Surface atomic imaging of La2CuO4 and superconducting Tl2Ba2Ca2Cu3O10

Surface structures of the high T_c oxide superconductors Tl₂Ba₂Ca₂Cu₃O₁₀ and La₂CuO₄ have been studied by high resolution electron microscopy. In addition to the single atomic layer of La on the (113) surface observed previously, several atomic layers of the C-form of La₂O₃ were found to coat the (001) surfaces of La₂CuO₄. Surface reconstruction with the incorporation of excess Ba on the (110) surface of Tl₂Ba₂Ca₂Cu₃O₁₀ has been observed together with a stepped (11l) surface produced by a combination of the (110) and (001) planes. The (001) surface of Tl₂Ba₂Ca₂Cu₃O₁₀ was also found to terminate with a Ba-O layer. Possible mechanisms for the formation of these surface structures are discussed.     

The degradation process in Tl2Ba2Ca1Cu2O10+x

Degradation processes in 2212 thallium-based superconductors have been investigated using X-ray diffraction and electron microscopy techniques. It has been shown that the formation of amorphous or microcrystalline material by decomposition of the superconducting phase is followed by the crystallization of BaCo₃ and other oxide compounds. The influence of preexisting BaCO₃ on the rate of this degradation process has also been studied, and the results indicate that the removal of this stable precursor compound is an important step in improving the long term stability of the 2212 phase.     

Studies on fabrication of Ag/Tl2Ba2Ca2Cu3O10/CdSe heterostructures with electrochemical technique

The Ag/Tl₂Ba₂Ca₂Cu₃O₁₀/CdSe heterostructure was fabricated at room temperature by soft electrochemical processing technique for the first time. The formation of the heterostructure with non-diffusive interfaces was confirmed by X-ray diffraction. The crystallite sizes determined for Tl-2223 and CdSe films were 33 nm and 25 nm, respectively. The Tl₂Ba₂Ca₂Cu₃O₁₀ film electrodeposited onto Ag-substrate has shown the superconducting transition temperature T_c at 116.5 K and J_c = 2.1 × 10³ A/cm². These values were found to improve after the deposition of CdSe onto Ag/Tl-2223 films. The effect of red He-Ne laser irradiation on the superconducting properties of heterostructure are studied and discussed at length in this paper.     

NMR study of local hole distribution, spin fluctuation and superconductivity in Tl2Ba2Ca2Cu3O10

⁶³Cu, ¹⁷O and ²⁰⁵Tl NMR have been performed in the high-T_c superconductor Tl₂Ba₂Ca₂Cu₃O₁₀ whose T_c(max) is 127 K. The hole densities at Cu and oxygen sites in the CuO₂ plane have been extracted from the nuclear quadrupole frequency ν_Q. The striking feature is that the Cu holes are significantly transferred to oxygen site due to strong hybridization between Cu and oxygen. From an analysis of T₁ and T_2G, it has been found that the spectral weight of the spin fluctuation is transferred to higher energy compared to YBa₂Cu₃O₇, while the magnetic correlation length ξ does not differ much. Thus, it is suggested that the higher T_c is due to higher characteristic energy of spin fluctuations, i.e. the superconductivity is spin fluctuation mediated. The superconducting properties are consistently explained by a d-wave superconductivity model with a finite density of states (DOS) at the Fermi level. We show that the disorder of the Ca/TlO layer caused by the partial inter-substitution of Tl and Ca is responsible for the potential scattering to produce such a DOS. It is found that if such a potential scattering were absent, T_c would go up to 132 K which is quite close to the record T_c realized in the Hg based compound.     

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.     

