Powder processing of high temperature ceramic superconductor Tl2Ba2Ca2Cu3O10

We have developed a technique to produce high quality Tl₂Ba₂Ca₂Cu₃O₁₀ powders used for making superconducting wire, tape, lead, shield, and other large scale bulk applications. Starting with T1₂O₃, BaO₂, CaO, and CuO, we mix and grind these chemicals with a machine ball mill and then press the ground mixture into pellets. The pellets are sintered at about 895‡C for at least 30 h in an oxygen atmosphere. The sintered material is mainly the Tl₂Ba₂Ca₂Cu₃O₁₀ compound. To get more homogeneous superconductor powders, we pulverize the sintered material and use a magnetic superconducting material selector to separate and grade the material. Finally, the top grade material has a phase purity of <98% and a T_c(r < 0) of 123–126K.     

Precipitation and pinning in Ca and Sr-Rich High-Tc superconducting “Bi2Sr2CaCu2O8” ceramics

From a consideration of the phase equilibrium diagram of the system Bi₂O₃-SrO-CaO-CuO, a simple annealing procedure was developed to precipitate Bi_2+xSr_2+xCuO_6+d, Sr₁₄Cu₂₄O_41−x, and Bi₂Sr₃O₆ in high-temperature superconducting Sr-rich “Bi₂Sr₂CaCu₂O₈” ceramics and Ca₂CuO₃ and a liquid in Ca-rich “Bi₂Sr₂CaCu₂O₈” ceramics. The transformation results in an increase of the critical current density of which is believed to express improved pinning properties of the superconducting crystals, in particular an increased pinning energy, which reduces the probability for thermally activated depinning. Possible pinning centers which were introduced during precipitation of the second phases are the surface of the precipitates.     

Dislocations and flux pinning in YBa2Cu3O7

The dislocation structures of bulk textured and epitaxial thin film YBa₂Cu₃O₇ superconductors are examined. Correlations between increases in flux pinning and dislocation densities are noted. A model for flux pinning by individual dislocations is presented. This gives a treatment of strain induced effects and effects of normal state region interactions. It is shown that the values of pinning predicted are in line with experimental observations.     

Kinetic Studies of the Interfacial Reaction of the Ba2YCu3O6+x Superconductor with a CeO2 Buffer

Interfacial reactions between the Ba₂YCu₃O_6+x superconductor and the CeO₂ buffer layers employed in coated conductors have been modeled experimentally by investigating the kinetics of the reaction between Ba₂YCu₃O_6+x films and CeO₂ substrates. At 810°C, the Ba₂YCu₃O_6+x -CeO₂ join within the BaO-Y₂O₃-CeO₂-CuO _x quaternary system is nonbinary, thereby establishing the phase diagram topology that governs the Ba₂YCu₃O_6+x /CeO₂ reaction. At a mole ratio of Ba₂YCu₃O_6+x :CeO₂ of 40:60, a phase boundary was found to separate two four-phase regions. On the Ba₂YCu₃O_6+x -rich side of the join, the four-phase region consists of Ba₂YCu₃O_{6 +x} , Ba(Ce_1−z Y _z )O_3−x , BaY₂CuO₅, and CuO _x ; on the CeO₂ rich side, the four phases were determined to be Ba(Ce_1−z Y _z ) O_3−x , BaY₂CuO₅, CuO _x and CeO₂. The Ba₂YCu₃O_6+x /CeO₂ reaction is limited by solid-state diffusion, and the reaction kinetics obey the parabolic rule, x = Kt ^1/2, where x = thickness of the reaction layer, t = time, and K = a constant related to the rate constant; K was determined to be 1.6 × 10⁻³ μm/s^1/2 at 790°C and 4.7 × 10⁻³ μm/s^1/2 at 830°C. The activation energy for the reaction was determined to be E _act = 2.67 × 10⁵ J/mol using the Arrhenius equation.     

Rare-earth-modified Sr0.5Ba0.5Nb2O6, ferroelectric crystals and their applications as infrared detectors

Rare-earth-modified ferroelectric crystals with the formula (Sr_1−xBa_x)1− 3y/2 R_yNb2₂O₆, where R = La, Nd, Sm, Gd, and Lu, have Been prepared and studied. When R = La, Nd, x ≃ .5 and y = 0.02, the modified material, at room temperature, exhibited twice the pyroelectric coefficient and four times the dielectric constant of the unmodified Sr_1−xBa_xNb₂O₆ (x ≃ .5). Curie temperatures decreased, dielectric constants increased, while loss factor and detector signal-to-noise ratios remained nearly the same with the addition of rare earth doping. The calculated response based on the measured properties agree with the measured response of actual detectors. These properties suggested that the modified SBN are good materials for small element or array pyroelectric infrared detector applications.     

