The effects of substrate temperature on the superconducting properties of Tl2Ca2Ba2Cu3O10 films sputter-deposited from stoichiometric oxide targets

The annealing characteristics and the superconducting properties of Tl₂Ca₂Ba₂Cu₃O₁₀ thin films sputter-deposited onto yttrium- stabilized ZrO₂ substrate at up to 500°C from two stoichiometric oxide targets are reported. The films deposited at 400–500°C were found to require a lower post-annealing temperature than the films deposited at lower temperatures to attain the highest T_c superconducting state, due to a more pronounced Ba diffusion toward the substrate as indicated by their secondary ion mass spectrometry depth profiles. The highest T_c achieved tends to degrade with increasing substrate temperatures, a zero resistance T_c of 121 and ≈90 K, respectively, being observed for the films deposited at -ambient temperature and at 500°C. The formation of the highest T_c phase (Tl₂Ca₂Ba₂Cu₃O₁₀) generally is associated with a sheet type of crystal growth morphology with smooth and aligned surfaces which can be obtained only from the films capable of sustaining prolonged annealing at 900°C. Annealing at lower temperatures (≈860°C) results in the formation of rod or sphere type of morphologies with rough and randomly oriented crystals and the lower T_c phases such as Tl₂Ca₁Ba₂Cu₂O₈.     

Effect of a magnetic field on MnAs0.88P0.12 below 80 K

MnAs_0.88P_0.12 has been studied by powder neutron diffraction in external magnetic fields up to 15.2 kOe and temperatures down to 4.2 K. MnAs_0.88P_0.12 takes the MnP type atomic arrangement and exists in para-, ferro- and different (essentially) helimagnetic states. The observation of a double 000^± satellite at 4.2 K < T 70 K adds further evidence to the chain of arguments for distinction between the helimagnetic states H'_a (4.2 K < T < T_S,1 ≈ 70 K) and H_a (T_S,2 ≈ 180 K < T < T_N = (243 ± 5) K). External magnetic fields at 4.2 K < T < 70 K evoke a new magnetic state, which is also characterized by a satellite doublet, and is tentatively designated H'_a,fan.     

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.     

Properties of a large La1.92Sr0.08CuO4+δ single crystal grown by the travelling-solvent floating-zone method

A centimeter size single crystal of La_2−xSr_xCuO_4+δ (volume=1.32 cm³) with x_Sr=0.08 has been grown by the travelling-solvent floating-zone (TSFZ) method using a double ellipsoidal-type optical furnace as the heat source. The crystallised phase was checked solvent free by X-ray powder diffraction experiments, the crystal dimensions and quality being investigated by X-ray and neutron Laüe techniques. Several rocking curves of the Bragg peaks were performed by neutron diffraction giving a full width at half maximum (FWHM) of 0.200° for (006) reflection and clearly showing the presence of twin domains as expected for such an orthorhombic structure. The superconducting critical temperature of the as-grown crystal under 2 oxygen bar was determined by SQUID measurements with T_c=18–20 K. Thermal treatments at different oxygen pressures were carried out showing no significant improvement of the transition sharpness and the T_c value. Normal state susceptibility was also measured from 6 to 800 K for two different field orientations and can be interpreted as an antiferromagnetic insulating state behaviour. The resistivity measurements display an insulating behaviour perpendicular to the CuO₂ planes and a metallic behaviour in the planes, with a high anisotropy ratio R_c/R_b350 at room temperature and a zero resistivity achieved at 27 K in both directions. The specific heat measurements have revealed no anomalies in the temperature range 15–300 K.     

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 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.     

Temperature dependence of the exafs spectrum in YBa2Cu3O7−δ compounds

The temperature dependence of the extended X-ray absorption fine structure (EXAFS) is studied in the high T_c superconductors, YBa₂Cu₃O_7−δ. The measurements were done at the Cu K-edge for samples of two orthorhombic phases (T_c≈90 K and ≈58 K, respectively) and a nonsuperconducting tetragonal phase. Interatomic distances and mean square relative displacements σ² for Cu-O bonds are determined by the least squares refinement. The results indicate that values of σ² increase near T_c for both the orthorhombic samples. It is concluded that this anomalous behavior related to T_c is caused by an anomalous vibration of oxygen atoms in the Ba-O layer. Changes in the Cu-O distances from 300 to 20 K are not found.     