Influence of the doping level on the charge distribution among the inequivalent CuO2 layers in Tl2Ba2Ca2Cu3O10−δ : a NMR study

and NMR measurements in the normal and superconducting states of Tl₂Ba₂Ca₂Cu₃O_10−δ with different δ are reported. In the overdoped Tl2223 sample with T_c=117 K (T_c^opt=123 K) and δ₁<δ^opt different temperature dependencies of the Knight shift are revealed for inequivalent CuO₂ layers. For the inner CuO₂ layer with the square oxygen coordination of Cu the decrease of with temperature is more gradual. In going towards the underdoped Tl2223 with T_c=104 K and δ₂>δ^opt the changes of with temperature are found to be the same for both types of copper layers. The quadrupole coupling constants for copper and oxygen from different CuO₂ layers were obtained. From the variations with doping of the valence contribution to the electric field gradient at copper sites, we estimate both the hole numbers at Cu and oxygen sites and the real concentration of mobile hole carriers n_h in each of inequivalent CuO₂ layers. In the overdoped Tl2223 sample the charge density in the inner layer differs from the one in the outer plane (with five-fold oxygen coordination for Cu). Our results show that the inhomogeneity of the charge distribution disappears in the underdoped regime. The results are compared with calculations of the charge distribution among the CuO₂ planes in multilayered cuprates reported by Haines and Tallon [E.M. Haines, J.L. Tallon, Phys. Rev. B 45 (1992) 3127].     

Low temperature magnetocaloric effects in Dy1Ba2Cu3O7−δ and Y1Ba2Cu3O7−δ high-Tc single crystals

The heat release has been measured in high temperature superconductors during and after a change of the external magnetic field μ₀H_a ≤ 0.5 T applied parallel to the c-axis at 0.1 K ≤ T ≤ 0.45 K. Two Y123 and one Dy123 twinned single crystals were investigated. An analysis of the heat release based on the Bean model and on a model for thin superconductors in perpendicular geometry recently proposed by Brandt et al. has been carried out. During field sweep we measured ∝ H_a²dH_a/dt. This dependence can be understood within the Bean model for longitudinal geometry. The critical current densities obtained with this method are in good agreement with those from magnetization measurements. We also present measurements, and a first quantitative analysis, of dissipation due to the time relaxation of the flux line lattice after a field sweep. For the heat release a t⁻¹ dependence has been found which corresponds to a logarithmic time dependence of the magnetization. The normalized relaxation rate we obtained is in agreement with literature values.     

Grain boundary compositions in stoichiometric and off-stoichiometric Y1Ba2Cu3O7−x

The grain boundary segregation behavior of stoichiometric and off-stoichiometric YBa₂Cu₃O_7−x has been studied with analytical electron microscopy (AEM) to complement previous results obtained with Auger electron spectroscopy (AES). It was observed that the grain boundary segregation levels varied from boundary to boundary. In stoichiometry material, excess copper and deficient oxygen were observed at the grain boundaries. In materials containing excess barium, excess yttrium and deficient copper levels were observed at the grain boundaries. The grain boundary segregation levels in the materials containing excess barium can be related to the resistivity and critical current density results. Preferential segregation to specific sites in grain boundaries was observed by AEM. The effect of grain boundary segregation on the superconducting properties of these materials is discussed in terms of the weak link behavior and a possible percolative mechanism in order to maintain a continuous current path.     

Preparation and superconducting properties of YBa2Cu4O8

Samples of YBa₂Cu₄O₈ are prepared by means of a new high oxygen pressure technique employing oxygen-HIP. Both magnetization and resistivity measurements show the superconductivity transition at 82.5 K. The lower and upper critical fields of YBa₂Cu₄O₈ are obtained from the magnetization measurements. The Ginzburg-Landau parameters, ζ(0)=17 Å, λ(0)=2400 Å, are estimated from these results.     

Electrical and structural properties of epitaxially grown Y1Ba2Cu3O7 − x and Y2Ba4Cu8O16 − x thin films using the BaF2 method

Thin films of Cu, Y and BaF₂ are co-condensed in ultrahigh vacuum onto SrTiO₃ (1 0 0)-substrates at room temperature without any additional oxygen supply. It is found that the temperature of the ex situ fluorine-oxygen exchange reaction in flowing wet oxygen essentially determines whether the Y₁Ba₂Cu₃O_{7 − x}-phase (T_ex = 850°C) or the Y₂Ba₄Cu₈O_{16 − x}-phase (T_ex = 800°C) forms or any mixture of both phases in between. Small-angle X-ray diffraction verifies the strictly epitaxial growth of the superconducting phases. The variation of the composition around the ideal 1,2,3-stoichiometry affects only the superconducting and normal conducting properties which are measured using the four-probe Montgomery method. The values of the normal state resistivity and its temperature dependence are discussed in combination with a reduced cross section of the conduction paths in the films.     

