Growth and characterization of laser-deposited Ag-doped YBa2Cu3O7−x thin films on bare sapphire

Microstructural and superconducting properties of YBa₂Cu₃O_7−x thin films grownin situ on bare sapphire by pulsed laser deposition using YBa₂Cu₃O_7−x targets doped with 7 and 10 wt% Ag have been studied. Ag-doped films grown at 730°C on sapphire have shown very significant improvement over the undoped YBa₂Cu₃O_7−x films grown under identical condition. A zero resistance temperature of 90 K and a critical current density of 1·2×10⁶ A/cm² at 77 K have been achieved on bare sapphire for the first time. Improved connectivity among grains and reduced reaction rate between the substrate and the film caused due to Ag in the film are suggested to be responsible for this greatly improved transport properties.     

The Underdoped Region of the Phase Diagram of YBa2Cu3O6+x

Here we present a reviewed phase diagram of the high-T _c superconducting YBa₂Cu₃O_{6+ x} compound, finely mapped in the strongly underdoped region (0 < x < 0.5), from the pure antiferromagnetic state to the superconducting regime. The Neèl and spin freezing temperatures have been measured by μSR experiments while the hole density per Cu atom in the CuO₂ planes has been determined from the resistive T _c and from Seebeck coefficients at 290 K. The phase diagram is discussed in comparison to those of La_{2− x} Sr _x CuO₄ and Y_{1− x} Ca _x Ba₂Cu₃O₆ cuprate systems.     

Synthesis of Y-Ba-Cu-O superconducting material by citrate chemical route—some observations

We present an overview of our powder synthesis procedure and give some initial results concerning the superconducting properties of YBa₂Cu₃O_7−x .     

Magnetic shielding using high-temperature superconductors

Magnetic shields of various high-temperature superconductors, YBa₂Cu₃O_7−x (YBCO), YBa₂Cu₃O_7−x -Ag composites (random inclusions as well as non-random coatings) and Bi₂Sr₂Ca₂Cu₃O _x (BSCCO) were prepared by uniaxial as well as isostatic compression with various dimensions. The shielding properties were measured at 77 K for dc and ac magnetic fields in the range of frequencies from 100 Hz to 10 kHz. The critical penetration field (CPF), defined as the value of the applied magnetic field at which a detectable field was observed inside the cylinder, varied from cylinder to cylinder and also with the ageing of the cylinders in the case of YBCO shields. The highest value of CPF was 16 G at 77 K for YBCO shield prepared by isostatic compression. Even though the stability of BSCCO shields with respect to ageing is good, the CPF values are very low compared to those for YBCO. Detailed studies were performed in the case of YBCO shields. The CPF decreased as a function of time over a period of 90 days. The CPF decreased as the frequency of the applied field was increased. The wave form of the field inside the pot for a sinusoidal applied field was highly distorted and showed the presence of higher harmonics with appreciable amplitude. The wave form was Fourier-analysed to yield the field inside the shield along with the harmonics. The shields with Ag addition seem to give better performance at high fields.     

Influence of transition metals substitution on the superconductor Bi4Ca3Sr3Cu4O y

The results of our investigation on the specimens Bi₄Ca₃Sr₃Cu_4−x T _xO _y (T=Fe, Co, Ni,x⩽0.5) synthesized in air are presented. Fe and Co substituents result in the formation of Bi₂Sr₂CuO _y -type of phase, with considerable depression ofT _c of the main phase. However, Ni is completely soluble with Cu in this concentration range without significant depression of superconducting transition temperature (T _c). This difference in the solubility behaviour of Fe and Co on the one hand and Ni on the other is explained taking into account ionic charge and coordination number mismatches.     

Effect of substitution at the barium site in YBa2Cu3O7-δ

The oxygen content in YBa₂Cu₃O_7-δ has been varied by substitution at Ba site with Sr or K and its influence on the structural and superconducting properties has been studied. These properties are compared with that of unsubstituted YBa₂Cu₃O_7-δ prepared by quenching. The increase inδ value of YBa₂Cu₃O_7-δ decreases theT _c drastically, whereas in YBa_2-χK_χCu₃O_7-δ system increase in theδ value (as high as 0·92) does not affect the superconducting transition temperature, which remains above 77 K. In the YBa_2-χSr_χCu₃O_7-δ system, as Sr content increases there is marginal decrease in the oxygen content as well as in the superconducting transition temperature.     

