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.     

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.     

Recent status on high temperature superconducting Bi2Sr2CaCu2O8+x wire development at NYSIS: 1-90 meter length Jcs and 3 meter diameter ring furnace design

The status of long length, Bi₂Sr₂CaCu₂O_8+x (Bi-2212) wire development at the New York State Institute on Superconductivity (NYSIS) is reviewed and updated. Transport J_cs (4.2K, 0 T) of Bi-2212/Ag oxide powder-in-tube singlefilamentary tapes have reached 70,000-80,000, 50,000-60,000, and 30,000–40,000 A/cm² for 1, 4–15, and 40–90 meter length tapes, respectively. The decrease in J_c as the tape length was increased from 15 to 90 meters was attributed to the (measured) sensitivity of J_c to temperature nonuniformities (±3‡C) in the box-type furnace used for annealing. To reduce this problem, a ringtype high-temperature furnace (∼3 meter diameter) was designed and constructed which provides a large-volume (∼13^w × 10^h × 1000¹ cm) processing zone with expected excellent temperature uniformity (±0.5‡C). The advantages of the ring-type furnace for processing of kilometer-length conductors are described.     

Techniques for texturing ceramic superconductors from an amorphous precursor

Amorphous Bi₂Sr₂CaCu₂O₈ (Bi-2212) was crystallized under a uniaxial load of 1500 N at temperatures up to 880°C without Ag and 850°C with Ag to induce texture. Well textured samples (19 mm in diameter and 0.15 mm thick) were obtained for samples heated to within 99% of the melting temperature and quenched for samples with and without Ag. The rate limiting step for formation of the Bi-2212 from the amorphous precursor is a diffusion limited intercalation of (SrCa)CuO₂ into Bi₂Sr₂CuO₆ (Bi-2201) at T>600°C. Samples rapidly heated to within a few degrees of the melting temperature and quenched show 20 to 30% Bi-2201 layers within the Bi-2212 structure. Annealing these samples at 850°C for >60 h eliminates most of the Bi-2201 layers resulting in sharper superconducting transitions and higher intracrystalline critical currents with no adverse effects on grain size or texture. It is more difficult to remove the intercalations in the Ag added material.     

On the role of Bi2Sr2Ca1Cu2O8 and Bi2Sr2Cu1O6 on the weak links and critical currents in (Bi,Pb)2Sr2Ca2Cu2O10/Ag superconducting tapes

Silver-sheated (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ (Bi2223) superconducting tapes with different Bi₂Sr₂CaCu₂O₈ (Bi2212) and Bi₂Sr₂Cu₁O₆ (Bi2201) concentrations, were prepared by using a two-step sintering processing and by varying cooling rates in the fabrication of the superconductors. The effect of residual Bi2212 and Bi2201 phases on weak links and critical currents of the Bi2223/Ag tapes was investigated. It was found that residual Bi2201 caused weak links at grain boundaries and limited the current-carrying capacity of the tapes. Comparatively, the residual Bi2212 phase had much less influence on both weak links and critical currents. Elimination of Bi2201 by sintering tapes at a low temperature in the final thermal cycle, or by cooling the tapes slowly, increased critical current by a factor of two. Flux pinning property was also improved by removing the residual Bi2201 phase.     

Electrical and infrared study of Bi2Sr2Ca1Cu2O8 in semiconducting,superconducting ceramic and superconducting glass ceramic state

We have studied the electrical and infrared properties of Bi₂Sr₂Ca₁Cu₂O₈ compound in three states. Electrical and IR measurements show that the pure powder state sample is a semiconductor, the ceramic Bi₂Sr₂Ca₁Cu₂O₈ sample prepared after annealing at 820°C for 240 hours shows a T_c of 85 K, whereas Bi₂Sr₂Ca₁Cu₂O₈ sample prepared through glassy route, i.e. melting at 1250°C and annealing at 820°C for 240 hours shows a drop of T_c by 5 K. The infrared spectra of superconducting ceramic and glass ceramic states in the available frequency range of measurement reveals the presence of three phonons. Since the vibrational mode around 595 cm^?1 is due to CuO₂ layers and as the CuO₂ layers are responsible for T_c in the ceramic superconductors, any change in these layers will affect the T_c. The shifting of the 595 cm^?1 mode towards lower frequencies in the glass ceramic due to different preparation process, indicates that there is a change in CuO₂ layers resulting in a change of T_c, which is confirmed by Four probe dc measurements.     

