Fabrication of NdBa2Cu3O7−δ single crystals by the top-seeded solution-growth method in 1%, 21%, and 100% oxygen partial pressure atmosphere

Single crystals of NdBa₂Cu₃O_7−δ (Nd123) have been successfully grown by the top-seeded solution-growth (TSSG) method in 1%, 21% and 100% oxygen partial pressure atmosphere ((P(O₂) = 0.01 atm, P(O)₂) = 0.21 atm and P(O₂) = 1.00 atm). Ba---Cu---O solvent with a Ba to Cu ratio of 3:5 was used in a Nd₂O₃ crucible. Nd is supplied by the reaction between the molten solvent and the Nd₂O₃ crucible. Compositions of Nd123 single crystals grown in different oxygen partial pressure atmospheres were analyzed by inductivity coupled plasma atomic emission spectrometry (ICP-AES) and confirmed to be Nd:Ba:Cu = 1.01:1.97:3.00 for P(O₂) = 0.01 atm, Nd:Ba:Cu = 1.07:1.95:3.00 for P(O₂) = 0.21 atm and Nd:Ba:Cu = 1.10:1.90:3.00 for P(O₂) = 1.00 atm, respectively. The Nd123 single crystals grown in different oxygen partial pressure atmospheres were annealed in a pure oxygen gas flow, and the temperature dependence of the DC magnetization for these crystals was measured using a superconducting quantum interference device (SQUID) magnetometer. The Nd123 single crystal grown in P(O₂) = 0.01 atm, and annealed at 340°C for 200 h showed a steep superconductive transition at 96 K. On the other hand, the Nd123 crystal grown in P(O₂) = 0.21, 1.00 atm and, annealed at 340°C for 200 h exhibited a broad transition at 92 K for P(O₂) = 0.21 atm and at 88 K for P(O₂) = 1.00 atm, respectively. Therefore for Nd123 single crystal production with high quality superconductive characteristics, a low oxygen partial pressure atmosphere during crystal growth is found to be effective for minimizing the substitution of Nd ions into Ba sites.     

Field-induced pinning effect of Nd(Ba1−xNdx)2Cu3O7−δ single crystals grown by the traveling-solvent floating-zone method

We have studied the superconducting properties of Nd(Ba_1−xNd_x)₂Cu₃O_7−δ (Nd123, x ≈ 0.1) single crystals grown by the traveling-solvent floating-zone method under 0.1% O₂ in Ar atmosphere. The enhancement of the magnetization with increasing field is observed in the hysteresis (M-H) loop in fields both parallel and perpendicular to the c-axis of the Nd123 single crystals as well as in the bulk crystals prepared by the oxygen-controlled-melt-growth (OCMG) method. The composition variation of Ba/Nd is observed in the matrix of Nd123 crystals by an analytical TEM equipped with a cold field-emission gun. It turns out that the enhancement is due to the field-induced pinning effect ascribed to the weak superconducting Nd---Ba substitution regions in the Nd123 matrix.     

Electrons and holes in undoped Nd2CuO4

Nd₂CuO_4±δ is the non-superconducting prototype of the Re_2−xM_xCuO₄t−y family (Re=Pr, Nd, Sm and M=Ceor Th) of n-type oxide superconductors. Four-probe DC conductivity, EMF in P(O₂) gradient, and thermopower measurements have been used to characterise its electric transport and defect structure between 300 and 900°C and between 5×10⁻⁴ and 1 atm oxygen partial pressure.

The results show that Nd₂CuO_4±δ can be oxygen under-stoichiometric (with n-type conductivity), near-stoichiometric, and over-stoichiometric (with p-type conductivity) in different T, P(O₂) ranges.     

Effect of oxygen partial pressure on the lower solubility limit of Nd1+xBa2−xCu3O7

The lower solubility limits of Nd_1+xBa_2−xCu₃O₇ (Nd123ss) in 1 bar, 0.2 bar, 0.01 bar, and 0.001 bar oxygen partial pressure (P_O2) were studed by differential thermal analysis (DTA) and X-ray diffraction (XRD). Large relative changes in stability with decreasing P_O2 explain why sharp superconducting transitions can be achieved in P_O2 ≤ 0.01 bar while processing in 0.2 to 1 bar P_O2 tends to produce broad transitions. While the lower solubility limits in 0.01 bar and 0.001 bar P_O2 remain at x = 0.00, the solubility limits in 0.2 bar and 1 bar P_O2 show a narrowing with decreasing temperature. Because of the narrowing of the solubility range in 1 bar P_O2, oxygen annealing of Nd123 initially processed in low P_O2 will result in precipitation of second phases which act as flux pinning centers.     