Low-temperature phase and magnetic interactions in FCC Fe-Cr-Ni alloys

The low-temperature (5 K < T < 300 K) magnetic properties of a set of nine isostructural fcc Fe-Cr-Ni (Fe ≈ 68 at %, Cr ≈ 20 at%, Ni ≈ 9 at%) alloys were studied by SQUID magnetometry, neutron diffraction and ultrasonic techniques. Type-1 antiferromagnetic (AF) ordering was observed below the Néel temperature, T_N. The dc susceptibility, χ(T), did not exhibit a simple Curie-Weiss dependence. Above T_N, atemperature independent component χ₀ was observed, i.e., χ(T) = χ₀ + C / (itT + θ. T_N was systematically influenced by the lattice parameter, a, decreasing from (47.9 ± 0.5) K to (35.0 ± 0.5) K as a increased by only 0.25%. The average magnetic moment of ≈ 0.6μ_B obtained from neutron scattering was lower than the ≈ 1 μ_B obtained from the SQUID data. Mean field estimates of antiferromagnetic nearest-neighbors exchange interaction (J₁) and ferromagnetic second-nearest-neighbors interaction (J₂) indicate that |J₂/J₁|≈ 1.5. We believe that this is evidence of the RKKY interaction, and self-consistently argue that only the external d electrons are responsible for the localized average moment. This may mean that s-d hybridization of the external electrons is weak in these alloys.     

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.     

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.     

Magnetic properties of Lu2Co17−xSix single crystals

The Co-sublattice anisotropy in Lu₂Co₁₇ consists of four competitive contributions from Co atoms at crystallographically different sites in the Th₂Ni₁₇-type of crystal structure, which result in the appearance of a spontaneous spin-reorientation transition (SRT) from the easy plane to the easy axis at elevated temperatures. In order to investigate this SRT in detail and to study the influence of Si substitution for Co on the magnetic anisotropy, magnetization measurements were performed on single crystals of Lu₂Co_17−xSi_x (x=0−3.4) grown by the Czochralski method. The SRT in Lu₂Co₁₇ was found to consist of two second-order spin reorientations, “easy-plane”–“easy-cone” at T_SR1≈680 K and “easy-cone”–“easy-axis” at T_SR2≈730 K. Upon Si substitution for Co, both SRTs shift toward the lower temperatures in Lu₂Co₁₆Si (T_SR1≈75 K and T_SR2≈130 K) with the further onset of the uniaxial type of magnetic anisotropy in the whole range of magnetic ordering for Lu₂Co_17−xSi_x compounds with x>1 due to a weakening of the easy-plane contribution from the Co atoms at the 6g and 12k sites to the total anisotropy.     

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.     

ESR of double-perovskite Sr2FeMoO6

We present an ESR study of Sr₂FeMoO₆ in the paramagnetic region. A single line at g≈2 was associated with Fe³⁺ ions. The intensity follows Curie–Weiss law in the whole T range. For T >500 K a secondary line is attributed to ferromagnetic (FM) impurities. The line width is described by ΔH_pp(T)=ΔH_pp(∞)(1−Θ/T) with a high value for ΔH_pp(∞). The absence of narrowing effects is a signature of double-exchange (DE) interactions and indicates that DE drives the FM ordering at a relatively high T_c.     

Superconductivity in non-stoichiometric and tin-substituted La2CuO4: preparation, characterization, Mössbauer and microwave-absorption studies

Two samples of non-stoichiometric La₂CuO₄ were synthesized, one with La/Cu<2, and the other with 10% Sn substituting Cu. They were investigated by X-ray diffraction, Mössbauer spectroscopy, and microwave-absorption techniques. The microwave-absorption data indicated that they were both superconducting, with the transition temperatures T_c of 40.5 and 41.5 K, the one doped with Sn possessing the higher T_c. The Mössbauer spectra revealed that there exist two kinds of Sn(IV) atoms disordered with Cu. Their isomer shift, δ=−0.244(4) mm/s, is in agreement with Sn(IV) coordinated by oxygen. One site was characterized by a single Mössbauer line, being associated with a weakly distorted environment, wherein the Sn, coordinated more symmetrically, is surrounded by four Cu²⁺ ions. On the other hand, the other site, characterized by a Mössbauer doublet exhibited a quadrupole splitting Δ=1.07(2) mm/s, being associated with a highly distorted coordination, explained to be due to Sn occupying two adjacent cationic sites. To our knowledge, such a substitution for copper ions not resulting in a decrease of T_c has not been reported previously.     