Phase relations and homogeneity region of the hightemperature superconducting phase (Bi,Pb)2Sr2Ca2Cu3O10+d

For the nominal composition of Bi_2.27−xPb_xSr₂Ca₂Cu₃O_10+d, the lead content was varied from x < 0.05 to 0.45. The compositions were examined between 800 and 890‡C which is supposed to be the temperatue range over which the so-called 2223 phase (Bi₂Sr₂Ca₂Cu₃O_10+d) is stable. Only compositions between x < 0.18 to 0.36 could be synthezised in a single phase state. For x <0.36, a lead-containing phase with a stoichiometry of Pb₄(Sr,Ca)₅CuO_d with a small solubiliy of Bi is formed, for x > 0.18 mainly Bi₂Sr₂CaCu₂O_8+d and cuprates are the equilibrium phases. The temperature range for the 2223 phase was found to be 800 to 890‡C but the 2223 phase has extremely varying cation ratios over this temperaure range. Former single phase 2223 samples turn to multiphase samples when annealed at slightly higher or lower temperaures. A decrease in the Pb solubility with increasing as well as decreasing temperature with a maximum at about 850‡C was found for the 2223 phase.     

Engineered flux-pinning centers in Bi2Sr2CaCu2Ox and TIBa2Ca2Cu3Ox superconductors

Three methods were used to introduce flux-pinning centers into Bi₂Sr₂CaCu₂O_x (Bi-2212) and TlBa₂Ca₂Cu₃O_x (Tl-1223) samples. It was found that carbon induced local decomposition, that nanosized Al₂O₃ additions created stable reaction products, and that second phases could be isolated in Tl-1223 during synthesis. Each of these defects enhanced flux pinning and was of most benefit at temperatures ≤ 35K.     

Microstructure and properties of Tl0.75Bi0.25Sr1.6Ba0.4Ca2Cu3Ox tapes

Ag-clad Tl_0.75Bi_0.25Sr_1.6Ba_0.4Ca₂Cu₃O_x tapes were fabricated by a powder-in-tube technique. The starting powders consisted of Bi₂Sr₂CaCu₂O_x plus simple oxides. The tapes were heated in flowing O₂ at 835–865 °C for 7.5–10 h. Room-temperature pressing at 1.0–1.5 GPa produced tapes with denser, more phase-pure cores, and transport critical current density J_c at 77 K in self-field that was increased by a factor of ≈2. The maximum J_c value of 6 × 10³ A/cm² was obtained with heating at 840 − 850 °C for ≈ 10 h, with three intermediate pressing steps. The cores of the best tapes were still rather porous and contained significant concentrations of nonsuperconducting phases.     

Crystal growth in Bi–Sr–Ca–Cu–O system

We report growth of Bi₂Sr₂CaCu₂O_8+δ single crystals with dimensions of 6×2×0.03 mm³ using a melt and growth technique. The oxygen content is determined to be δ≈0.13 by iodometric titration. The crystal is shown to be homogeneous and close to stoichiometric cation ratio. The superconducting temperature with a sharp transition width (10–90% level) of 6–8 K was determined to be T_c=92 K from resistivity and dc susceptibility measurements. The predominant impurity phase is a Cu-free crystal, whose composition is identified as Bi₁₀Sr₁₁Ca₅O_x. The crystal structure of Bi₁₀Sr₁₁Ca₅O_x is monoclinic with a=11.108(1) Å, b=5.9487(1) Å; c=19.838 (3) Åand β=101.5° (P2_1/c space group).     