Oxygen nonstoichiometry and phase transitions of the neodymium-rich Nd1+xBa2−xCu3Oz solid solution

On the basis of chemical, thermal analysis and Cu K-edge X-ray absorption measurements, oxygen content in the Nd_1+xBa_2−xCu₃O_z solid solution was determined between 1000°C in air and 400°C in oxygen for x=0.05–0.9 compositions. It has been observed that the oxygen nonstoichiometry Δz of the Nd_1+xBa_2−xCu₃O_7+x/2−Δz solid solution decreases 2–2.5 times for a large substitution (Δz≈0.3–0.33 for x=0.9), despite of the acclaimed higher total oxygen content. The difference in nonstoichiometry is explained by a higher average value of the copper oxidation state (ACV), which is vital for the solid solution with large x even at elevated temperatures (ACV≈2–2.05 for x>0.3 at 1000°C, PO₂=0.21 atm). On the contrary, the ACV after complete oxygenation is almost constant (about 2.25–2.3) for the whole series. The x-dependence of the oxygen content is not monotonous and structural phase transitions can be observed at x=0.3 and x=0.6, as confirmed by the X-ray diffraction and the Raman scattering spectroscopy. The first well-known transition is connected with the oxygen disorder due to the Nd substitution for Ba at random Ba-sites. In the present work, it is proved by the apical oxygen mode broadening in Raman spectra. Ordering of the Nd and Ba atoms with a subsequent orthorhombic distortion of the lattice may occur even at 1000°C in air due to the second transformation at x≈0.6. The invariable orthorhombicity of the Nd-rich solid solution with x>0.6 is not caused by the oxygen absorption as in the x=0.05 case. Existence of high- and low-temperature orthorhombic modifications of this solid solution has been observed for the first time. Finally, a tentative 3D (z–x–T) diagram is suggested for the Nd_1+xBa_2−xCu₃O_z solid solution up to 1000°C in air, including the new x=0.6–0.9 region.     

Phonon Raman scattering in Nd1+xBa2−xCu3O7−δ and Pr1+xBa2−xCu3O7−δ single crystals

The polarized Raman spectra of Nd_1+xBa_2−xCu₃O_7−δ (−0.023≤x≤0.107) and Pr_1+xBa_2−xCu₃O_7−δ (0.01≤x≤0.15) single crystals have been investigated. It was found that the Cu(2) A_g mode softens by 6 cm⁻¹ in Nd 1:2:3 and 4 cm⁻¹ in Pr 1:2:3 as x increases. These frequency shifts cannot be explained by the change in the relevant bond lengths due to Nd(Pr)-substitution for Ba. The variations with x of the two low frequency modes may be affected by change of their hybridization and/or change of their force constants. The linewidths of Ba mode in Pr 1:2:3 are broader than those in Y 1:2:3. This result suggests that the Pr substitution on Ba sites occurred even in a very small value of x. In x(yy) geometry the relative intensity of the Ba and O(4) modes in Nd 1:2:3 is greater than those in Pr 1:2:3. The difference between Nd 1:2:3 and Pr 1:2:3 in the relative intensity of the Ba and O(4) modes may be produced by the chains.     

Phase equilibria at low oxygen partial pressure in the Y---Ba---Cu---O system

The phase equilibria around YBa₂Cu₃O_7−x (123) and YBa₂Cu₄O₈ (124) phases at low oxygen partial pressure (1 atm) were investigated by X-ray diffraction and thermal analysis. The coexistence of 123 and 124 phase was confirmed under 1 atm oxygen pressure. By using the high temperature X-ray diffraction method, the univariant reaction YBa₂Cu₃O_7−x+Cu₂OY₂BaCu₂O₂+O₂ was identified. The oxygen partial pressure dependence of several univariant reactions has been investigated and the existence of two invariant reactions of L+O₂YBa₂Cu₃O_7−x+ BaCuO₂+CuO+Cu₂O and L+Y₂BaCuO₅+O₂YBa₂Cu₃O_7−x+CuO+Cu₂O was deduced to occur at 1103 K under 0.0032 atm O₂ and at 1143 K under 0.0085 atm O₂, respectively.     

