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.     

Role of lead in the growth of the highT c phase in the Bi2−x Pb x Sr2Ca2Cu3O y systems

Bi_2−x Pb _x Sr₂Ca₂Cu₃O _y superconducting samples with 0<x<0·3 have been synthesized and characterized using X-ray powder diffraction.T _c and superconducting volume fraction have been measured using a.c. magnetic susceptibility, d.c. electrical resistivity as well as X-band microwave surface resistance in the normal state. The data indicate the growth of the highT _c (2223) phase with corresponding reduction of the lowT _c (2122) phase with increasingx, up to 0·25. Beyond this value ofx there is a slight deterioration of the superconducting behaviour.     

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.     

Solution-sol-gel processing of superconductors

Bulk materials and thin films of pure and homogeneous YBa₂Cu₃O_7−x and Bi₂Sr₂CaCu₂O_8+x compounds were prepared by a nanocomposite solution-sol-gel (SSG) method. The superconducting oxides of YBa₂Cu₃O_7−x and Bi₂Sr₂CaCu₂O_8+x were prepared at very low temperatures i.e. 750°C and 850°C, respectively by SSG method. Pellets sintered from these nanophasic sol powders showed sharp resistivity drops atT _c ∼ 90°K for YBa₂Cu₃O_7−x andT _c∼67°K for Bi₂Sr₂CaCu₂O_8+x . Thin films were prepared using triphasic sol of Y, Ba, Cu and tetraphasic sol of Bi, Sr, Ca and Cu on MgO and SrTiO₃ substrates. The triphasic sol coated on SrTiO₃ substrates and calcined at 800°C for 12h showed the formation of superconducting phase, YBa₂Cu₃O_7−x with preferred orientation along theC-axis. X-ray diffraction patterns of the Bi₂Sr₂CaCu₂O_8+x films on MgO substrate showed the formation of the superconducting phase with preferential orientation along the C-axis and the microwave absorption data as a function of temperature of this film revealed the onset temperature to be 90°K.     

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.      

Partial substitution of Li for Cu in superconducting YBa2Cu3Oy

0.33–33% of the Cu in superconducting YBa₂Cu₃O _y has been replaced by Li (i.e.,x=0.01–1 in single-phase or nominal YBa₂Cu_3–x Li_xO_y). X-ray diffraction powder patterns remain the same as for YBn₂Cu₃O _y , with identical patterns up to about 17% substitution (i.e.,x=0.5). At higher percentages an additional phase appears. Electrical conductivity measurements indicate a small elevation ofT _c at low Li content. Starting at about 5% Li (x=0.15),T _c declines progressively and its width increases asx is raised.     

Superconductivity at 103 K in CdBa2(Ca0.7Y0.3)Cu2Oy

A cadmium analogue of the mercury system with nominal composition CdBa₂(Ca_1–xY_x)Cu₂O_y has been synthesized. Thex=0 samples contain about 12 vol.% of the 1212 phase but are not superconducting. Thex=0.3 samples are superconducting atT _on = 103 K. The EDX analysis of 18 microcrystals shows a broad cationic distribution of the different components. The observed broad superconducting transition is attributed to the variousT _c of the different microcrystals.     

Magnetic-Field Induced Superconductor–Antiferromagnet Transition in Lightly Doped RBa2Cu3O6+x (R = Lu, Y) Crystals

The remarkable sensitivity of the c-axis resistivity and magnetoresistance in cuprates to the spin ordering is used to clarify the doping-induced transformation from an antiferromagnetic (AF) insulator to a superconducting (SC) metal in RBa₂Cu₃O_6+x (R = Lu, Y) single crystals. The established phase diagram demonstrates that the AF and SC regions apparently overlap: The superconductivity in RBa₂Cu₃O_6+x , in contrast to La_2−x Sr _x CuO₄, sets in before the long-range AF order is completely destroyed by hole doping. Magnetoresistance measurements of superconducting crystals with low T _c ≤15–20 K give a clear view of the magnetic-field induced superconductivity suppression and recovery of the long-range AF state. What still remains to be understood is whether the AF order actually persists in the SC state or just revives when the superconductivity is suppressed, and in the former case, whether the antiferromagnetism and superconductivity reside in nanoscopically separated phases or coexist on an atomic scale.     