Fabrication of Bi2Sr2CaCu2O x and Bi2Sr2Ca2Cu3O x Superconductor Thick Films by Using Cu-Free Precursors on Ni Substrates

We studied the formation of Bi₂Sr₂CaCu₂O _x (Bi-2212) and Bi₂Sr₂Ca₂Cu₃O _x (Bi-2223) thick films in a heat treatment process of the Ni-sheathed Bi-Sr-Ca-Cu-O (BSCCO) system. Cu was electrodeposited initially on the Ni substrates (Cu/Ni). Well-oriented Bi-2212 superconductor thick films were formed successfully on Ni tapes by liquid reaction between Cu-free precursors and Cu/Ni tapes. However, only a small amount of Bi-2223 was formed. Thick films were prepared by screen-printing with Bi₂O₃, SrCO₃, and CaCO₃ powders on Cu/Ni tapes and heat treating them. Heat treatment was performed in the temperature range of 750–850°C in a tube furnace for several minutes to hours. The phases and the microstructures of the high temperature superconductor thick films were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. Electrical properties were examined by the standard four-probe method. At the heat treatment temperature, the specimens were in a partially molten state during reaction between the oxidized copper layer and the screen-printed precursors on the Cu/Ni tapes.     

Chemistry of electron doped Ln2−xCexCuO4 superconductors

The electron doped Ln_2−xCe_xCuO₄ (Ln=lanthanide) oxides have intergrowth structures consisting of superconductively active CuO₂ sheets alternating with inactive (Ln, Ce)₂O₂ fluorite layers along the c-axis. Stabilization of such intergrowth structures requires bond length matching across the intergrowth interface. The bond length matching criterion causes a monotonic decrease in the Ce solubility limit from x=0.24 to x=0.15 as the size of Ln³⁺ decreased from Ln=La_0.5Nd_0.5 to Ln=Gd. Annealing in N₂ atm of Ln_2−xCe_xCuO₄ at temperatures above 900°C creates oxygen vacancies and the number of vacancies decreases with increasing Ce content. The value of x at which a semiconductor to superconductor transition occurs in Ln_2−xCe_xCuO₄ increases with decreasing size of Ln³⁺ due to an increasing Madelung energy caused by a decreasing Cu−O bond length.     

Growth of single unit-cell superconducting La2−xSrxCuO4 films

We have developed an approach to grow high quality ultra-thin films of La_2−xSr_xCuO₄ with molecular beam epitaxy, by adding a homoepitaxial buffer layer in order to minimize the degradation of the film structure at the interface. The advantage of this method is to enable a further reduction of the minimal thickness of a superconducting La_1.9Sr_0.1CuO₄ film. The main result of our work is that a single unit cell (only two copper oxide planes) grown on a SrLaAlO₄ substrate exhibits a superconducting transition at 12.5 K (zero resistance) and an in-plane magnetic penetration depth λ_ab(0)=535 nm.     

The Power Factor of Bi<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Tl<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>3</Subscript> Single Crystals

Single crystals of the ternary system Bi_2−x Tl _x Se₃ (nominally x = 0.0 to 0.1) were prepared using the Bridgman technique. Samples with varying content of Tl were characterized by measurement of lattice parameters, electrical conductivity σ _⊥c, Hall coefficient R _H(B║c), and Seebeck coefficient S(ΔT⊥c). The measurements indicate that incorporation of Tl into Bi₂Se₃ lowers the concentration of free electrons and enhances their mobility. This effect is explained within the framework of the point defects in the crystal lattice, with formation of substitutional defects of thallium in place of bismuth (Tl_Bi) and a decrease in the concentration of selenium vacancies (V_Se ^{+ 2} V_{\rm{Se}}^{ + 2} ). The temperature dependence of the power factor σS ² of the samples is also discussed. As a consequence of the thallium doping we observe a significant increase of the power factor compared with the parent Bi₂Se₃.     

Increased pinning in “Bi2Sr2CaCu2O8” ceramics

From a consideration of the phase equilibrium diagram of the system Bi₂O₃-SrO-CaO-CuO, a simple annealing procedure was developed to transform single phase 2212 ceramics with compositions Bi_2.18Sr_1.75Ca_1.25Cu₂O_8+d and Bi_2.3Sr₂CaCu₂O_8+d into multi phase samples containing Ca₂CuO₃ and/or liquid. The transformations result in increases of the critical current densities at 1 T of 5–10 times, which is believed to reflect the increased pinning properties of these ceramics. The exact nature of the resulting pinning centres has not been determined yet.     

