Spin crossover in the magnetic phase transition in YBa2(Cu1−x Fex)3O7±δ superconductors

All iron ions in the Cu1 and Cu2 local lattice sites of the YBa₂(Cu_0.9 ⁵⁷Fe_0.1)₃O_7.01 superconductor with T _c=31 K experienced magnetic ordering below T _m=22 K. Therefore, at T < T _m, magnetic ordering coexisted with superconductivity. According to the Mössbauer spectroscopy data, iron ions in Cu2 (Fe2) sites were in the low-spin state at T < T _m(S= 3/2 or 1/2), whereas an equal number of iron ions in Cu1 (Fe1) sites were in the high-spin Fe³⁺ state (S=5/2). The magnetic transition near T _m changed iron ion spin states-low-spin ions turned into high-spin ions, and vice versa. This preserved the spin balance between iron ions in the Cu1 and Cu2 layers. Control measurements on other samples of the YBa₂(Cu_{1? x} Fe_x)₃O_7±δ series substantiated these conclusions.     

Magnetism and superconductivity in R1.5Ce0.5MSr2Cu2O10‐δ (M=Ru and Fe) compounds

It is shown here, that the superconducting (SC) R_1.5Ce_0.5RuSr₂Cu₂O_10-δ (RCeRuSCO, R= Eu and Gd) materials (T_c ～ 32 and 42 K) are also antiferromagnetically (AFM) ordered at T _N(Ru) ～ 122 and 180 K, respectively, thus, T_N ? T_c, a trend which is contrary to that obtained in “magnetic‐SC” intermetallic systems. Mössbauer spectroscopy (MS) on 0.5% ⁵⁷Fe doped samples shows that all Fe ions reside in the Ru site which is magnetically ordered, whereas SC is confined to the CuO₂ planes. On the other hand, for Y_1.5Ce_0.5FeSr₂Cu₂O₉ (YCeFSCO) no SC is found and the Cu–O planes order AFM at T _N(Cu)=31 K. MS studies reveal two in equivalent Fe sites, and that Fe resides predominantly (60%) in the Cu(1) site. In both sites, the Fe does not order magnetically, and the low T _N(Cu) obtained is due to frustration of the Cu moments by the presence of Fe. T _N is sensitive to oxygen concentration and shifts toward 260 K when oxygen is depleted.     

Re-entrant superconductivity in a magnetically ordered superconductor: La1-xGdxRu2

We have measured the critical temperature (T_c) and the upper critical magnetic field (H_c2) of La_1-xGdxRu₂. At low concentrations of the magnetic impurity (Gd), the suppression of T_c follows the expected Abrikosov-Gorkov (A-G) pair breaking curve. However, for larger concentrations, strong deviations below A-G are observed. Samples in this region (4. ? × ? 5. at. %) exhibit two T_c's. La_1-xGd_xRu₂ is known to order magnetically, probably as a spin glass, and the magnetic ordering temperature (T_M) has been measured in the normal state. This T_M curve intersects the T_c curve in the concentration range where the T_c curve is re-entrant and we therefore attribute the re-entrant T_c behavior to the magnetic ordering of the Gd³⁺ ions.     

NMR experiment on high-T c oxides at Tokyo Metropolitan University

NMR experiments on high-T _c oxides done at Tokyo Metropolitan University are reviewed. The first is⁸⁹Y NMR in YBCO with Y site dilutely substituted by Gd ions. The second isT ₂ ^t-1 of^63,65Cu NQR in YBCO. The third is¹H NMR from probe material coated on YBCO and BSCCO.     

Superconductivity and magnetic order in RBa2Cu3Oz

Mössbauer studies of⁵⁷Fe in RBa_2?y K _y (Cu_1?x Fe _x )₃O_z, with R=Y and Pr;y=0 and 0.5;x=0.01, 0.05 and 0.1 andz between 5.9 and 7.1, have been performed. A minority of the iron ions enter the Cu(2) site and reveal its magnetic order. In nonsuperconducting YBa_1.5K_0.5(Cu_0.95Fe_0.05)₃O_6.1 two distinctly inequivalent magnetic iron sites are observed, probably corresponding to iron in the Cu(2) site with different Ba?K neighbours. In superconducting (T _c =60 K) YBa_1.5K_0.5(Cu_0.95Fe_0.05)₃O_6.5 one Cu(2) subsite remains magnetic (T _N=440 K). The implications of these findings on the valencies of the Cu ions are discussed.     

