Structure and properties of Bi2Sr2CaCu2Ox/Bi2Sr2CuOx superlattices prepared by RF magnetron sputtering

We have prepared Bi₂Sr₂CaCu₂O_x/Bi₂Sr₂CuO_x (2212/2201) superlattices with various stacking periodicity by multitarget RF magnetron sputtering. Their crystal structure and electrical properties were investigated. The superlattice was found to be successfully constructed from the data of XRD patterns, AES, etc. The critical temperature increased almost linearly with increasing thickness of the 2212 phase up to a thickness of 6 unit cells. On the other hand, it did not decrease as the thickness of the 2201 layers was increased. The unit cell/unit cell superlattice showed T_{c zero} of 30 K.     

Magnetic properties of the Bi1.95Sr2.05−xLaxCuOy (Bi-2201) superconducting phase

We have investigated the reversible mixed-state magnetization M of three lanthanum substituted Bi_1.95Sr_2.05−xLa_xCuO_y (Bi-2201) ceramic samples having different critical temperatures T_c ranging from 20.0 to 35.5 K. As for the Bi₂Sr₂CaCu₂O_8+δ (Bi-2212) phase, we found that anisotropy of Bi-2201 is large. A manifestation of this anisotropy is the field independent magnetization M^* observed at a temperature T^*. In the framework of the London model, and including thermal fluctuations of vortices, we found for the temperature dependence of the penetration depth λ_ab(T) = λ_ab(0)[1 − (T/T_c0)ⁿ]^−1/2, with n 1.7 and λ_ab (T = 0) 4000 Å. The estimated upper critical fields μ₀H_c2,c are of the order of 10 T. We observe a peculiar negative slope M/T at low temperature and sufficiently high external magnetic field. This feature seems to be a characteristic of the Bi-2201 phase. However, we do not know whether it is associated with the superconducting mixed-state. A small amount of magnetic impurities could also be responsible for this behavior. Finally, the behavior of the reversible magnetization of the Bi-2201 samples investigated, which are situated at the optimal and in the overdoped region, did not indicate any unusual temperature dependence for the upper critical field H_c2,c.     

The incommensurate modulation in the Bi2Sr2−xCaxCuO6 superconductor, and its relation to the modulation in Bi2Sr2−xCaxCu2O8

The modulation of the (221) superconducting Bi₂Sr_2−xCa_xCuO₆ phase has been analyzed by X-ray diffraction, using four-dimensional symmetry theory. The pseudo-orthorhombic diffraction pattern is a superposition of two twin related components, such that the main reflections with hkl and hk m superimpose, but the satellite hklm and hk m do not. The latter feature allows separation of the twin intensities. The modulation analysis in superspace group P:Aa:1 shows displacements similar to those observed in the 2212 compound [Y. Gao et al., Science 241 (1988) 954] but with generally larger displacements. In particular, the c-axis displacement amplitude of the Cu atoms is increased to almost 0.5 Å. This and the obliqueness of the q vector (q=0.214a^*+0.61c^*) indicate the absence of a restraining influence exerted by the CuO₂/Sr(Ca)/CuO₂ double layers in the multi-Cu layer phases.     

(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.     

A 62 K superconductor with an original structure: Sr4−xBaxTlCu2CO3O7

A new superconductor with an original structure, Sr_4−xBa_xTlCu₂CO₃O₇ has been isolated for 1≤x≤2. It crystallizes in a A-type space group with a=3.84 Å≈a_p, b≈8 × a_p, c≈17.0 Å. The HREM study of this new curprate shows that it derives from the Tl_0.5Pb_0.5Sr₄Cu₂CO₃O₇ structure by a shearing mechanism. Indeed, it can be described as ribbons of the latter structure, four octahedra thick, shifted c/2 with respect to each other. It results in infinite single perovskite layers waving along the (001) plane and connected through flat mixed layers [(TIO)₄(CO)₄]∞. This oxycarbonate can also be described as a 1201-type structure in which the [TIO]∞ layers are replaced by mixed [(TIO)₄(CO)₄]∞ layers. The susceptibility measurements show that this cuprate exhibits a significantly higher critical temperature than the 1201-cuprates. The T_{c onset} of the synthesized phase is 56 K and it can be increased up to 62 K by hydrogen annealing; in the same way, one observes a large Meissner volume fraction of 35% at 4.2 K.     

Effects of 230 MeV Au irradiation on Bi2Sr2CaCu2Ox

Bi₂Sr₂CaCu₂O_x tapes were irradiated using 230 MeV Au¹⁴⁺ ions. Columnar defects were presumably produced due to irradiation. Zero-field-cooling (ZFC) magnetization increased up to a fluence of 1.6 × 10¹¹ Au⁺/cm², but field-cooling (FC) magnetization decreased, indicating the strong pinning effects resulting from the columnar defects. The critical current density as well as the irreversibility field, obtained from the hysteresis loops, were enhanced. Irreversibility fields are fitted by H_irr = A exp(−T/T_A). An effective activation energy for flux motion was obtained from the measurements of magnetization relaxation. The features of flux pinning as a result of the columnar defects were compared with those of point defects brought about by 120 MeV O⁷⁺ irradiation.     