The formation mechanism of Bi2Sr2Ca2Cu3Ox superconducting phase

The mechanism and dynamic model of the formation of 2223 phase are presented and verified in the paper. It reveals that with the solubilization of part of the 2212 phase, 2223 phase is formed by the reaction being carried out according to a nucleation and growth mechanism in the presence of liquid phase, which conforms to the JMA dynamics equation. The addition of a little 2223 phase as nucleator, regrinding and resintering can promote the formation of 2223 phase. But the quick formation rate of 2223 phase may lead to irregularity of the 2223 phase structure, which degrades its electric and magnetic properties, while annealing treatment can improve its superconductivity.     

Mechanism responsible for the modification of the band spectrum and superconducting properties in the Tl2Ba2Ca1 ? x Y x Cu2 ? y Co y O z system

The modification of the temperature dependences of the thermopower coefficient for the Tl₂Ba₂Ca_{1 − x} Y _x Cu_{2 − y} Co _y O _z system is investigated as a function of the dopant content. The model of an asymmetric narrow band is shown to be applicable to high-temperature superconductors in the thallium system. The parameters of the band spectrum and charge carrier system for samples of a close-to-optimum composition are determined by analyzing the temperature dependences of the thermopower coefficient within the narrow band model. The character and mechanism of their variation in the course of the transition to an underdoped regime are analyzed together with the dynamics of changes in the superconducting properties. The critical temperature T _c is found to correlate with the effective conduction-band width W _D . It was shown that the dependence T _c (W _D ) for Tl₂Ba₂Ca_{1 − x} Y _x Cu_{2 − y} Co _y O _z has a close-to-universal character, but the suppression of T _c upon the broadening of the band occurs faster than in the case of the yttrium system. Original Russian Text ? O.A. Martynova, V.é. Gasumyants, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 9, pp. 1537–1542.     

Effect of annealing temperature on the decomposition of reactively sputtered Ag2Cu2O3 films

Ag₂Cu₂O₃ films were deposited on glass substrates by reactive sputtering of a composite silver-copper target. The deposited films were annealed in air at 100, 200 and 300 °C. The structure of the films was studied using X-ray diffraction (XRD), their surface morphology was characterised using scanning electron microscopy (SEM) and their electrical resistivity at room temperature was measured using the four point probe method. The 100 °C annealing did not modify either the film structure or the film morphology. On the other hand, Ag₂Cu₂O₃ films were partially decomposed into Ag and CuO after a 200 °C annealing. The decomposition was complete for a 300 °C annealing. The evolution of the film surface morphology as a function of the annealing temperature was discussed in connection to the evolution of the molar volume of the phases constituting the films.     

X-ray single crystal analysis of HgBa2Ca2Cu3O8+δ and influence of oxygen stoichiometry on the superconducting properties

X-ray diffraction analyses of good-quality single crystals of HgBa₂Ca₂Cu₃O_8+δ, synthetized by a closed-vessel technique at low pressure, have lead to more definite results with respect to previous structural studies. Samples with T_c = 135 K showed a Cu occupancy of 16.1% on the Hg site at the origin of the unit cell. Excess oxygen appears to be present only in the basal plane at the interstitial site , 0 with an occupancy δ = 0.190 ± 0.015. This compound has the shortest copper oxygen apical distance within the mercury family (2.696(3) Å) together with an almost complete planarity of the CuO₂ planes. Variations in the excess oxygen content upon different heat treatments were analyzed by thermogravimetry and magnetic-susceptibility measurements. A correlation between δ and T_c could be derived, showing in particular that superconductivity exists down to a very low interstitial oxygen content.     

A low temperature internal friction study of Y0.85Ca0.15Ba2Cu3O7−δ with different oxygen content

The ceramic sample of Y_0.85Ca_0.15Ba₂Cu₃O_7−δ was prepared by standard solid-state reaction method, and samples with different oxygen concentration were obtained by quenching from high temperature. The internal friction was measured using the vibrating reed method from liquid-nitrogen temperature to room temperature at kilohertz frequency. An internal friction peak was observed around 250 K in Y_0.85Ca_0.15Ba₂Cu₃O_7−δ quenched from 1023 K. The peak is related to the one observed around 220 K (labeled as P3 peak) in undoped YBa₂Cu₃O_7−δ (Y123). This result shows the dependence of P3 peak on carriers density and P3 peak has a strong correlation to the abnormal behavior of Y123 in the underdoped range. The variation of two low temperature thermal activated relaxation peaks (P1 and P2) on oxygen content were also investigated. And consistent explanations were given based on all recent researches.     