Crystal structure and resistivity studies on PrBa2 −x Pr x Cu3O7 −y oxide system

The compound PrBa₂Cu₃O_{7 −y} is not superconducting while most other RBa₂Cu₃O_{7 −y} (R=rare earth) compounds exhibit superconductivity in the 90K range. The system PrBa_{2 −x} Pr _x Cu₃O_{7 −x} has been prepared to study the effect of excess Pr at the Ba site on the structure, resistivity and magnetic behaviour of this system. It is observed that single-phase compounds in the above series form forx=0·8—that is up to the composition Pr_1·8Ba_1·2Cu₃O_{7 −y} . While stoichiometric PrBa₂Cu₃O_{7 −y} is orthorhombic, the compounds with excess Pr show tetragonal structure. Four-probe dc resistivity measurements show that all the single-phase compounds in the above series do not exhibit superconductivity and are semiconducting down to 12 K. Magnetic susceptibility measurements reveal deviation from Curie-Weiss behaviour starting at a characteristic temperature, which is taken to be the ordering temperature (T _N ) of the Pr moments. BothT _N and overall resistivity decrease with increasingx and may have a common origin.     

Superconducting Properties of Iodine-Intercalated Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+<Emphasis Type="Italic">x</Emphasis></Subscript>

The superconducting properties of iodine-intercalated high-temperature superconducting Bi₂Sr₂Ca₂Cu₃O_10+x phase (Bi-2223) were systematically studied. It was found that for samples containing a significant amount of Bi₂Sr₂CaCu₂O_8+x , iodine intercalation results in the dramatic decrease of the inter-granular critical current density, as well as a significant decrease of the critical temperature (T _c), the critical current density in the grains (J _cg), and of the amount of Bi-2223. For samples with a large amount of Bi-2223, T _c changes insignificantly, whereas J _cg can even increase. We argue that the different behavior of the superconducting parameters is the result of various oxygen concentrations, and we explain the effect of iodine intercalation based on the parabolic dependence between T _c and the number of holes per CuO₂ layer. The H(T) curves (determined from the peak position in the loss signal of ac susceptibility) for intercalated samples deviate significantly from the quasi 2D-like behavior, pointing toward an enhancement of the 3D fluctuations of vortices. For the change in the values and dimensionality of the flux pinning in the process of the intercalation, we attempted a qualitative explanation based on the models proposed in literature.     

Superconductivity in Na-doped Bi2Sr2CaCu2O y system

Samples with the nominal composition Bi₂Sr₂Ca_1−x Na _x Cu₂O _y (x=0, 0·1, 0·2 and 0·3) were prepared by solid-state reaction of the individual compounds. X-ray diffraction patterns indicate that the samples have a majority 2212 phase with 2223 also being present. From the DC four-probe resistance data, we have observed that the furnace-cooled samples show metallic behaviour while the quenched samples show superconductivity up to 97 K.     

High-temperature ceramic oxide superconductors

High-temperature superconductivity in oxides of the type La_2−x Ba _x (Sr _x )CuO₄, YBa₂Cu₃O_7−δ , La_3−x Ba_3+x Cu₆O₁₄ and Bi(Tl)-Ca-Sr(Ba)-Cu-O systems is discussed, with special emphasis on the experimental findings from the author’s laboratory. The importance of holes on oxygen and of the Cu¹⁺ (d ¹⁰) state is examined. A transition is shown to occur from chain- to sheet-superconductivity in YBa₂Cu₃O_7−δ accompanying a change in oxygen stoichiometry. Some of the important material parameters and technological applications are briefly presented. There is every hope that materials withT _c close to room temperature will be discovered in the near future. All the highT _c oxides found hitherto have perovskite-related structures with two-dimensional Cu-O sheets. Contribution No. 485 from the Solid State and Structural Chemistry Unit.     