Peculiarities of performance of the spin valve for the superconducting current

The spin valve effect for the superconducting current based on the superconductor/ferromagnet proximity effect has been studied for a CoO _x /Fe1/Cu/Fe2/Cu/Pb multilayer. The magnitude of the effect ΔT _c = T _c ^AP ? T _c ^P , where T _c ^P and T _c ^AP are the superconducting transition temperatures for the parallel (P) and antiparallel (AP) orientation of magnetizations, respectively, has been measured for different thicknesses of the Fe1 layer d _Fe1. The obtained dependence of the effect on d _Fe1 reveals that ΔT _c can be increased in comparison with the case of a half-infinite Fe1 layer considered by the previous theory. A maximum of the spin valve effect occurs at d _Fe1 ～ d _Fe2. At the optimal value of d _Fe1 almost full switching from the normal to the superconducting state when changing the mutual orientation of magnetizations of the iron layers Fe1 and Fe2 from P to AP is demonstrated.     

Unusual behavior of nuclear relaxation in CeCu2Si2 “possible evidence for triplet superconductivity”

Nuclear relaxation of ⁶³Cu in the superconducting state of the Kondo-lattice system CeCu₂Si₂ has been studied with the use of the ⁶³Cu nuclear quadrupole resonance technique under zero field and down to 65mK. The nuclear spin-lattice relaxation rate (1/T₁) decreases drastically just below T_c=0.67 K down to 0.5T_c without the apparent enchanced behavior and then is found to be almost temperature independent below 0.3T_c. These results suggest that the superconductivity in CeCu₂Si₂ is not in the usual BCS regime. The analysis based upon the existing triplet pairing model with an anisotropic energy gap describes well the behavior from T_c down to 0.5T_c, while the temperature independence below 0.3T_c remains unexplained.     

Photoemission on the highT c superconductors Y−Ba−Cu−O

XPS and UPS photoemission experiments on the highT _c superconductors (T _c ≈90 K) with nominal composition YBa₂Cu₃O_9-y (y≈2) show the following:

1. The density of electronic states at the Fermi energy is very small, much smaller than in pure Cu.
2. The Cu 2p spectra show only a Cu²⁺ contribution.
3. The Ba core levels show a structure with two components of nearly equal magnitude, which leads to the suggestion that these compounds have large O^2? vacancies coordinated to Ba²⁺ sites.
4. Annealing at 400°C under UHV conditions leads possibly to a partial reduction of Cu²⁺ to lower Cu valence states and to a small increase of the O^2? vacancy component of the Ba²⁺ line.

     

On field effect studies and superconductor-insulator transition in high-Tc cuprates

We summarize previous field effect studies in high-T _c cuprates and then discuss our method to smoothly tune the carrier concentration of a cuprate film over a wide range using an applied electric field. We synthesized epitaxial one-unit-cell thick films of La_2?x Sr _x CuO₄ and from them fabricated electric double layer transistor devices utilizing various gate electrolytes. We were able to vary the carrier density by about 0.08 carriers per Cu atom, with the resulting change in T _c of 30 K. The superconductor-insulator transition occurred at the critical resistance very close to the quantum resistance for pairs, R _Q = h/(2e)² = 6.5 kΩ. This is suggestive of a quantum phase transition, possibly driven by quantum phase fluctuations, between a “Bose insulator” and a high-T _c superconductor state.     

Quantum theory of nonresonant electromagnetic and ultrasonic absorption in glasses

We develop quantum theory of nonresonant ultrasonic and electromagnetic absorption in glasses at low temperatures. In the quantum region where ?ω?kT the nonresonant absorption coefficients are proportional to ω³ which seems to be in agreement with the existing experimental data.The existence of characteristic temperature T_c (or characteristic energy E_c = kT_c) of the order of 10 + 20 K is established. At higher interlevel spacing E the concept of two-level systems in their conventional form is not applicable because of their strong coupling to the phonons. Neither the perturbation theory is applicable for calculation of absorption in the frequency interval ?ω?_c or at temperature interval T?T_c = E_c/k.     

Checkerboard patterns and magnetic resonance peak in cuprate superconductors

We investigate a kind of spin-Peierls transition (SP) in high T_c superconductivity. It is found the antiferromagnetic exchange integral of SP corresponds to the magnetic resonance peak. The kind of spin-Peierls transition applied to cuprate superconductors is that without dimerization of lattice ions and with dimerization of localized hole h_Cu attached to the ion. Absence of the magnetic resonance peak in La-Sr-Cu-O results from the dimerized state of localized hole, h_Cu below T_c into tetramerized phase above T_c in SP transition without dimerization of copper-ion. The checkerboard patterns with four unit cell period originate from the SP of electronic part without ion-dimerization and from charge occupation probability of oxygen-atom around Cu.     

