Alkoxide Route to La0.5Sr0.5CoO3 Films and Powders

An all-alkoxide route to films and nano-phase powders of the La_0.5Sr_0.5CoO₃ perovskite is described. To our knowledge, this is the first purely alkoxide-based route to (La_{1− x} Sr _x )CoO₃, and it yields phase-pure and elementally homogeneous perovskite at 700°C by heating at 2°C/min. At 700°C, a cubic unit cell was obtained with a _c=3.853Å, and after further heating to 1000°C, a rhombohedral cell could be indexed: a _r=5.417 Å, α_r=59.94°. Ninety to 130 nm thick films of La_0.5Sr_0.5CoO₃ were obtained by spin coating. The gel-to-oxide conversion was studied in some detail, using thermo-gravimetric analysis, differential scanning calorimetry, powder X-ray diffraction, IR spectroscopy, and transmission electron microscope equipped with an energy-dispersive X-ray spectrometer.     

The Optical Properties and Band Gap Energy of Nanocrystalline La0.4Sr0.6TiO3 Thin Films

The effects of microstructure on the optical properties of La_0.4Sr_0.6TiO₃ thin films were investigated. Dense films with the thickness of ∼200 nm and grain size 14–30 nm were produced on monocrystalline sapphire substrates by using a polymeric precursor spin coating technique at annealing temperatures under 800°C. X-ray data showed the formation of a single-phase cubic perovskite-type structure similar to undoped SrTiO₃ for annealing temperatures >500°C. The results of optical measurements showed that the optical spectra varied with the change of the grain size. From these data, the absorption coefficients were calculated and the band gap energy determined. In agreement with the quantum confinement model, it was shown that the band gap energy increased as the grain size decreased.     

Fabrication and Characterization of Pyroelectric Ba0.8Sr0.2TiO3 Thin Films by a Sol-Gel Process

A sol-gel process was used to prepare pyroelectric Ba_0.8Sr_0.2TiO₃ thin films with large columnar grains (100–200 nm in diameter) on Pt/Ti/SiO₂/Si substrates, via using a 0.05 M solution precursor. The relationship between dielectric constant and temperature (ɛ_r- T ) showed two distinctive phase transitions in the Ba_0.8Sr_0.2TiO₃ thin films. Both the remnant polarization and the coercive field decreased as the temperature increased from −73°C to 40°C. Its low dissipation factor (tan δ= 2.6%) and high pyroelectric coefficient ( p = 4.6 × 10⁻⁴ C·(m²·K)⁻¹ at 33°C), together with its good insulating properties, made the prepared Ba_0.8Sr_0.2TiO₃ thin films promising for use in uncooled infrared detectors and thermal imaging applications.     

Electrical Conduction Behavior of La1+xSr1−xGa3O7–δ Melilite-Type Ceramics

Ceramics of the melilite-type compound La_{1+ x} Sr_{1− x} Ga₃O_7−δ were prepared by conventional ceramic processing. Samples prepared represented the entire homogeneity region of the phase (i.e., x =−0.15 to 0.60). Electrochemical characterization under variable temperature and atmospheric conditions in the vicinity of air entailed four-point direct-current conductivity measurements and electromotive force measurements. La_{1+ x} Sr_{1− x} Ga₃O_7−δ samples exhibited a p -type behavior with generally increased conductivity with increased substitution of lanthanum for strontium, which reached a saturation value of ∼10⁻¹ S·cm⁻¹ at 950°C.     

High-Temperature Creep Behavior of Mixed Conducting La0.5Sr0.5Fe1−xCoxO3-δ (0.5≤x≤1) Materials

Steady-state compressive creep rate of La_0.5Sr_0.5Fe_0.5Co_0.5O_3−δ (LSFC) and La_0.5Sr_0.5CoO_3−δ (LSC) is reported in the temperature region 900°–1050°C and stress range 5–28 MPa. The stress exponents for the two materials were 1.71±0.18 and 1.24±0.15, respectively. The activation energy for creep was considerably higher for LSC (619±56 kJ/mol) than for LSFC (392±28 kJ/mol). The grain size exponent for LSC was 1.28±0.14. Considerably higher creep rates were observed for both materials in N₂ compared with air. Relaxation by creep of chemical-induced stresses in oxygen-permeable membranes is addressed, especially at low partial pressure of oxygen.     