Self-doping Effects on the Superconducting Properties of Cu0.5Tl0.25M0.25Ba2Ca2Cu3O10−δ (M = Bi, Hg, Nb, Pd, Li, Na, K)

The effect of self-doping and substitution of elements of higher and lower electronegativity, such as Bi, Hg, Nb, Pd, Li, Na, K, on the superconducting properties of Cu_0.5Tl_0.5−x M _x Ba₂Ca₂Cu₃O_10−δ with x=0.25 is investigated. These experiments demonstrated that the elements of lower electronegativity such as Li, Na, and K can easily liberate their outer most s-electron that could be supplied to the conducting CuO₂ planes of Cu_0.5Tl_0.5−x M _x Ba₂Ca₂Cu₃O_10−δ superconductor, and as a result, we get enhanced superconducting properties. However, highly electro-negative elements hinder the transfer of carriers from charge reservoir layer to the conducting CuO₂ planes and promote inferior superconducting properties. In the present studies, we have investigated the effect of post-annealing in nitrogen and oxygen atmospheres for optimizing the carriers in conducting CuO₂ planes of Cu_0.5Tl_0.5−x M _x Ba₂Ca₂Cu₃O_10−δ (M=Bi,Hg,Nb,Pd,Li,Na,K) superconductor. These studies are important since the density of carriers in the conducting CuO₂ planes determines the Fermi-vector k _F and Fermi velocity v _F of the carriers, which ultimately brings about the final superconducting state of the system.      

Superconducting transition temperatures in the Ru-1232 system, RuSr2(Gd1? x Ln x Ce1.8Sr0.2)Cu2O z (Ln = Sm, Dy, and Ho)

We have investigated effects of the lanthanide element Ln and the composition changes on the superconducting transition temperatureT _c in the Ru-1232 system, RuSr₂(Gd_1−x Ln _x Ce_1.8Sr_0.2)Cu₂O _z (Ln = Sm, Dy, and Ho). At first, in the case of the samples with Ln = Sm among almost the single 1232 phase samples, the values of the superconducting onset temperatureT _co are almost the same forx=0.00−0.15, and each of the lattice parametersa andc is almost constant. While, in each of the cases of the samples with Ln = Dy and Ho, the sample withx=0.05 shows the maximum values for both the superconducting onset temperatureT _co and the zero resistivity temperatureT _cz. Especially for the sample with Ln = Dy, the values ofT _co andT _cz are 18.5 and 6.5 K, respectively. These are higher than those of the mother sample of RuSr₂(GdCe_1.8Sr_0.2)Cu₂O _z . Moreover, from variations ofT _co, lattice parameters ofa andc in the RuSr₂(Gd_1−x Dy _x Ce_1.8Sr_0.2)Cu₂O _z system as a function of Dy contentx, the relationship between the superconducting transition temperature and the lattice parameters in the present system are investigated.     

Oxygen content determination of Bi2Sr2Ca2Cu4O11+x superconductor by thermogravimetric analysis

Thermogravimetric analysis of the individual, binary, ternary, and bismuth-based superconductor mixtures have been carried out to elucidate the excess oxygen content of the Bi₂Sr₂Ca₂Cu₄O_11+x . Our systematic approach eliminates the need to assume initial phase present, original oxygen content, and degree of reduction as in other TG studies. The excess oxygen content of the bismuth superconductor increases fromx=0.38 tox=0.64 after three heating cycles in oxygen atmosphere. Most of the excess oxygen is associated with the highly oxidized copper (Cu³⁺) in the superconducting phase/phases.     

Polymeric encapsulation of 1-2-3 ceramic superconductors

YBa₂Cu₃O_7−x pellets have been found to degrade and lose superconducting properties when exposed to the normal atmosphere for long durations. Hence, coating the superconducting pellets with a polymer to protect it from moisture and CO₂ of the ambient atmosphere is highly desirable. In this paper the criteria of selection of a polymer and some preliminary studies on polymeric encapsulation of 1-2-3 pellets are reported. Fevitite epoxy and stycast have been found to show encouraging results.     

Effect of oxygen content on the electrical properties of YBa2Cu3O7−x single crystals

The effect of oxygen content in the single crystals of high-temperature superconductor YBa₂Cu₃O_7−x on the electrical resistivity, the Hall effect in the plane perpendicular to thec axis and the energy gap Δ, measured with tunnelling electron microscope, has been studied. The distribution of the gap along the surface of the crystal was also studied. The results of the study on the relationship between the magnitude of the energy gap Δ and the superconducting transition temperatureT _c of single crystals with various oxygen contents are approximated by the linear dependence 2Δ_av=4·4kT _c .     