MgB2 coated superconducting tapes with high critical current densities fabricated by hybrid physical-chemical vapor deposition

The MgB₂ coated superconducting tapes have been fabricated on textured Cu (0 0 1) and polycrystalline Hastelloy tapes using coated conductor technique, which has been developed for the second generation high temperature superconducting wires. The MgB₂/Cu tapes were fabricated over a wide temperature range of 460-520 °C by using hybrid physical-chemical vapor deposition (HPCVD) technique. The tapes exhibited the critical temperatures (T_c) ranging between 36 and 38 K with superconducting transition width (ΔT_c) of about 0.3-0.6 K. The highest critical current density (J_c) of 1.34 × 10⁵ A/cm² at 5 K under 3 T is obtained for the MgB₂/Cu tape grown at 460 °C. To further improve the flux pinning property of MgB₂ tapes, SiC is coated as an impurity layer on the Cu tape. In contrast to pure MgB₂/Cu tapes, the MgB₂ on SiC-coated Cu tapes exhibited opposite trend in the dependence of J_c with growth temperature. The improved flux pinning by the additional defects created by SiC-impurity layer along with the MgB₂ grain boundaries lead to strong improvement in J_c for the MgB₂/SiC/Cu tapes. The MgB₂/Hastelloy superconducting tapes fabricated at a temperature of 520 °C showed the critical temperatures ranging between 38.5 and 39.6 K. We obtained much higher J_c values over the wide field range for MgB₂/Hastelloy tapes than the previously reported data on other metallic substrates, such as Cu, SS, and Nb. The J_c values of J_c(20 K, 0 T) ∼5.8 × 10⁶ A/cm² and J_c(20 K, 1.5 T) ∼2.4 × 10⁵ A/cm² is obtained for the 2-μm-thick MgB₂/Hastelloy tape. This paper will review the merits of coated conductor approach along with the HPCVD technique to fabricate MgB₂ conductors with high T_c and J_c values which are useful for large scale applications.     

Frequency dependent magnetic susceptibility and spin glass freezing inPtMn alloys

We report measurements of the low-field complex magnetic susceptibility on Pt_1?x Mn _x forx=0.01, 0.025 and 0.05 and for frequencies ν between 10 and 4,000 Hz. A strong frequency dependence of the freezing temperatureT _f is observed: ΔT _f /T _f Δ lnv=0.025 (decade ν)^?1 for all three alloys. These results as well as previous other measurements are interpreted in terms of a phenomenological model.     

Imperfection of the clustered perovskite structure, phase transitions, and magnetoresistive properties of ceramic La0.6Sr0.2Mn1.2 ? x Ni x O3 ± δ (x = 0–0.3)

Ceramic samples of lanthanum strontium manganite perovskites La_0.6Sr_0.2Mn_{1.2 ? x} Ni _x O_{3 ± ??} (0 ?? x ?? 0.3) have been investigated using the X-ray diffraction, magnetic (??_ac), ⁵⁵Mn NMR, resistive, and magnetoresistive methods. The specific features of the influence of the composition on the structure and properties of nonstoichiometric manganite perovskites have been established. It has been found that the rhombohedrally (R $\bar 3$ c) distorted perovskite structure contains cation and anion vacancies, as well as nanostructured clusters with Mn²⁺ ions in the A-positions. The substitution of Ni³⁺ ions (r = 0.74 ?) for Mn³⁺ ions (r = 0.785 ?) leads to a decrease in the lattice parameter a, the ferromagnetic-paramagnetic phase transition temperature T _C, and the metal-semiconductor phase transition temperature T _ms due to the disturbance of the superexchange interactions between heterovalent manganese ions Mn³⁺ and Mn⁴⁺. The observed anomalous magnetic hysteresis at 77 K has been explained by the antiferromagnetic effect of the unidirectional exchange anisotropy of the ferromagnetic matrix structure on the magnetic moments of the superstoichiometric manganese Mn²⁺ ions located in nanostructured planar clusters. An analysis of the asymmetrically broadened ⁵⁵Mn NMR spectra of the compounds has revealed a high-frequency electronic superexchange of the ions Mn³⁺ ? O^2? ? Mn⁴⁺; a local heterogeneity of their surrounding by other ions, vacancies, and clusters; and a partial localization of Mn⁴⁺ ions. The local hyperfine interaction fields on ⁵⁵Mn nuclei have been determined. The concentration dependences of the activation energy and charge hopping frequency have confirmed that the Ni ions decrease the electrical conductivity due to the weakening of the electronic superexchange Mn³⁺ ? O^2? ? Mn⁴⁺. Two types of magnetoresistive effects have been found: one effect, which is observed near the phase transition temperatures T _C and T _ms, is caused by scattering at intracrystalline nanostructured heterogeneities, and the other effect, which is observed in the low-temperature range, is induced by tunneling through intercrystalline mesostructured boundaries. The phase diagram has demonstrated that there is a strong correlation between magnetic and electrical properties in rare-earth manganites.     