Effects of Heating Rate on the Sintering Behavior and the Dielectric Properties of Ba0.7Sr0.3TiO3 Ceramics Prepared by Boron-Containing Liquid-Phase Sintering

The effects of heating rate on the sintering behavior and the dielectric properties of Ba_0.7Sr_0.3TiO₃ ceramics prepared by boron-containing liquid-phase sintering were investigated. When 0.5 wt% B₂O₃ was added to Ba_0.7Sr_0.3TiO₃, sintering was achieved at ∼1150°C, and the overdoped B₂O₃ did not form an adequate amount of liquid phase or volatilize; it remained in the samples and formed a secondary phase. A transition broadening was observed as the heating rate increased. As the heating rate increased, the Curie temperature increased and the maximum dielectric constant ( k _max) at the Curie temperature decreased. This result is attributable to a decrease in the diffuseness parameter (δ) and the tetragonality ( c / a ).     

Recrystallization of Oxygen Ion Implanted Ba0.7Sr0.3TiO3 Thin Films

The crystallization behavior of chemical-solution-deposited and amorphous Ba_0.7Sr_0.3TiO₃ (BST) thin films was analyzed with respect to the evolution of the structural and dielectric properties of the films as a function of the annealing temperature. The amorphous films were produced by oxygen ion implantation into crystalline BST thin films. In the amorphous thin films, the crystallization to the perovskite phase occurred at T = 550°C, whereas the as-deposited CSD films showed the first crystalline XRD-reflex only after annealing at T = 650°C. Here a carbon-rich intermediate phase delayed the crystallization process to higher temperatures.     

Dielectric Behavior of Na0.5Bi0.5TiO3-Based Composites Incorporating Silver Particles

The dielectric properties of Na_0.5Bi_0.5TiO₃ (NBT) -based composites incorporating silver particles prepared by sintering at a low temperature of ∼900°C are reported. The dielectric constant increases with the amount of metal silver particles in the measured frequency range (150 Hz to 1 MHz), and could be enhanced up to ∼20 times higher than that of pure NBT ceramics, which was ascribed to the effective electric fields developed between the dispersed particles in the matrix and the percolation effect. Further investigation revealed that the dielectric constant of the composites has weak frequency and temperature dependence (−50°C to +50°C).     

30 kbar Phase Equilibria of the La2O3–SrO–CuO System at 950°C

Phase equilibria of the La₂O₃–SrO–CuO system have been determined at 950°C at 30 kbar (3 GPa). Stable phases at the apexes of the ternary phase diagram are CuO, La₂O₃, and SrO. Stable intermediate phases are La₂, CuO₄ and La₂Cu₂O₅ in the LaO_1.5–CuO binary and Sr₂CuO₃, SrCuO₂, and Sr₁₄Cu₂₄O₄₁ in the CuO–SrO binary. The La_{2– x} Sr _x -CuO_4–δ solid solution is stable for 0.00 is ≤ x ≤ 1.29, the La_{2– x} Sr_{1+ x} Cu₂O_6+δ solid solution is stable for 0.03 ≤ x ≤0.20, the La_{2– x} Sr _x Cu₂O_5–δ solid solution is stable for 0.00 ≤ x ≤1.08, and the La _x Sr_{14– x} Cu₂₄O₄₁ solid solution is stable for 0.00 ≤ x ≤ 6.15. The 30 kbar phase diagram differs from the 1 atm (0.1 MPa) and 10 kbar (1 GPa) results principally in the absence of La_{1– x} Sr_{2+ x} Cu₂O_5.5+δ as a stable phase and the extended range of the La_{2– x} Sr _x Cu₂O_5–δ solid solution at 30 kbar.     

