y, Ce)2Cu2O10+δ

Bi_2-xPb_xSr₂(Y, Ce)₂Cu₂O_10+δ, a new family of lead containing Bi-2222 compounds has been synthesized and effects of annealing in high pressure of oxygen studied. Lead-free Bi₂Sr₂(Y, Ce)₂Cu₂O_10+δ synthesized under flowing oxygen is known to be non-superconducting, but annealing under high oxygen pressure (100 bar) at 500°C, induced superconductivity with T_c=25 K. On substitution of lead (x>0.4), the superconductivity appears even in samples synthesized under flowing oxygen (1 bar). T_c increases with oxygen annealing pressure for all compositions, and it also increases with Pb content at a given oxygen pressure. These findings are discussed.     

The role of Bi2O3 as a network modifier and a network former in xBi2O3 · (1 − x)LiBO2 glass system

The effect of Bi₂O₃ on the glass transition temperature, electrical conductivity and structure of LiBO₂ glass has been investigated. T_g vs. composition curve shows three different linear regions, while there is an overall decrease in T_g with the increase in Bi₂O₃ content. The slope of these three straight lines is in a decreasing order. These results are interpreted in terms of the increase in the number of non-bridging oxygen atoms, substitution of Bi-O bond in place of B-O bond and change in Li⁺ ion concentration. The conductivity vs. composition curve exhibits two maxima which are interpreted in terms of the structural modification effect of Bi₂O₃ on LiBO₂ network and mixed-former effect, respectively. Results obtained from the XPS studies of the samples of composition x 0.005, have shown that the number of non-bridging oxygen atoms from B-O bond increases with the increase in Bi₂O₃ content. It has a maximum value at x = 0.003 where the conductivity has also exhibited a maximum value. Further increase of Bi₂O₃ content causes decrease in it. For higher Bi₂O₃ content (x * > 0.005), O 1s spectra of Bi₂O₃ has been separated out from that of Bi₂O₃. Bismuth ions have been substituted for boron ions as network former ions.     

Picosecond nonlinear optical response of Ba0.5Sr0.5TiO3 thin films fabricated by pulsed laser deposition

Well-crystallized Ba_0.5Sr_0.5TiO₃ thin films with good surface morphology were prepared on MgO(1 0 0) substrates by pulsed laser deposition technique at a deposition temperature of 800 °C under the oxygen pressure of 2 × 10⁻³ Pa. X-ray diffraction and atomic force microscopy were used to characterize the films. The full width at half maximum of the (0 0 2) Ba_0.5Sr_0.5TiO₃ rocking curve and the root-mean-square surface roughness within the 5 μm × 5 μm area were 0.542° and 0.555 nm, respectively. The nonlinear optical properties of the films were determined by a single beam Z-scan method at a wavelength of 532 nm with laser duration of 55 ps. The results show that Ba_0.5Sr_0.5TiO₃ thin films exhibit a fast third-order nonlinear optical response with the nonlinear refractive index and nonlinear absorption coefficient being n₂ = 5.04 × 10⁻⁶ cm²/kW and β = 3.59 × 10⁻⁶ (m/W), respectively.     

Effect of WO3 on the spectroscopic properties in Er/Yb co-doped bismuth–borate glasses

The spectroscopic properties of Er³⁺/Yb³⁺ co-doped Bi₂O₃–B₂O₃–WO₃ (BBW) glasses were analyzed and discussed. The effect of WO₃ content on the absorption spectra, the Judd–Ofelt parameters Ω_t (t=2, 4, 6), emission spectra and the lifetime of the ⁴I_13/2 level and the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition were also investigated. With the substitution of WO₃ for B₂O₃, the measured lifetime of the ⁴I_13/2 level and the quantum efficiency of Er³⁺:⁴I_13/2→⁴I_15/2 transition increase from 0.98 to 1.31 ms and from 38.2% to 49.2%, respectively. The effective width of emission band and the emission cross-section both decrease slightly. And the emission spectra is analyzed via the different curve (σ_e−σ_a) of BBW glasses, the influence of OH⁻is also discussed.     

Na2TiGeO5: Crystal structure stability at low temperature and high pressure

The temperature evolution of the lattice parameters measured from 295 to 125 K exhibits a small instability below T_c≈278 K, indicating ferroelastic properties of Na₂TiGeO₅. The behavior is related to the specific crystal structure built of polyhedral layers with shared TiO₅ pyramids and GeO₄ tetrahedra, alternating with layers of Na⁺ cations. Antiparallel alignment of the short apical titanyl bond in adjacent rows of the polyhedral layer gives rise to spontaneous strain, when a distortion of the TiO₅ groups occurs. Single-crystal structures determined at room temperature and 120 K suggest that {1 1 0} domains, developing below T_c, entail a tetragonal-to-orthorhombic symmetry change. The mechanism is attributed to a shortening of the O–O distance between the polyhedral layers, and to minor shifts of the positions of the Ti atoms and the correlated oxygen atoms along the c-axis. The structure distortion, however, is too small to allow any unambiguous determination of the symmetry-breaking effects. The bulk modulus and its pressure derivative have been determined as B₀=89(2) GPa and . A pressure-induced phase transformation takes place at P_c≈12.5 GPa, presumably to an orthorhombic structure. The pressure effect on the transition temperature is given by ΔT_c/ΔP≈1.76 K/GPa.     