Synthesis and characterization of HgBa2Can−1CunO2n+2+δ (n = 1, 2, and 3)

We have successfully prepared the first three members of the mercury-based superconducting compounds Hg--- Ba₂Ca_n−1Cu_nO_2n+2+δ, namely Hg---1201, Hg---1212 and Hg---1223 with high purity and very good quality. T he influence of the synthesis parameters is studied in detail. Using the sealed quartz tube method, very simple procedures are found to ensure a 100% reproducibility of nearly 100% pure Hg---1201 and 85–90% Hg---1212 and Hg---1223. Oxygen annealing of the sample Hg---1201 at 300°C for 18 h results in an enhancement of its critical temperature up to 97 K. The symmetry of the first and second members is tetragonal with lattice parameters a = 3.8831 (1) Å, C = 9.5357 (2) Å, and A = 3.8624 (1) Å, C = 12.7045 (2) Å, respectively. X-ray diffraction lines of Hg---1223 can be indexed in a tetragonal cell with a = 3.8564 (1) Å and C = 15.8564 (9) Å as well as in an orthorhombic cell with lattice parameters a = 5.4537 (1) Å, B = 5.4247 (1) Å, and C = 15.8505 (7) Å.     

Study on the superconducting composite material formation in the system Bi2Sr2CaCu2O8+x/Al-containing phases

Phase evolution in the Bi---Sr---Ca---Cu---Al---O system was studied. Two Al-containing phases BiSr_1.5Ca_0.5Al₂O_z and (Sr_1−xCa_x)₃Al₂O₆ (x = 0.4 − 0.45) were determined to be chemically compatible with Bi_2.18Sr₂CaCu₂O_8+x (Bi-2212) at temperatures of the samples processing. The phase equilibria in the title system were investigated above the solidus temperature. The BiSr_1.5Ca_0.5Al₂O_z was found to be in equilibrium only with the melt and the (Sr_1−xCa_x)₃Al₂O₆ phase. This latter aluminate equilibrated with Ca,Sr cuprates, CaO, the Cu-free phase, and the liquid. The melting and solidification in Bi-2212, doped with the aluminate, corresponded to the reversible reaction Bi-2212 + BiSr_1.5Ca_0.5Al₂O_z ↔ (Sr_1−xCa_x)₃Al₂O₆ + liquid. Two sets of superconducting composite materials with initial compositions Bi-2212 + nBiSr_1.5Ca_0.5Al₂O_z and Bi-2212 + m(Sr_1−xCa_x)₃Al₂O₆ were prepared by solidification from the partial melt. The former material was composed mostly of large Bi-2212 lamellas separated by the BiSr_1.5Ca_0.5Al₂O_z phase, which destroyed superconducting links between Bi-2212 grains. The latter material consisted of a Bi-2212 polycrystalline matrix with high concentration of small (ca. 3 μm) grains of (Sr_1−xCa_x)₃Al₂O₆ imbedded in Bi-2212 lamellas. The Bi-2212 + m(Sr_1−xCa_x)₃Al₂O₆ materials displayed a trend to enhance flux pinning at T = 60 K with the increase of aluminate phase content.     

Observation of hotspot in BSCCO thin film structure by fluorescent thermal imaging

Hotspot formation is observed in a structured thin superconducting film of Bi₂Sr₂CaCu₂O_x (BSCCO) using the fluorescent thermal imaging technique. The BSCCO film is deposited on SrTiO₃ (STO) and has a superconducting transition at 80 K. A film of rare-earth doped polymer film deposited directly on the superconductor is used as thermal sensor down to 4 K.     

Oxygen nonstoichiometry effect on structural modulation in Bi-2212 cuprate superconductors

The X-ray diffraction patterns for Bi₂Sr₂Ca_1−xY_xCu₂O_8+y sintered in air or Ar indicated that the reduction in the number of excess oxygen ions induced a structural change from orthorhombic to pseudotetragonal. When the oxygen contents decreased with the reducing treatment, the period of modulation in Bi₂Sr₂Ca_1−xY_xCu₂O_8+y increased. This result supported the model of excess oxygen ions in the Bi---O sheet. However, it was difficult to understand the change of modulation period with increasing Y contents using the model of excess oxygen ions in the Bi---O layers. Also, it is included that the Y substitution for Ca and La substitution for Sr in the Bi₂Sr₂CaCu₂O_8+y system result in parallel effects for the modulation structure.     