Crystal and magnetic structure of the sulfur spinels Cu0.45Co0.55Cr2S4 - xSex

The magnetic and crystal structures of the metallic sulfospinels Cu_0.45Co_0.55Cr₂S_{4 - x}Se_x have been investigated for x = 0, 0.42 and 1.0 by neutron powder diffraction techniques. The data have been analyzed by the Rietveld method. All three compositions show ferrimagnetism at low temperatures with a chromium moment of (2.7±0.1)μ_B and a cobalt moment of (2.8±0.1)μ_B. The Curie temperature varies from 293 to 253 K.     

Effect of lead addition to Bi-based 2222 superconducting cuprates Bi2-xPbxSr2(Y, Ce)2Cu2O10+δ

Bi_2-xPb_xSr₂(Y, Ce)₂Cu₂O_10+δ, a new family of lead containing Bi-2222 compounds has been synthesized and effects of annealing in high pressure of oxygen studied. Lead-free Bi₂Sr₂(Y, Ce)₂Cu₂O_10+δ synthesized under flowing oxygen is known to be non-superconducting, but annealing under high oxygen pressure (100 bar) at 500°C, induced superconductivity with T_c=25 K. On substitution of lead (x>0.4), the superconductivity appears even in samples synthesized under flowing oxygen (1 bar). T_c increases with oxygen annealing pressure for all compositions, and it also increases with Pb content at a given oxygen pressure. These findings are discussed.     

Synthesis and superconducting properties of the infinite-layer compounds Sr1−xLnxCuO2(Ln=La, Nd, Sm, Gd)

Infinite-layer-type superconductors Sr_1−xLn_xCuO₂ are synthesized under high pressure of 3 GPa for Ln=Sm, Gd as well as for Ln=La, Nd. Their chemical and superconducting properties are systematically studied as functions of doping concentration and the kind of lanthanide ion. As a result, it is demonstrated that the variation of these properties with doping concentration is similar for all the examined Ln³⁺ ions. The solubility limit lies at x ≈ 0.10. CuO₂ sheets are expanded with increasing x, while their spacing decreases. The T_c onset determined by magnetic measurements remains constant for any doping concentration; only the Meissner fraction increases with increasing x.     

Temperature dependence of the critical current in YBa2Cu3O7−δ and Bi2Sr2Ca1Cu2O8 Josephson junctions

We have studied the stationary Josephson effect on YBa₂Cu₃O_7−δ (T_c=90 K) and Bi₂Sr₂Ca₁Cu₂ O₈ (T_c=80 K and 87 K for two samples of different origin) ceramic based junctions. The temperature dependence of the critical current near T_c has been found as I_c≈(T_c-T) for the Y-Ba-Cu-O samples indicating that they should be classified as S-N-I-N-S type junctions. The I-V curves of the Bi-Sr-Ca-Cu samples show the typical behaviour of S-I-S structures. Using Ambegaokar-Baratoff's theory for Bi₂Sr₂Ca₁Cu₂O₈, the temperature dependence of the superconducting state gap Δ(T) was calculated and it was evaluated that 1.452Δ(0)/k_BT_c3.5.     

Effect of Cu doping in MgB2 superconductor at various processing temperatures

The effects of Cu doping in MgB₂ superconductor has been studied at different processing temperatures. The polycrystalline samples of Mg_1−xCu_xB₂ with x = 0.05 were synthesized through the in-situ solid sate reaction method in argon atmosphere at different temperature range between 800–900 °C. The samples were characterized through X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and low temperature R–T measurement techniques for the phase verification, microstructure and superconducting transition temperature, respectively. The XRD patterns of Mg_1−xCu_xB₂ (x = 0.05) do not exhibit any impurity traces of MgB₄ or MgB₆ and they show the sharp transition in the samples prepared at 850 °C. The onset transition temperature of the prepared samples is around 39 K, which is almost the same as that for the pure MgB₂. This indicates that Cu doping in MgB₂ does not affect the transition temperature. The SEM micrograph of Mg_0.95Cu_0.05B₂ has shown that the sample is dense with grain size smaller than 1 μm.     

Disruption of antiferromagnetic order in Zn-doped La2CuO4

The magnetic phase diagram of La₂(Cu_1−xZn_x)O₄ has been determined from zero-field muon-spin-rotation (ZF-μSR) data taken at LAMPF for 0 ≤ x ≤ 0.10. Antiferromagnetic onset temperatures follow T_N(x) from susceptibility measurements on the same samples. However, the order becomes long range, as evidenced by a well-defined internal magnetic field, only at temperatures well below T_N. Extrapolation of our results yields T_N → 0 K at x = 0.11 for a single (Cu_1−xZn_x)O₂ plane, and comparison with YBa₂(Cu_1−xZn_x)₃O₆ implies identical disruption of magnetism by Zn doping in the single- and double-plane systems.