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.     

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.     

Superconductivity and Ferromagnetism of the Ru-1232 Compounds in the (Ru1?xNbx)Sr2(GdCe1.8Sr0.2)Cu2Oz System

The Ru-1232 compounds have been synthesized in the (Ru_1–xNb _x )Sr₂(GdCe_1.8Sr_0.2)Cu₂O _z system, and effects of Nb substitution for Ru on superconductivity and ferromagnetism of the Ru-1232 compounds have been investigated. First, X-ray powder diffraction study shows that nearly the single 1232 phase samples can be obtained in the x composition range from 0.0 to 0.3. Then, from the electrical resistivity study, it is found that each of the samples shows resistivity dropping phenomenon at two temperatures of T _c ^l and T _c ^h, which originates from superconductivity of the Ru-1232 phase and the Ru-1222 one, respectively. Both of the starting temperatures are lowering with increasing Nb content x. Lastly, from the magnetic susceptibility study, it is found that superconducting transition temperature T _c is 20 K for the Ru-1232 sample with x = 0.0 and the ferromagnetic transition temperature T _m is about 90 K. This study also shows that both of the values of T _c and T _m become low with increasing x from 0.0 to 0.3.     

Specific heat of the high-Tc oxide superconductors

We review the specific heat measurements on La₂CuO₄, La_2–xM_xCuO₄ (M = Ca, Sr, and Ba), YBa₂Cu₃O₇, and the Bi-Ca-Sr-Cu-O and Tl-Ca-Ba-Cu-O systems. Tables of properties derived from the data are presented. Results on RBa₂Cu₃O₇ (R=rare earth elements other than Y) are summarized, as are results on YBa₂(Cu_3–xM_x)O₇ (M=Zn, Cr, Fe, or Ni). The difficulties of analyzing the specific heat data, and specifically the separation of the contributions associated with magnetic impurities, are discussed. It is tentatively concluded that the data nearT _c are consistent with BCS theory, although they show evidence of fluctuation effects. It is also concluded that the low-temperature zero-field data on a majority of the high-T _c oxide superconductors provide evidence of anintrinsic term that is proportional toT, a result that is inconsistent with a gap in the electronic density of states.     

Dynamic Inhomogeneities in the La2CuO4-Based Superconductors

Polarization-dependent X-ray-absorption fine-structure (XAFS) measurements on the local structure of the La₂CuO₄-based high-T _c superconductors La_2–x Sr _x CuO₄, La_2–x Ba _x CuO₄, and La_1.6–x Sr _x Nd_0.4CuO₄ find, among others, orientation disorder induced in the Cu–O₂ planes by doping Sr, Ba, and alloying Nd atoms, all such atoms residing in La-sites. The orientation disorder is of two types: mostly static-buckling disorder, and dynamic disordering of the tilt angles of the Cu–O₆ octahedra correlated in nanoscale regions, with respect to neighboring nanoscale regions. Buckling disorder in the Cu–O₂ planes has the greatest detrimental effect on T _c and conductivity for such foreign atoms.     

Prediction ofT c for YBa2Cu3Oz doped with Ca using neural network

In order to predict the superconducting transition temperatureT _c of YBa₂Cu₃O_z doped with Ca, we have constructed a neural network NN which is composed of three layers; we considered 28 constituent elements and their concentration in the input layer to provideT _c in the output layer. The NN was trained by the error-back-propagation method using data from the database “SUPERCON” for high-T_c superconducting materials. The effect of Ca doping onT _c of (Y_1-x-Ca_x)Ba₂Cu₃O_z and Y(Ba_2-xCa_x)Cu₃O_z was investigated using this method. It turned out that a higherT _c is expected for the sample withx = 0.3 andz = 6.5 in the former system and that the oxygen concentrationz can be varied for different Ca contents in the latter system.     