Phase diagrams of YBa2Cu4O8 and YBa2Cu3.5O7.5 in the pressure range 1 bar≤PO2≤3000 bar

The P-T-x phase diagram of the pseudobinary system (Y-Ba-Cu-O)-O₂ has been further investigated in the oxygen pressure range between 1 and 3000 bar. The stability ranges of the phases YBa₂Cu₄O₈ (124), YBa₂Cu_3.5O_7.5−x (123.5) and YBa₂Cu₃O_7−x (123) have been determined. Long duration experiments showed that the 123 phase is not stable at least down to 7 bar≤P≤20 bar oxygen and 900°C. It is not clear whether at lower pressures and temperatures the 123 phase is thermodynamically stable or metastable due to low reaction rates. In the presence of excess CuO, the 124 is the stable phase. The melting of 124 pellets at P_O2=2800 bar shows that even at this pressure the 124 compound melts incongruently. Using the phase diagram data we could change the T_c of 123.5 from 16 to 70 K by varying systematically the nonstoichiometry. Due to a narrow homogeneity range the T_c of 124 remained constant but is different for powder pellets (81 K) and for crystals (70 K), probably due to the influence of the flux. Single crystals of both 124 and 123.5 with dimensions up to 4 mm were grown from the flux under high oxygen pressure.     

Preparation of melt-textured NdBa2Cu3Oy bulk with Nd4Ba2Cu2O10 addition

The NdBa₂Cu₃O_y (Nd123) bulk superconductor, to which Nd₄Ba₂Cu₂O₁₀ (Nd422) particles were intentionally added, was prepared through the so-called MMTG process in Ar (99% purity) flowing atmosphere at an ambient pressure. The quasi-single crystal thus grown was about 1 cm × 1 cm × 1 cm in dimension. It turned out that the Nd422 particles were uniformly distributed in the Nd123-phase matrix in a fashion similar to the distribution of the intentionally added Y211 particles in the Y123 phase matrix. The superconducting transition temperature T_c for the sample subjected to post-annealing in oxygen atmosphere was 94 K. The critical current density J_c was determined to be 45 000 A/cm² at 77 K and 1 T, when the field was applied parallel to the c-axis of the sample. To the best of our knowledge, the J_c value is the highest and the size of the quasi-single crystal is the largest in the melt-textured Nd123 bulk superconductors so far reported.     

Non-steady state solidification of the Nd-123 superconducting oxides

Crystal growth of the melt-textured bulk Nd_1+xBa_2−xCu₃O_6+d (Nd123) superconducting oxides was investigated by employing isothermal undercooling solidification with hot-seeding in air. From the relationship between growth length and holding time, the Nd123 crystal was found to have almost stopped growing after a certain growth period, while the growth length increased proportionally to the holding time at an early stage of the crystal growth. As a result of quantitative analysis for the Nd123 crystal of which solidification was terminated, the distribution of the Nd/Ba substitution was observed to decrease in the Nd123 single crystal matrix from the seed crystal to the edge of the Nd123 crystals. Also, the substitution content at the edge of the Nd123 crystal, which corresponds to that at the final stage of the crystal growth, was found to be in good agreement with the minimum substitution of the Nd123 solid solution phase in the equilibrium phase diagram at this process temperature. These compositional changes could be explained using the equilibrium phase diagram as associated with the solid solution formation, which is responsible for the non-steady state solidification of the Nd123 crystals even for the isothermal undercooling processing.     

Oxygen ion conductivity of yttria-niobia mixed oxide with fluoride related structure

The oxygen ion conductivity of Y₂O₃---Nb₂O₅ with a fluorite-like structure was studied. Substitutional solid solutions of Nb₂ O₅ in Y₂O₃ lattice formed the defect fluorite phase and remarkably enhanced the oxygen ion conductivity. Doping with tetravalent cations, especially Ti⁴⁺ or Ce⁴⁺, in yttria-niobia oxide is effective in enhancing the oxygen ion conductivity. Although the n-type semiconducting property appeared below P_O2 = 10⁻¹⁸ atm at 1243 K, the yttria-niobia mixed oxide doped with Ce⁴⁺, Ti⁴⁺, and Zr⁴⁺ stably exhibited oxygen-ion conduction in the wide range of oxygen partial pressures studied.     