Nd substitution in y/ba sites in melt processed YBa2Cu3O7− δ through Nd2O3 additions

YBa₂Cu₃O_{7− δ} (Y123) samples with excess Nd₂O₃ and Y₂O₃ additions in the same molar ratios were melt textured in air. In the Nd-doped samples, in addition to Y ion site substitution, partial substitution into the Ba²⁺ sites is anticipated because of the similar ionic sizes of Nd³⁺ and Ba²⁺. The microstructure, T_c, and magnetic properties of Nd-doped samples were analyzed and compared with undoped Y123 and samples with excess Y₂O₃. The Nd₂O₃ additions lead to significant magnetization improvements, likely due to both rare earth- and Ba-site substitution by the doped Nd³⁺ ions, and to increases in T_c. Y₂O₃ additions resulted in no marked property enhancement.     

Effects of platinum and oxygenation on microstructure in YBa2Cu3O7−δ/Y2BaCuO5 bulk materials

Transmission electron microscopy examinations have been conducted on undoped and PtO₂ doped YBa₂Cu₃O_7−δ, with excess Y₂BaCuO₅ (211) in the molar ratio of 5∶1 (123/211), processing using the solid liquid melt growth technique. Magnetization hysteresis suggests that addition of Pt strongly influences the pinning behavior. Considerable differences in dislocation and stacking fault densities were observed. Dislocation nets and tangles were commonly observed in the Pt doped samples. In both samples, stacking faults were observed near 211 precipitates, interplatelet boundaries, and dislocations. Dislocations appear to be formed during high temperature processing, while stacking faults appear to be generated during the final oxygenation step. The density and distribution of fine precipitates (∼25–100 nm) were comparable in both specimens suggesting that Pt additon affects the size and acicular morphology of only the coarser 211 (∼1–10 μm). It is proposed that the observed increase in J_c due to Pt addtion may be attributed to the increase in defect density rather than fine precipitates.     

Preparation and characterization of thin films of MgO,Al2O3 and MgAl2O4 by atomic layer deposition

MgO, Al₂O₃ and MgAl₂O₄ thin films were deposited on silicon substrates at various temperatures by the atomic layer deposition (ALD) method using bis(cyclopentadienyl)magnesium, triethylaluminum, and H₂O and were characterized systematically. High-quality polycrystalline MgO films were deposited for a substrate temperature above 500°C, and amorphous thin films were deposited around 400°C. The deposited Al₂O₃ and MgAl₂O₄ thin films were characterized as amorphous in structure. Applicability of ALD to complex oxides is discussed.     

Internal friction of superconducting YBa2Cu3O6+x wires at 200 kHz under in situ heat treatment

Using piezoelectric LiNbO₃ crystal oscillator method at 200 kHz, we have measured internal friction and modulus of YBa₂Cu₃O_6+x short wires with 1 mm-diameter and about 5mm length under in situ cyclic heating-cooling treatment at temperatures of 300–1020K. Polycrystalline YBa₂Cu₃O_6+x wires show anelastic behavior as well as orthorhombic-to-tetragonal (O-T) phase transition within present temperature range. There appears a strong internal friction peak below the O-T transition temperature, corresponding to the atomic site relaxation between oxygen and a vacancy in the Cu-O plane of oxygen defective YBa₂Cu₃O_6+x. A novel peak is observed after the cyclic heat treatments at around 700K. This relaxation is attributed to the hopping movement of oxygen in the defective local structure of YBa₂Cu₃O_6+x.     

Processing of large YBa2 Cu3Ox domains for levitation applications by a Nd1+x Ba2−x Cu3 Oy-Seeded melt-growth technique

YBa₂Cu₃O_x domains for levitation applications have been produced by a seeding technology that includes Nd_1+x Ba_2−x Cu₃O_y seeds and melt-processing technologies such as conventional melt-textured growth, melt-texturing with PtO₂ and Y₂BaCuO₅ additions, and the new solid-liquid-melt-growth technology. Large domains (∼20 mm) with high levitation forces (F₁ up to 8.2 N) have been produced. The reproducibility of the results is good, and the capability of producing a large number of pellets in a single batch indicates good potential for the production of large amounts of this material.     

Effect of thermal oxide on the crystallization of the anodic Ta2O5 film

SEM and TEM investigations of the crystallization process have been performed on amorphous Ta₂O₅ films grown by electrochemical oxidation of Ta foils. It was found that kinetics of crystallization and final structure of the anodic Ta₂O₅ film depend strongly on the thickness of the thermal oxide layer on the surface of the original Ta substrate. Two different modes of crystallization were detected for the substrate with native surface oxide and with the thermal oxide grown at elevated temperatures. Aborting of the crystallization was shown to be possible using short heating of the Ta₂O₅/Ta san dwiches which cuts crystalline inclusions grown into the amorphous matrix of the anodic Ta₂O₅ film from the Ta surface.     