Evidence for Irradiation Triggered Nonuniform Defects Distribution in Multiharmonic Magnetic Susceptibility of Neutron Irradiated YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7−</Subscript><Subscript><Emphasis Type="Italic">δ</Emphasis></Subscript>

Multiharmonic ac-magnetic susceptibilityx ₁,x ₂,x ₃, of neutron irradiated Li-doped YBa₂Cu₃O_7−x has revealed a nonmonotonic dependence of all harmonics on the neutron fluence. The irradiation has a strongly depressive influence on the intergrain connection suggesting an increase of the effective thickness of the intergranular Josephson junction at a neutron fluence of 0.98 × 10¹⁷ cm⁻². Less damaged are the intragrain properties. A spectacular enhancement of the superconducting intragranular properties reflected in the characteristics of all harmonics was observed at highest fluence φ=9.98 × 10¹⁷ cm⁻². We assume that this effect results from the development of a space inhomogeneous distribution with alternating defectless and defect-rich regions.     

Bulk thermal expansion studies of BiCaSrCu2O x and Bi2CaSr2Cu2O x

The compounds BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x were prepared by ceramic techniques and characterized by X-ray powder diffractometry (XRD) and microthermogravimetry (TG) and their bulk thermal expansion measurements were carried out using dilatometry in the temperature range 298T1073 K in air. The results have been analyzed and are compared with those obtained earlier for YBa₂Cu₃O₇. The XRD analysis shows that both BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x are single phase in nature, having an orthorhombic symmetry. The TG analysis carried out in oxygen, air, and nitrogen shows negligible weight loss (R~0.1%) on heating to 1073 K, indicating that these two compounds, unlike YBa₂Cu₃O₇, are quite stable. The analysis of bulk thermal expansion data reveals that the average linear thermal expansion coefficient ( ₁) for both BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x is almost the same ( ₁ 10.5×10^–6 K^–1) and is found to be nearly half of that for YBa₂Cu₃O₇ ( ₁ 18×10^–6 K^–1), suggesting that the interatomic bonding in both BiCaSrCu₂O _x and Bi₂CaSr₂Cu₂O _x is stronger as compared to YBa₂Cu₃O₇.     

Chemical solution deposition of YBa2Cu3O7−x coated conductors

At present, the development of superconducting YBa₂Cu₃O_7−x coated conductors attracts much attention due to their enormous application potential in electric power systems. Worldwide research is focused on the investigation and improvement of buffer materials and YBa₂Cu₃O_7−x superconducting properties as well as low-cost manufacturing processes in cooperation with industrial companies. Accordingly, chemical solution deposition has emerged as a highly competitive, versatile, and cost-effective technique for fabricating coated conductors of high performance. New chemical solution approaches are under development for buffer layer deposition. In order to achieve high critical current carrying YBa₂Cu₃O_7−x layers, the established trifluoroacetate route is favored. This paper reviews the most recent work on chemical solution deposition within the IFW Dresden while also considering achievements on this specific research topic worldwide.     

Effect of praseodymium substitution on the growth and properties of Y1−x Pr x Ba2Cu3O7−δ (o <x < 0·4) single crystals

In the present paper, a modified self-flux technique has been successfully employed for the growth of pure and praseodymium substituted (partially) large single crystals of high temperature superconducting Y_1−x Pr _x Ba₂Cu₃O_7−δ (x = 0·0,0·2,0·4). Typical sizes of the platy and bulky crystals of pure YBCO(123) material are ≈ 2 × 2 × 0·1 mm³ and 4 × 1 × 1 mm³, respectively. In case of Pr-substitution, the typical sizes of platy and bulky crystals of Y_0·8Pr_0·2Ba₂Cu₃O_7−δ and Y_0·6Pr_0·4Ba₂Cu₃O_7−δ materials are ≈ 2 × 3 × 0·1 mm³ and 5 × 1 × 1 mm³ and ≈ 1 × 1·5 × 0·1 mm³ and 7 × 0·2 × 0·1 mm³, respectively. The morphology and growth habit of the as-grown single crystals and the critical transition temperature (T _c) of the oxygenated crystals were found to depend on the Pr-content. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995