Niobium based tetragonal tungsten bronzes as potential anodes for solid oxide fuel cells: synthesis and electrical characterisation

In this paper we report studies on a range of niobate based tungsten bronzes, with a view to analysing their potential as anode materials in SOFCs. Six systems were studied, (Sr_1−xBa_x)_0.6Ti_0.2Nb_0.8O₃, Sr_0.6−xLa_xTi_0.2+xNb_0.8−xO₃, (Sr_0.4−xBa_x)Na_0.2NbO₃, (Ba_1−xCa_x)_0.6Ti_0.2Nb_0.8O₃, Ba_0.5−xA_xNbO₃ (A=Ca, Sr), and Ba_0.3NbO_2.8, and the electrical conductivities were examined over a range of oxygen partial pressures (10⁻²⁰–1 bar). All the systems showed good conductivity in low oxygen partial pressures, with values as high as 8 S cm⁻¹ at 930°C (P(O₂)=10⁻²⁰ bar). As the oxygen partial pressure was raised the conductivity dropped showing in most cases an approximate [P(O₂)]^−1/4 dependence and good re-oxidation kinetics. Of all the samples studied the (Sr_1−xBa_x)_0.6Ti_0.2Nb_0.8O₃ and (Ba_1−xCa_x)_0.6Ti_0.2Nb_0.8O₃ systems appear most promising for potential use as anode materials in SOFCs.     

Oxygen diffusion and surface exchange in La1−xSrxFe0.8Cr0.2O3−δ (x=0.2, 0.4 and 0.6)

Oxygen tracer diffusion (D*) and surface exchange rate constant (k*) have been measured, using isotopic exchange and depth profiling by secondary ion mass spectrometry (SIMS), in La_1−xSr_xFe_0.8Cr_0.2O_3−δ (x=0.2, 0.4 and 0.6). Measurements were made as a function of temperature (700–1000 °C) and oxygen partial pressure (0.21–10⁻²¹ atm) in dry oxygen, water vapour and water vapour/hydrogen/nitrogen mixtures. At high oxygen activity, D* was found to increase with increasing temperature and Sr content. The activation energies for D* in air are 2.13 eV (x=0.2), 1.53 eV (x=0.4) and 1.21 eV (x=0.6). As the oxygen activity decreases, D* increases as expected qualitatively from the increase in oxygen vacancy concentration. Under strongly reducing conditions, the measured values of D* at 1000 °C range from 10⁻⁸ cm² s⁻¹ for x=0.2 to 10⁻⁷ cm² s⁻¹ for x=0.4 and 0.6. The activation energies determined at constant H₂O/H₂ ratio are 1.21 eV (x=0.2), 1.59 eV (x=0.4) and 0.82 eV (x=0.6).

The surface exchange rate constant of oxygen for the H₂O molecule is similar in magnitude to that for the O₂ molecule and both increase with increasing Sr concentration.     

The crystallographic symmetries of single BaPb1−xBixO3 crystals grown from BaCO3-PbO2-Bi2O3 solutions

Single crystals of Perovskite-type oxide BaPb_1−xBi_xO₃ are grown from BaCO₃-PbO₂-Bi₂O₃ solutions which are weighed in two kinds of mixing ratios: X/2 mol % BaCO₃ − (100−X) mol % PbO₂ − X/2 mol % Bi₂O₃ and (10+X/2) mol % BaCO₃ − (90−X) mol % PbO₂ − X/2 mol % Bi₂O₃ These room temperature crystal structures are examined by using an X-ray powder diffraction method. The crystals grown from X/2−(100−X)−X/2 mol % solutions are orthorhombic at room temperature, while the structures are tetragonal with crystals grown from relatively Ba rich and Pb poor ( (10+X/2)−(90−X)−X/2 mol % ) solutions. This result indicates that the difference in the mixing ratio of the initial materials brings about a drastic structural change. The orthorhombic and the tetragonal crystals of x0.25 exhibit superconducting transition at 10K and 12K, respectively. The transition temperature in the latter is 2K higher than the former. In the light of this result, some difference between orthorhombic and tetragonal crystals is considered to influence superconductivity in this system.     

Zero-field current-voltage characteristics in high-temperature superconductors

We have observed the anomalous magnetization of Bi₂Sr₂CaCu_2−xNi_xO₈ (x = 0 and 0.02) single crystals. Anisotropy decreases with iodine intercalation although it expands the space between CuO₂ layers. Iodine intercalation seems to suppress the magnetization anomaly for Ni = 1% crystals, but not for Ni = 1% substituted crystals. We have discussed these results in terms of the increase of anisotropy by Ni substitution and the dimensional crossover of flux lines. Effects of both oxygen concentration and substitution of a magnetic element for the Cu site on the anisotropy of Bi₂Sr₂CaCu₂O₈ crystals show the same tendency as the case of the YBa₂Cu₃O₇ superconductor.     