Thermoelectric power and irreversibility field of (Hg,Tl)2Ba2Can−1CunOy (n=2–5) superconductors

We have measured the thermoelectric power, S, and the irreversibility field, H_irr, of the superconducting samples of (Hg,Tl)₂Ba₂Ca_n−1Cu_nO_y (n=2–5). S values for the (Hg,Tl)-22(n−1)n above their T_c's drastically increase with increasing n. Judging from the S values at room temperature, the n=2 and 3 samples are located in the overdoped region, the n=4 is in the almost optimally doped and the n=5 is in the underdoped region. H_irr values for the n=4 and 5 samples are higher than those for the as-synthesized and annealed n=3 samples. It is considered that the enhancement in H_irr is due not only to the increase of hole concentration but to the increase in the number of CuO₂ sheets.     

Superconductivity at 27 K in Nb-1222 cuprate: NbSr2(GdCe)2Cu2Oy

Samples of NbSr₂Gd_2−xCe_xCu₂O_y have been prepared by solid state reaction. The X-ray powder diffraction patterns show that a single phase can be formed in the composition range of 0.49<x<0.51 that has TaSr₂ (NdCe)₂Cu₂O_y structure [1], the cell parameters being a=3.8669±0.0046 Å and c=28.742±0.0048 Å. Superconductivity was found by resistance measurements in the sample of NbSr₂Gd_1.5Ce_0.5Cu₂O_y: the onset transition temperature is 27.4 K, and zero resistance appears at approximately 13 K.     

Evidence for pinning by (Sr,Ca)2CuOy particles in partial-melting processed bulk Bi2Sr2CaCu2O8+δ ceramics

Flux distributions of partial-melting processed Bi₂Sr₂CaCu₂O_8+δ ceramics are obtained using magneto-optic imaging. In remanent states (μ₀H_a=0 T), large amounts of trapped flux are observed along (Sr,Ca)₂CuO_y particles embedded in the Bi₂Sr₂CaCu₂O_8+δ matrix. Despite the relatively large size of these particles (up to 30 μm), the pinning effect is similar to that of Y₂BaCuO₅ particles in melt-processed YBa₂Cu₃O_7−δ. Furthermore, we discuss how the pinning capability of non-superconducting particles of different sizes and densities will show up in magneto-optic images.     

Crystal orientation in Bi-based superconducting glass-ceramics prepared in high magnetic field

A high magnetic field of 10 T was applied to the crystallization process of Bi₂Sr₂CaCu₂O_x superconducting precursor glasses, and the effect of high magnetic field on crystal grain orientations and superconducting properties were examined from electrical resistivity measurements, X-ray diffraction analyses and scanning electron microscope observations. The glass-ceramics prepared in a high magnetic field show better superconducting properties (higher critical temperature, larger critical current density, and smaller normal-state resistivity) compared with the samples crystallized in a normal heat-treatment with no magnetic field. It was found that Bi2212 crystal grains with a plate-like shape tend to stack to the direction of the magnetic field, i.e., the orientation of the c-axis of the Bi2212 phase to the direction of the magnetic field.     

Fabrication, microstructure and critical current density of screen-printed Ag-(Bi, Pb)2Sr2Ca2Cu3Ox superconducting tapes

The influence of the sintering conditions on the microstructure and critical current density J_c has been studied on screen-printed Ag-(Bi, Pb)₂Sr₂Ca₂Cu₃O_x tapes with a ceramics mono-layer core. Three kinds of fabrication processes, which consist of a combination of cold working (rolling and/or pressing) and sintering, are applied. Four times repetition of pressing and sintering after the pre-sintering produces the highest c-axis alignment and achieves J_c= 1.5 × 10⁴ A/cm² (77 K, 0 T). The J_c versus θ data with an angle θ between B and the c-axis elucidate the relation between the anisotropy ratio γ=J_c(Bc)/J_c(B|c and the half-height angular width Δθ of a peak for Bc. This is related to both grain alignment and the J_c value. An increase in J_c, which comes from an improvement for grain alignment, enhances γ and narrows Δθ. The J_c versus θ data are fitted to the expression J_c(B, θ)=J _c(B, 90°)/[(γ−1)|cos θ|ⁿ+1] by regarding both γ and n as adjustable parameters. Fabrication of screen-printed tapes with multilayers (1≤N≤5) is presented, where the critical current increases from 8.0 A to 30.2 A at 77 K and 0 T as N increases.     