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.     

Thermoelectric Properties of (Pb,Sn,Ge)Te-Based Alloys

The search for alternative energy sources is presently at the forefront of␣applied research. In this context, thermoelectricity for direct energy conversion from thermal to electrical energy plays an important role. This␣paper is␣concerned with the development of highly efficient p-type [(PbTe)(SnTe)(Bi₂Te₃)] _x (GeTe)_1−x alloys for thermoelectric applications using spark plasma sintering (SPS). Varying the carrier concentration of GeTe was achieved by alloying of PbTe, SnTe, and/or Bi₂Te₃. The rhombohedral to cubic phase transition temperature, T _c, was found to be sensitive to the degree of alloying. Highest power factor values (P ≤ 33 μW/cm K²) were obtained for (GeTe)_0.95(Bi₂Te₃)_0.05 composition.     

Damage constant and deep-level transient spectroscopy in neutron irradiated GaAsP alloys

Damage produced in VPE GaAs_{1− x P x} . alloys by fast neutron irradiation at room temperature was studied, in light emitting diodes, through the evolution of device carrier lifetime, photoluminescence, electroluminescence and transient capacitance spectroscopy characteristics. Neutron fluxes were in the 10¹³−10¹⁴ neutrons/cm² range so as not to heavily damage the devices. Damage constants are 10⁻⁵ to 10⁻⁶ cm²/s for 0.3 ≤x ≤ 1. The carrier removal rate was ≈; 10 cm⁻¹. Deep-level transient spectroscopy in n-type layers revealed that fast neutrons created a broad center atE _c − 0.7 eV, and at a ≈;1 cm⁻¹ generation rate. For thex ≥ 0.4 composition range studied, trap characteristics and introduction rates were rather independent ofx. From photocapacitance quenching measurements it is suggested that the neutron generated centers are EL2-related.     

Rapid synthesis of Y- and Bi-based high-Tc cuprates by microwave irradiation

High-T_c superconducting samples of YBa₂Cu₃O_7−x with T_c∼90 K and Bi_2.2Sr_1.8Cu_1.05O_x with T_c∼9 K have been prepared for several ten min, using a domestic microwave oven operated at 2.45 GHz, without any post-heat-treatment. Post-heat-treatment is not necessary due to improvement of the sample environment during the microwave process. That is, a pellet of mixed powder of starting materials is surrounded by mixed powder of starting materials and, subsequently, wrapped in glass wool in order to suppress rapid dissipation of heat from the surface of the pellet. This leads to successful preparation of homogeneous and oxygenated samples. In addition, we have attempted to prepare Bi-2212 and Bi-2223 phases. A sample whose major phase was Bi-2212 was obtained. However, no sample with the Bi-2223 phase could be obtained.     

Effect of site-selective substitution in bulk superconducting Tl2Ba2CaCu2O8

Magnetization measurements were carried out on bulk Tl₂Ba₂CaCu₂O₈ (referred to as Tl-2212) and on various site-selective substituted Tl-2212 samples. At 5K between 0 and 4.5 T, the 5 at. % Mg-doped Tl-2212 (Tl,Mg-2212) samples displayed enhanced pinning as demonstrated by a field dependent increase of the magnetic critical-current density J_c by 18 to 25 percent over that of pristine Tl-2212. Excess Mg (10–15 at. %), however, is deleterious. Rietveld refinement of the x-ray diffraction pattern showed Mg on the Tl sites. Auger electron spectroscopy analysis showed part of the Mg on grain boundaries. The flux-creep activation energies are higher for flux expulsion than for flux penetration in both Tl-2212 and Tl,Mg-2212 samples; the latter displays higher individual values. Our results demonstrate an increase in the number density of flux lines as a result of increased density of atomic-size-structural, defects by Mg (5 at. %) doping. In the Tl_2−yBa₂(Ca_1−zY_z)Cu₂O_8−x(z=0–0.3; single phase; x and y represent oxygen and thallium vacancies) system also studied, the T_c decreases as z increases. At z=0.3, the sample becomes an antiferromagnetic semiconductor.