(Tl, Pb, Cu)Sr2(Tl, Pb, Cu)2Cu2O8−δ: a nonsuperconducting Tl-1222 cuprate with both heavy atom single and oxygen depleted double layer motifs

An account is given of the synthesis and structural investigation of a newly discovered tetragonal (Tl, Pb, Cu)Sr₂(Tl, Pb, Cu)₂Cu₂O_8−δ compound (Tl-1222^* phase) with both (Tl, Pb, Cu)O single and oxygen depleted (Tl, Pb, Cu)₂O_x double layer motifs, space group I4/mmm, lattice parameters a=3.8405(2), c=29.2536(5) Å, and D_x=7.46 g cm⁻³. Micaceous and highly reflecting black single crystals of 1 mm×1 mm×3–5 μm size were obtained from a Tl₂O₃- and CuO-rich partial melt. The as-grown compound is nonsuperconducting. The very thin crystals are extremely liable to bend out of shape. Deterioration could not be observed within the period of a year under ambient conditions. The complex crystal structure has been solved using single crystals. We take note of the similarity of the unit cell dimensions to superconducting (Tl, Cu)₂Ba₂(Ca, Tl)Cu₂O₈ (Tl-2212 phase) with TlO double rocksalt layers, and compare crystal-chemical details of similar compounds. Apart from the possibility of obtaining superconducting properties by suitable doping, the mechanical properties of the new material are very attractive from the point of view of its use as highly scattering composite layers of an X-ray monochromator.     

铀在Nd_2Zr_2O_7烧绿石中的固溶量及重离子辐照效应

Nd_2Zr_2O_7烧绿石因其稳定的物理化学性质和辐照稳定性可以作为高放废物中锕系核素的固化基材.通过溶胶凝胶—喷雾热解—高温烧结方法制备了含铀的Nd_2Zr_2O_7烧绿石固化体;开展了Nd_2Zr_2O_7和Nd_(1.9)U_(0.1)Zr_2O_7固化体的重离子辐照实验,辐照剂量为1 dpa和3 dpa;利用X射线衍射和Raman光谱对固化体结构进行了分析.研究发现铀在Nd_2Zr_2O_7烧绿石体系的固溶量仅为10 at%,高价态铀掺杂导致固化体结构向无序化转变.重离子辐照实验表明, Nd_2Zr_2O_7烧绿石基材具有较高的抗辐照稳定性;而Nd_(1.9)U_(0.1)Zr_2O_7在较低辐照剂量下,固化体烧绿石体系结构破坏,重离子辐照诱导固化体结构转变为更加无序化的萤石结构.低固溶量和抗辐照能力减弱主要是由于锕系核素烧绿石固化体的结构无序化所致.     

Thermal transport in the oxygenated magnetic superconductor, Eu1.5Ce0.5RuSr2Cu2O10+δ

The thermal conductivity and thermopower are reported for a hole doped Eu_1.5Ce_0.5RuSr₂Cu₂O_10+δ sample that has been annealed at 1100 K under an oxygen pressure of 54 atm. At T_c=45 K superconductivity and weak ferromagnetism coexist (T_m=180 K). Weak features in the thermopower, S(T), and thermal conductivity, κ(T), are observed both at T_m and at T^*=140 K. The thermopower begins to decrease sharply toward zero at T_c, and there is an extremely sharp increase of about 30% in the thermal conductivity at T_c. This “first order” transition may be related to the sudden appearance of a spontaneous vortex phase at T_c. A small shoulder is observed in κ(T) in the temperature range T=5–13 K.     

Defects in Nd2CuO4 and Nd1.815Ce0.185CuO4 single crystals

We describe here four kinds of defects found in Nd₂CuO₄ and Nd_1.815Ce_0.185CuO₄ single crystals grown by the traveling solvent floating zone method. These defects include: (1) cracks, (2) inclusions, (3) gas bubbles and (4) uneven distribution of Ce⁴⁺. The formation mechanism of these defects and the measures of eliminating these defects are discussed. It is thought that the preparation of raw materials and stringent growth conditions are necessary to obtain high quality of Nd₂CuO₄ and Nd_1.815Ce_0.185CuO₄ single crystals.     

Low-temperature studies of two Y-type hexagonal ferrites: BaZnFe6O11 and BaCoFe6O11

Single-crystal X-ray diffraction studies have been performed at low temperature (T=15 K) on the BaZnFe₆O₁₁ and BaCoFe₆O₁₁ (Y-type) room-temperature ferrimagnetic hexagonal ferrites. From the refined structures, we notice high thermal vibrations for the oxygen anions, especially for the O3 one which lies around the large Ba cation. From powder neutron diffraction at T=2 K we confirm the collinear Gorter model of the magnetic structure in the basal plane for BaZnFe₆O₁₁; the reductions of the magnetic moments located on the (6c^*_IV) and (6c_IV) sites are discussed from superexchange qualitative considerations.