The properties of the Y2O3 films exposed at elevated temperature

Yttrium trioxide (Y₂O₃) thin films have been deposited on silicon (1 1 1) substrates by RF magnetron sputtering. The influences of thermal exposure at high temperature in air on the structure, the surface morphology, roughness, and the refractive index of the Y₂O₃ thin film were investigated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), atomic force microscopy (AFM), and spectroscopic ellipsometry (SE). The results indicate that chemical composition of the as-deposited Y₂O₃ film is apparently close to the stoichiometric ratio, and it has a cubic polycrystalline structure but the crystallinity is poor. The monoclinic and cubic phases can coexist in the Y₂O₃ film after thermal exposure to 900 °C, and the monoclinic phase disappears completely after 300 s exposure to 950 °C. The changes of the surface morphology, roughness, and the refractive index of the Y₂O₃ film are closely related to the crystal structure, the internal stress, and various defects influenced by thermal exposure temperature and time.     

TEM investigation of YBa2Cu3O7 thin films on SrTiO3 bicrystals

YBa₂Cu₃O₇ films in c-axis orientation on bicrystalline SrTiO₃ substrates are investigated by TEM. The films and the substrates are examined in cross-section and in plane view. The grain boundary of the bicrystal substrate contains (110) faceted voids, but is otherwise straight on a nanometer scale. Contrary to this, the film grain boundary is not straight grain boundary can be up to 100 nm for a 100 nm thick film. The deviation from the intended position of the YBCO grain boundary can already occur at the film/substrate interface where it can be as much as ±50 nm.     

Synthesis of YBa2Cu3O7−x superconducting thin films on LaAlO3 by means of PAMOCVD

High-T_c superconducting thin films have been deposited in situ by means of a plasma assisted metal-organic chemical vapour deposition (PAMOCVD) process on LaAlO₃. An EMCORE high-speed rotating disc reactor was used to deposit the films at a substrate temperature of 600°C to 800°C. The system is equipped with a (remote) 120 W microwave plasma generator. The oxidising plasma gas is N₂O and/or O₂ while Ar was used as the inert carrier gas for the different metal-organics. The influence of different process parameters (such as the temperatures of the metal-organics, substrate temperature, and plasma gas composition) on the superconductive properties and on the morphology of the films was investigated. Surface morphology and composition were studied by SEM/EDX or EPMA, and AC susceptibility measurements were used to investigate the superconductive properties (T_c and J_c). X-ray diffraction measurements indicated that single-phase YBa₂Cu₃O_7−x films were epitaxially grown with the 00l orientation perpendicular to the substrate surface. The critical temperature (T_c) of the films is about 90 K and the critical current density (J_c) is higher than 10⁶ A/cm² at 77 K and zero field.     

Crystal structure of Tl0.5Pb0.5Sr2Ca2Cu3O9 at 300 K and around Tc (118 K)

The crystal structure including the cation distribution, of a polycrystalline sample of nominal composition Tl_0.5Pb_0.5Sr₂Ca₂Cu₃O₉ with T_c = 118.2 K has been determined using resonant synchrotron X-ray diffraction data collected at the Cu K, Tl L_III and Sr K edges and time-of-flight powder neutron diffraction data. No oxygen deficiency was observed, but cation disorder at all the non copper sites according to the formula (Tl_0.60Pb_0.40)(Sr_1.60Ca_0.40)(Ca_1.93Tl_0.07) Cu₃O₉ gives a mean hole concentration of 0.18(1) per Cu atom for the three CuO₂ planes, consistent with the high T_c for this material. Analysis of five time-of-flight powder neutron diffraction data between 80 and 150 K have revealed a possible discontinuity in the variation of the c lattice parameter at T_c, due to an anomaly in the position of the apical oxygen atoms.     

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.