Phase Equilibria of the La2O3-SrO-CuO System at 950°C and 10 kbar

Phase equilibria of the La₂O₃-SrO-CuO system have been determined at 950°C and 10 kbar (1 GPa). Stable phases at the apices of the ternary phase diagram are CuO, La₂O₃, and SrO. Stable intermediate phases are La₂CuO₄ in the LaO_1.5-CuO binary and Sr₂CuO₃, SrCuO₂, and Sr₁₄Cu₂₄O₄₁ in the CuO-SrO binary. The La_2-xSr _x CuO_4-δ solid solution is stable where 0.0 ≤ x ≤ 1.3, the La_2-xSr_1+xCu₂O_6+δ solid solution is stable where 0.0 ≤ x ≤ 0.2, the La_8-xSr _x Cu₈O_20-δ solid solution is stable where 1.3 ≤ x ≤ 2.7, the La _x Sr_14-x-Cu₂₄O₄₁ solid solution is stable where 0 ≤ x ≤ 6, and the La_1+xSr_2-xCu₂O_5.5+δ phase is stable where 0.04 ≤ x ≤ 0.16. The La₂O₃-SrO-CuO phase diagram at 950°C and 10 kbar is almost identical to that determined by other authors at 950°C and 1 atm, in terms of phase stability and solid-solution ranges.     

Molten-Salt Synthesis of Ba1–xPbxTiO3 in the System BaTiO3–PbCl2

Ba_{1– x} Pb _x TiO₃ powder with a fixed composition was prepared by the reaction of BaTiO₃ powders with molten PbCl₂at various PbCl₂/BaTiO₃ molar ratios at 600° and 800°C in a nitrogen atmosphere. When 0.1 μm powder was used, the reaction was finished when x = 0.9. Two phases of BaTiO₃and a solid solution of Ba_{1– x} Pb _x TiO₃ coexisted, but the final phase gave a solid solution of Ba_{1– x} Pb _x TiO₃ at 800°C. When 0.5 μm powder was used, the two phases coexisted in the products at 600°C at PbCl₂/BaTiO₃= 1.0. A sintered compact of Ba_{1– x} Pb _x TiO₃ powders solid solution was prepared by hot isostatic pressing, and its dielectric constant was measured in the temperature range 20°–550°C.     

The Li2O–Nb2O5–TiO2 Composite Microwave Dielectric Ceramics with Adjustable Permittivities

A group of new y M-phase/(1− y ) Li_{2+ x} Ti_{1−4 x} Nb_{3 x} O₃ composite ceramics with adjustable permittivities for low-temperature co-fired ceramic applications was initially investigated in the study. The 0.5 M-phase/0.5 Li_{2+ x} Ti_{1−4 x} Nb_{3 x} O₃ ( x =0.01, 0.02, 0.04, 0.06, 0.081) composite ceramics were first investigated to find the appropriate "Li₂TiO₃ss" composition ( x value). The best dielectric properties of ɛ_r=40.1, Q × f values up to 9318 GHz, τ_f=25 ppm/°C, were obtained for the ceramics composites at x =0.02. Based on the good dielectric properties, the suitable "Li₂TiO₃ss" composition with x =0.02 was mixed with the Li_1.0Nb_0.6Ti_0.5O₃ powder as the ratio of y "M-phase"/(1− y ) "Li₂TiO₃ss" ( y =0.2, 0.4, 0.5, 0.6, 0.8). By adjusting the y values, the group of composite ceramics could exhibit largely are adjustable permittivities varying from ∼20 to ∼60, while Q × f and τ_f values relatively good. Nevertheless, in this study, because there are interactions between the M-phase and Li₂TiO₃ss during sintering process, their microwave dielectric properties could not be predicted precisely by the empirical model.     