On the Presence of 1D-Like Stripes in Superconducting Epitaxial La2-xSrxCuO4 thin Films

A large positive magnetoresistance (up to tens of percents) is observed in both underdoped (x < 0.15) and overdoped superconducting La_{2− x}Sr_xCuO₄ (LSCO) epitaxial thin films, at temperatures far above the superconducting critical temperature T _c . In the underdoped regime, this magnetoresistance cannot be described by the Kohler rule and is due to the influence of superconducting fluctuations. On the other hand, in the overdoped regime, the Kohler rule does not seem to be violated. The strong magnetoresistance above T _c can be related to the preformed superconducting pairs existing well above T _c but forming a phase coherent superconducting state below T _c . The observations support the idea of a close relation between the pseudogap and the superconducting gap and provide evidence for the presence of pre-pairs above T _c . Both the observed fluctuations and the observed magnetoresistance are in accordance with the existence of 1D-like stripes. These results are further supported by recent high magnetic field measurements (up to 55 T) of the transverse magnetoconductivity σ _xy, which goes to zero for T→0 K.     

Enhancement ofT c (∼ 103 K) in calcium-free Tl2Ba2CuO x (2201) compound

EnhancedT _c in calcium-free Tl compounds of the series Tl _m Ba₂Ca _n−1Cu _n O _x (2201) has been reported. Three different starting compositions (2201, 1201 and 2202) were studied extensively with varying conditions of preparation. Under optimized conditions (sintering temperature 970°C and duration 3–10 min) the highestT _c(onset) ranges from 103 K to ∼ 115 K andT _c (zero) ∼ 95 K was found. XRD studies showed the transformation of all the three nominal compositions into 2201 phase with differentT _cs.     

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.     

Suppression of Anti-ferromagnetism by K Doping in?(Cu0.5Tl0.5?xKx)Ba2Ca2Cu3O10?δ Superconductors

In the inner CuO₂ planes (IP) of (Cu_0.5Tl_0.5)Ba₂ Ca₂Cu₃O_10−δ superconductors the density of the carriers is in the under-doped state which promotes enhancement in the anti-ferromagnetism. Consequently, the critical temperature of the final compound is suppressed. In the present studies, we have enhanced the density of mobile carriers in the inner CuO₂ planes by doping K at the charge reservoir layer by preparing (Cu_0.5Tl_0.5−x K _x )Ba₂Ca₂Cu₃O_10−δ superconductors. The higher density of mobile carriers increases the Fermi velocity V _F, and hence enhances the superconductivity parameters such as T _c, H _c, and J _c. The main objective of these experiments was to suppress the anti-ferromagnetism in the final compound. We have enhanced the inter-plane coupling by partially substituting Be and Mg at the Ca sites. The melting point of the final compounds is significantly reduced with the incorporation of Be and Mg. The incorporation of these elements has been found to facilitate the formation superconductors with higher numbers of CuO₂ planes, i.e., (Cu_0.5Tl_0.5−x K _x )Ba₂Ca_3−y M _y Cu₄O_12−δ .     

NMR studies of Nd2−x Ce x CuO4

Copper NMR has been studied as a function of temperature in a number of superconducting Nd_2−x Ce _x CuO₄ samples. The electric field gradient is very small and the Knight shift is 2380 ppm at room temperature, both of these implying that the copper is in a Cu⁺ state. The Knight shift decreases with temperature particularly belowT _c . The spin contribution to the Knight shift is estimated to be ∼ 200 ppm (about a factor ten smaller than in YBa₂Cu₃O₇) indicating thatN _s (E _F ) at the copper sites is small in this material.