New experimental evidence of the structural modification in single crystal Bi2Sr2CaCu2Oy by X-ray diffraction observation

The variations of the high angle 00 peak-shape by means of X-ray l scans of the 00l fundamental reflections were investigated in detail for a highly oriented Bi₂Sr₂CaCu₂O_y (Bi2212) crystal with sufficiently small intrinsic mosaicity and the same crystal annealed in air at 250, 300, 400, 600, and 750°C for 20 h in consequence. For the first time, we observed a new additional reflection almost overlapped original 00l fundamental reflection at annealing temperature below 400°C by X-ray diffraction measurement, which shows that there coexisted two sets of lattice periodicity in the c-direction of the annealed crystal. The new additional reflection appeared at 250°C and disappeared at 400°C. Its intensity was increased at 300°C. The measurements of the AC susceptibility, c-axis parameter and full width at half maximum (FWHM) of the 00 peaks showed that the new additional reflection was associated with the oxygen diffusion in CuO₂ planes and the changes of strain field. The results provide the new experimental evidence that the structural distortion is more sensitive to the oxygen diffusion in CuO₂ planes than to that in Bi–O layers.     

Crystal structure, superconductivity and magnetic properties of the superconducting ferromagnets Gd1.4−xDyxCe0.6Sr2RuCu2O10 (x=0–0.6)

The structural, electrical and magnetic properties of the superconducting ferromagnets, Gd_1.4−xDy_xCe_0.6Sr₂RuCu₂O₁₀ (x=0–0.6) are systematically investigated as a function of Dy doping and temperature. These compounds are characterized by high temperature superconductivity (T_c ranging from 20 to 40 K depending upon the Dy content) co-existing with weak ferromagnetism with two magnetic transitions (T_M2 ranging from 95 to 106 K and T_M1 around 120 K). Doping with Dy gives no significant structural changes except for a minor change in the c/a ratio. However the superconducting transition temperature is significantly suppressed and magnetic ordering temperature enhanced on Dy doping. These effects are described and discussed.     

Atomic resolution STM observation of the Bi---O surface of yttrium substituted Bi2Sr2CaCu2Oy single crystals

We first examined Bi---O surfaces of Bi₂Sr₂CaCu₂O_y single crystals, whose Ca sites were substituted by Y ions, using an ultra-high vacuum scanning tunneling microscope (UHV-STM). Atomic resolution surface images were obtained for both the unsubstituted superconducting crystals and non-superconducting crystals, whose 60% Ca sites were substituted by Y ions. We found a lot of unperiodic disorder in the surface structure of the Y substituted crystal. The disorder seems to be caused by the random distribution of the Y ions.     

O KVV Auger emission versus resonant photoemission at the O K edge of high-Tc superconductors

Photoelectron spectroscopy results on single crystals of the superconductors Bi₂Sr₂CaCu₂O₈,Bi₂Sr₂CuO₆, Ba_0.6K_0.4BiO₃ and the semiconductor Ba_0.9K_0.1BiO₃ are reported for the photon energy region around the O K absorption threshold. The development of the O-KVV Auger structure has been carefully monitored as a function of photon energy. A non-monotonic behavior displaying a feature at a constant binding energy of about 14 eV was found for Bi₂Sr₂CaCu₂O₈ and Bi₂Sr₂CuO₆ in a narrow photon energy region of 1 eV at the main edge of the O K absorption spectrum around 530 eV. The corresponding enhancement, connected with the autoionization of O 2p states, is absent in Ba_1−xK_xBiO ₃ in contrast to Bi₂Sr₂CaCu₂O₈ and Bi₂Sr₂CuO₆. The resonant enhancement is more pronounced for Bi₂Sr₂CuO₆ as compared to Bi₂Sr₂CaCu₂O₈, which can be explained by a lower charge carrier concentration in the former case, leading to a more localized nature of intermediate O 2p states. The model parameters Cu d–d and O p–p Coulomb interactions and the charge transfer energy Δ are estimated from the experiments.     

Bi2Sr2CaCu2O8的晶体结构与超导性能

本文研究了Bi-Sr-Ca-Cu-O体系中理想成份为Bi₂Sr₂CaCu₂O₈化合物的超导性能和晶体结构。名义成份为BiSrCaCu₂O_5.5零电阻超导转变温度T_c(0)=81.5K。用X射线粉末衍射方法测定了Bi₂Sr₂CaCu₂O₈的晶体结构,其基本结构属体心四方晶系,空间群为D_4h¹⁷-l4/mmm,点阵常数a=3.825?,c=30.82?。每单胞化合式单位为2.2Ca占据2(a)等效点系,4Sr,4Bi和4Cu占据三组4(e)位置,其原子参数z分别为0.110,0.302和0.445,16O分别占据8(g),z=0.445和二组4(e),z=0.210和0.380。Bi₂Sr₂CaCu₂O₈晶体结构可认为是阳离子沿z轴的(00z)和((1/2)(1/2)z)交错排列,由Aurivillius相导生出来的。讨论了在Bi-Sr-Ca-Cu-O体系中可能存在的其它沿z轴不同堆垛层数的超导相。 关键词：