X-ray Diffraction and Microstructural Investigation of the Al2O3-La2O3-TiO2 System

The ternary phase diagram of Al₂O₃-La₂O₃-TiO₂ at 1400°C was determined with 12 compatibility triangles. Al₂O₃ stabilizes the A-site-deficient La_2/3TiO₃ perovskite structure. According to XRD and microstructural investigations, the solid solution extends along the La_2/3TiO₃-LaAlO₃ tie line from at least 4 mol% LaAlO₃ to pure LaAlO₃. With increasing LaAlO₃ content, the stabilized La_2/3TiO₃ structure changes from orthorombic via tetragonal to cubic.     

Electrical Conduction in Nano-Structured La0.9Sr0.1Al0.85Co0.05Mg0.1O3 Perovskite Oxide

Nanocrystalline La_0.9Sr_0.1Al_0.85Co_0.05Mg_0.1O₃ oxide powder was synthesized by a citrate–nitrate auto-ignition process and characterized by thermal analysis, X-ray diffraction, and impedance spectroscopy measurements. Nanocrystalline (50–100 nm) powder with perovskite structure could be produced at 900°C by this process. The powder could be sintered to a density more than 96% of the theoretical density at 1550°C. Impedance measurements on the sintered samples unequivocally established the potential of this process in developing nanostructured lanthanum aluminate-based oxides. The sintered La_0.9Sr_0.1Al_0.85Co_0.05Mg_0.1O₃ sample exhibited a conductivity of 2.40 × 10⁻² S/cm in air at 1000°C compared with 4.9 × 10⁻³ S/cm exhibited by La_0.9Sr_0.1Al_0.85Mg_0.15O₃.     

Metal Propionate Synthesis of Magnetoresistive La1−x(Ca,Sr)xMnO3 Thin Films

A flexible chemical solution deposition (CSD) method for the preparation of magnetoresistive La_1−x (Ca,Sr)x MnO₃thin films based completely on metal propionates is pre-sented.A number of polycrystalline thin films with varying stoichiometries were deposited on different substrate ma-terials at temperatures between 550° and 850°C. The crys-tallization behavior on selected substrates was found to de-pend on the thin film stoichiometry. Magnetoresistivity and magnetization were measured as a function of temperature. For the selected samples, a magnetic Curie temperature TC, a metal–semiconductor transition, and magnetoresistive behavior were observed. These measurements demon-strated that La_1−x(Ca,Sr)x MnO₃ thin films with properties well known from films deposited by PLD or sputtering can be prepared by a simple, propionate-based CSD method.     

A Novel Temperature-Compensated Microwave Dielectric (1−x)(Mg0.95Ni0.05)TiO3−xCa0.6La0.8/3TiO3 Ceramics System

The microstructure and microwave dielectric properties of a (1− x )(Mg_0.95Ni_0.05)TiO₃− x Ca_0.6La_0.8/3TiO₃ ceramics system have been investigated. The system was prepared using a conventional solid-state ceramic route. In order to produce a temperature-stable material, Ca_0.6La_0.8/3TiO₃ was added for a near-zero temperature coefficient (τ_f). With partial replacement of Mg²⁺ by Ni²⁺, the dielectric properties of the (1− x )(Mg_0.95Ni_0.05)TiO₃− x Ca_0.6La_0.8/3TiO₃ ceramics can be promoted. The microwave dielectric properties are strongly correlated with the sintering temperature and the composition. An excellent Q × f value of 118,000 GHz can be obtained for the system with x =0.9 at 1325°C. For practical application, a dielectric constant (ɛ_r) of 24.61, a Q × f value of 102,000 GHz, and a temperature coefficient of resonant frequency (τ_f) of −3.6 ppm/°C for 0.85(Mg_0.95Ni_0.05)TiO₃−0.15Ca_0.6La_0.8/3TiO₃ at 1325°C are proposed. A parallel-coupled line band-pass filter is designed and simulated using the proposed dielectric to study its performance.     