用溶胶-凝胶法制备的Cu2Bi2Cr2O8薄膜 及其光学和铁磁性能研究

以硝酸铜Cu(NO₃)₂·3H₂O、硝酸铬Cr(NO₃)₃·9H₂O、硝酸铋Bi(NO₃)₃·3H₂O和乙二醇为原料,利用溶胶-凝胶工艺在石英衬底上制备了纳米Cu₂Bi₂Cr₂O₈薄膜。通过X射线衍射(X-Ray Diffraction, XRD)和拉曼测试对样品进行了表征。结果表明,Cu₂Bi₂Cr₂O₈薄膜具有良好的光学特性,其禁带宽度为1.49 eV;在磁性测试方面,Cu₂Bi₂Cr₂O₈薄膜呈现出了良好的铁磁性。     

Phase and magnetic properties of iron oxide clusters in 20CaO·20SiO2·7Fe2O3·6FeO glasses

The annealing of 20CaO·20SiO₂·7Fe₂O₃·6FeO glasses at 973K in vacuo produced clusters of iron oxide, the shape of which was nearly spherical and the diameter distributed in the narrow range 25–115Å. The phase of clusters was identified to be Fe³⁺(Fe³⁺ _{poststagger|1.30}Fe²⁺ _{poststagger|0.55}V_0.15)·O₄ in the inverse spinel structure based upon the Mössbauer spectra and x-ray diffraction profiles. The clusters exhibited superparamagnetism and their effective anisotropy energy constant was inversely proportional to the cluster diameter. The magnetization of the glasses measured by a vibrating sample magnetometer was 7.2 × 10^-6 Wbmkg^-1 at 10 kOe at room temperature and smaller than the value calculated assuming that the whole clusters have superparamagnetism. These results suggest the pinning of spins near the cluster surface.     

The phase transformation of Bi-Pb-Sr-Ca-Cu-O bulk materials are rapidly melted and solidified by a CO2 laser

The phase transformation of Bi_1.7Pb_0.4Sr_1.6Ca_2.4Cu_3.6O_y bulk materials rapidly melted and solidified by a CO₂ laser with the scanning speed of 40 mm/s were investigated. Results of x-ray diffraction pattern, scanning electron microscopy and energy-dispersive x-ray analysis showed the decomposition of the high-T_c phase in the laser irradiated region. Nonsuperconducting phases such as CaO and (Sr_1−xCa_x)CuO_y were found to be in the melting zone. On the other hand, (Sr_1−xCa_x)CuO_y and 2212 phase were also found in the heat-affected zone. When the irradiated samples were treated with 835‡C for 72 h in air, the laser treated region changed into the high-T_c as a major phase, in addition to the low-T_c phase and nonsuperconducting phase. However, the high-T_c phases are piled up randomly. The transport critical-current density of the laser treated samples after annealing is lower than that of the original sintered one, i.e. at 77K and zero magnetic field.     

Superconducting Properties of (M x /YBa2Cu3O7−δy )N Multilayer Films with Variable Layer Thickness x

The superconducting properties of (M _x /YBa₂Cu₃O_7−δy )_N multilayer films were studied for varying layer thickness x. Different M phases were examined including green-phase Y₂BaCuO₅ (211), Y₂O₃, BaZrO₃, CeO₂, SmBa₂Cu₃O_7−δ (Sm123), brown-phase La₂BaCuO₅ (La211), and MgO. Multilayer (M _x /YBa₂ Cu₃O_7−δy )_N structures were grown by pulsed laser deposition onto SrTiO₃ or LaAlO₃ single-crystal substrates by alternate ablation of separate YBa₂Cu₃O_7−δ (123) and M targets, at temperatures of 750°C to 790°C. The x layer thickness was varied from 0.1 nm to 4.5 nm, and the y 123 layer thickness was kept constant within a given range of 10 to 25 nm. Different M phase and x layer thicknesses caused large variations of the microstructural and superconducting properties, including superconducting transition (T _c), critical current density as a function of applied magnetic field J _c(H), self-field J _c(77 K), and nanoparticle layer coverage. Strong flux-pinning enhancement up to 1 to 3x was observed to occur for M additions of 211 and BaZrO₃ at 65 to 77 K, Y₂O₃ at 65 K, and CeO₂ for H < 0.5 T. BaZrO₃ had a noticeably different epitaxy forming smaller size nanoparticles ∼8 nm with 3 to 4x higher areal surface particle densities than other M phases, reaching 5 × 10¹¹ nanoparticles cm⁻². To optimize flux pinning and J _c (65 to 77 K, H = 2 to 3 T), the M layer thickness had to be reduced below a critical value that correlated with a nanoparticle surface coverage <15% by area. Unusual effects were observed for poor pinning materials including Sm123 and La211, where properties such as self-field J _c unexpectedly increased with increasing x layer thickness.     