Shaped crystal growth and scintillating properties of Yb:(Gd,Lu)3Ga5O12 solid solutions

Shaped single crystals of (Lu_xGd_1−x)₃Ga₅O₁₂ (0.0x1.0) and (Yb_0.05Lu_xGd_0.95−x)₃Ga₅O₁₂ (0.0x0.9) were grown by the modified micro-pulling-down method. Continuous solid solutions with garnet structure and a linear compositional dependency of crystal lattice parameter in the system Yb:(Gd,Lu)₃Ga₅O₁₂ are formed. Measured optical absorption spectra of the samples show 4f–4f transitions related to Gd³⁺ ion at 275 and 310 nm, and also an onset of charge transfer transitions from oxygen ligands to Gd³⁺ or Yb³⁺ cations below 240 nm. A complete absence of Yb³⁺ charge transfer luminescence under X-ray excitation in any of the investigated samples was explained by the overlapping of charge transfer absorption of Yb³⁺ by that of Gd³⁺ ions. For specific composition of Lu_1.5Gd_1.5Ga₅O₁₂ an intense defect-host lattice-related emission, which achieve of about 40% integrated intensity compared with Bi₄Ge₃O₁₂, was found.     

Structure and optical properties of sol–gel derived Gd2O3 waveguide films

Pure and rare earth doped gadolinium oxide (Gd₂O₃) waveguide films were prepared by a simple sol–gel process and dip-coating method. Gd₂O₃ was successfully synthesized by hydrolysis of gadolinium acetate. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study the thermal chemistry properties of dried gel. Structure of Gd₂O₃ films annealed at different temperature ranging from 400 to 750 °C were investigated by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that Gd₂O₃ starts crystallizing at about 400 °C and the crystallite size increases with annealing temperature. Oriented growth of (4 0 0) face of Gd₂O₃ has been observed when the films were deposited on (1 0 0) Si substrate and annealed at 750 °C. The laser beam (λ=632.8 nm) was coupled into the film by a prism coupler and propagation loss of the film measured by scattering-detection method is about 2 dB/cm. Luminescence properties of europium ions doped films were measured and are discussed.     

Absorption coefficients of O3 at CO2 laser wavelengths

The O₃ absorption coefficients for the rotational lines P(12)–P(28) of the 9.4 μm emission band of the CO₂ laser are presented. Measurements were made in O₃–air dilute mixtures (20–600 ppm) at 25°C and a total pressure of 1013.25 h Pa using a frequency stabilized cw CO₂ laser and values have been determined with greater precision than in previously reported studies.     

New red Y0.85Bi0.1Eu0.05V1−yMyO4 (M=Nb, P) phosphors for light-emitting diodes

The Y_0.85Bi_0.1Eu_0.05V_1−yM_yO₄ (M=Nb, P) as new near-ultraviolet excited phosphors were synthesized and their luminescence properties under 365 nm excitation were investigated in detail. It indicated that by doping small amount of P⁵⁺ into V⁵⁺ sites, the excitation intensity of charge transfer (CT) band of Bi–O (330–400 nm) was greatly improved. By substituting Nb⁵⁺ for V⁵⁺, both the CT bands of Bi–O and Eu–O (240–320 nm) were significantly enhanced. As a result, the emission intensity of Y_0.85Bi_0.1Eu_0.05V_1−yM_yO₄ (M=Nb, P) could be improved about 90% by doping 5 mol% P⁵⁺ and 110% by doping 5 mol% Nb⁵⁺. Comparing with the commercial Y₂O₂S:Eu³⁺ phosphors, the Y_0.85Bi_0.1Eu_0.05V_0.95M_0.05O₄ (M=Nb, P) phosphors exhibited excellent color purity and much higher brightness. The results showed that these Y_0.85Bi_0.1Eu_0.05V_1−yM_yO₄ (M=Nb, P) phosphors could be considered as promising red phosphors for application in LED.     

Dielectric and magnetic properties of xNiFe2O4+(1−x)Ba0.9Sr0.1TiO3 composites

Magnetoelectric composites, namely, xNiFe₂O₄+(1−x)Ba_0.9Sr_0.1TiO₃ were prepared by standard double sintering ceramic method. The X-ray diffraction analysis was carried out to check the phases formed during sintering and to calculate the lattice parameters. Scanning electron microscope (SEM) micrographs were taken to understand the microstructure of the samples. The dielectric constant (ε′) and loss tangent (tan δ) were measured as a function of frequency in the frequency range 100 Hz–1 MHz. Variation of dielectric constant and loss tangent with temperature and composition has been reported. The hysteresis measurements were done to determine saturation magnetization (M_S) and coersivity (H_c). The variation of saturation magnetization and magnetic moment is interpreted in terms of composition.