Surface Chemical and Leakage Current Density Characteristics of Nanocrystalline Ag–Ba0.5Sr0.5TiO3 Thin Films

Nanocrystalline x Ag–(1− x )Ba_0.5Sr_0.5TiO₃ (Ag–BST, 0≤ x ≤0.1, where x is the mole fraction of Ag) thin films have been deposited on Pt/Ti/SiO₂/Si substrates by a sol–gel method. The films have been characterized by X-ray diffraction (XRD), scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS). The core-level XPS of oxygen (O1 s ) of the Ag–BST films indicate that an optimum amount of Ag ( x =0.02 or 2 mol%) enhances the binding energy of oxygen, possibly through a mechanism in which the electrophilic oxygen dissociates from the Ag surface and fills the oxygen vacancies. Similarly, the binding energy of Ag (Ag3 d ) shows a shift toward a higher value with increasing Ag up to 4 mol%, probably because of the chemical shift of Ag in BST along the surface layers, surface relaxation, or changes in the Fermi level of small Ag particles in the solid solution range of Ag in BST films ( x ≤0.04). The leakage current density of 2 mol% Ag-added BST (∼10⁻⁶ A/cm²) is less by about an order of magnitude than pure BST at an electric field of 200 kV/cm. A defect model is proposed to explain the observed leakage current density of Ag–BST films satisfactorily.     

Electrical Characterization of a Joined Electroceramic, La0.85Sr0.15MnO3

Pieces of saw-cut La_0.85Sr_0.15MnO₃ were joined at 1150° and 1250°C under a compressive stress. The strains to form the joints were ∼0.1. Joints formed by plastic deformation were examined using scanning electron microscopy, and they were indistinguishable from the bulk. The room-temperature direct-current resistivity of the joined pieces was identical to that measured in the bulk material. This indicated that a sound, electrically conducting joint could be formed using plastic deformation (grain-boundary sliding) with little surface preparation.     

Low-Temperature Sintering of (Ba0.6Sr0.4)TiO3

An addition of just 0.4 wt% Li₂O to (Ba_0.6Sr_0.4)TiO₃ powder was able to reduce the sintering temperature to ≤900°C and produce ceramics with a relative density of 97%. Small amounts of two secondary phases were formed during this process: Li₂TiO₃ and Ba₂TiO₄. The addition of Li₂O depresses the ferroelectric character of the (Ba_0.6Sr_0.4)TiO₃ and, as a result, reduces the permittivity, improves the temperature coefficient of permittivity, and reduces the dielectric losses. The tunability shows no significant variation with Li₂O concentration and remains between 16.5% and 13.5%. A low-temperature sintering mechanism was proposed. The mechanism involves the intermediate formation of BaCO₃, its melting and the incorporation of Li⁺ into the BST. The sintering mechanism can be characterized as reactive liquid-phase sintering.     

Subsolidus Relations in the La2O3─CuO─CaO Phase Diagram and the La2O3─CuO Binary Join

The phase diagram for the CuO-rich part of the La₂O₃─CuO join was redetermined. La₂Cu₂O₅ was found to have a lower limit of stability at 1002°± 5°C and an incongruent melting temperature of ∼1035°C. LagCu₇O₁₉ had both a lower (1012°± 5°C) and an upper (1027°± 5°C) limit of stability. Subsolidus phase relations were studied in the La₂O₃─CuO─CaO system at 1000°, 1020°, and 1050°C in air. Two ternary phases, La_1.9Ca_1.1Cu₂O_5.9 and LaCa₂Cu₃O_8.6, were stable at these temperatures, with three binary phases, Ca₂CuO₃, CaCu₂O₃, and La₂CuO₄. La₂Cu₂O₅ and La₈Cu₇O₁₉ were stable only at 1020°C, and did not support solid-solution formation.