Properties of solid-state electrochromic cells using Ta2O5 as electrolyte

Solid-state electrochromic (EC) cells (ITO/WO₃/Ta₂O₅/ITO), where ITO is indium-tin-oxide, were fabricated. Individual films were prepared by rf sputtering. The conduction mechanism in the Ta₂O₅ electrolyte was considered from the measurement of ac conductivity. Absorption spectra, coloration efficiency and memory characteristics of the EC cells were investigated. These results are compared with those of EC cells with liquid electrolytes.     

The growth of low dislocation density Sr1−x,Bax Nb2O6 crystals

The dislocation structures of both pure and Nd doped strontium barium niobate crystals, grown by the Czochralski method, were studied using an etch pit technique. It was determined that dislocations in the boule were being propagated from the seed and were confined to the center of the crystal. Typical dislocation density was 5x10⁴ cm⁻². Through the careful control of growth parameters and use of seed material cut from the dislocation free outer portion of a crystal, it was possible to grow crystals with very low dislocation densities, 1x10² cm⁻², and on occasion dislocation free crystals.     

Enhanced superconductivity in Nd1+xBa2-xCu3O7+δby low oxygen partial pressure annealing

Previous work has shown that unlike YBa₂ Cu₃ O_7-δ (Y123), the Nd-Ba-Cu-O system exhibits a solid solution Nd_1+xBa_2-x Cu₃O_7+δ (Nd123ss) for 0.04≤ × ≤0.6.^1–3) An earlier paper showed that although the superconducting properties decrease nonlinearly for increasing x, T_c can be varied by increasing the annealing temperature without changing the low temperature oxygen soak.² The changes in microstructure and T_c with increasing x are analogous with Y123 with increasing δ except that the total hole concentration remained constant. T_c was modeled in terms of oxygen disorder resulting from Nd³⁺ atoms on the Ba sites relocating chain oxygens to anti-chain sites. The variability in T_c as a function of x and processing conditions can be explained by the number of fourfold coordinated coppers on the chain sites. In this paper, the model has been further substantiated by processing in 1% O₂. The annealing in a reduced oxygen partial pressure followed by a 450°C oxygen soak resulted in a marked increase in T_c compared to the 100% PO₂ anneal. The low PO₂ anneal favors pairing of Nd³⁺ substituting for Ba²⁺ to conserve oxygen ions, resulting in fewer disrupted fourfold-coordinated coppers thus increasing charge transfer from the planes to the chains.     

Dry etch selectivity of Gd2O3 to GaN and AlN

Gd₂O₃ is a promising gate dielectric for GaN, but little is known of its dry etching characteristics. We achieved Gd₂O₃ etch rates up to ～600 Å · min^?1 in high density Cl2-based discharges, with maximum selectivities of ～15 over GaN and ～4 over AlN. Pure Cl₂ discharges produced reverse selectivities for both Gd₂O₃/GaN and Gd₂O₃/AlN, with typical values between 0.1–0.4. When a rare gas additive such as Ar or Xe was added to the plasma chemistry, the nitrides etched faster than the oxide. This indicates that volatile etch products (GaCl₃, AlCl₃, N₂) form in Cl₂-based plasmas once the GaN or AlN bonds are broken by ion bombardment, but that GdCl_x species are not volatile. In conjunction with the low efficiency for Gd₂O₃ bond-breaking at low ion energies, this leads to low selectivity.     

Effect of gas mixing ratio on etch behaviors of Ba2Ti9O20 (BTO) and Pt thin films in Cl2/Ar inductively coupled plasma

An investigation of the Ba₂Ti₉O₂₀ (BTO) and Pt thin films etch mechanism in the Cl₂/Ar inductively coupled plasma was carried out. It was found that an increase in Ar mixing ratio at fixed gas pressure and input power causes a fast decrease in the BTO etch rate (26.9-1.2 nm/min for 0-100% Ar) while the Pt etch rate increases slightly from 17.4-23.0 nm/min. Langmuir probe diagnostics and zero-dimensional plasma modeling provided the data on plasma parameters, steady-state composition and fluxes of active species on the etched surface. From the model-based analysis of etch kinetics, it was shown that the behavior of the BTO etch rate corresponds to the reaction-rate-limited etch regime, where the etch rate is limited neither by physical sputtering of the main material nor by the ion-stimulated desorption of low-volatile reaction products. The etch process of Pt appears in the transitional regime and is controlled by the neutral and ion fluxes together.