57Fe and119Sn Mössbauer study of Ti-Containing highT c superconductors

⁵⁷Fe and¹¹⁹Sn Mössbauer spectroscopy as well as X-ray diffractometry were used to study Ti?Ca?Ba?Cu?O high T_c superconductors (T_c=106K) in the 4 to 300 K temperature range. X-ray diffractograms showed the dominant phase of these supercondutors to be 2-1-2-2 type. Three main iron sites were found and associalted with Fe in Cu sites in the real crystal. The dopublet with IS=0.25 mm/s and QS=0.7 mm/s at RT was attributed to the regular Cu site. No magnetic splitting was observed either in Sn or in Fe spectra taken even at 4 and 5K.     

Pressure-induced phase transformation in In2Bi

We have made measurements of the pressure dependence of the superconducting transition temperature, T_c, for In₂Bi and related alloys. For In₂Bi- phase alloys, a large discontinuity in T_c is seen at 15–20 kbar, which we associate with a phase transformation first seen by Bridgman [1]. Our measurements suggest that this transformation is produced by the decomposition of In₂Bi into In₅Bi₃ and an In-rich phase. In the low pressure phase, T_c shows a minimum at 9–15 kbar whereas it depends linearly on pressure in the high pressure phase with ?T_c/?P equal to -4.9 × 10^-5 K bar^-1.     

Magnetic properties of high-T c superconductors from NQR and NMR measurements

NMR and NQR spectra and spin-lattice relaxation measurements carried out in LASCO and YBCO-type crystals are presented and analyzed in order to derive insights on the correlations and spin-dynamics of the Cu²⁺ ions and on the microscopic mechanisms of high-T _c superconductivity. As an illustrative example on how the magnetic correlation length and spin dynamics properties can be extracted from the relaxation rateW, the³⁵Cl NMR data in the two-dimensional Heisenberg system Sr₂CuCl₂O₂, around the paramagnetic-antiferromagnetic (PA-AF) transition are first considered. Then the¹³⁹La NQR relaxation measurements in La_2?xSr_xCuO₄ are briefly reviewed and it is shown how a simple picture of localized Cu²⁺ magnetic moments, whose spin fluctuation times are controlled by the charge defects induced by the doping, leads in a direct way to quantitative estimates for the progressive shift, on cooling, of the spectral density of the low-frequency spin excitations towards the high frequency range. This phenomenon can be described in terms of effective spin at the Cu²⁺ ions, and its similarities with the analogous effect of progressive delocalization in Heavy Fermions systems are pointed out. Thus, the superconducting transition appears to occur in an unconventional Fermi liquid with AF correlations among itinerant pseudoparticles, possibly involving a mechanism not directly related to the magnetic correlated dynamics. In fact, a universal behavior of the relaxation rates as a function of temperature is observed, regardless of the transition temperatureT _c. The independence ofT _c from the low frequency static and dynamical spin properties is also indicated by⁸⁹Y Knight shifts and from⁶³Cu relaxation rates in systems like YBa₂Cu₄O₈ (Y124), whereT _c can be changed by atomic substitutions and by controlling the oxygen stoichiometry. The effect of an external magnetic field on the correlated spin dynamics of the AF Fermi liquid is investigated and from a comparison of Cu NQR relaxation and NMR relaxation in oriented powder of YBCO and LASCO it is shown that the external field has the small but unambiguous effect of depressing the relaxation rates aboveT _c, besides strongly enhancing them in the superconducting phase. A maximum in the ratio \({{W\left( {NQR} \right)} \mathord{\left/ {\vphantom {{W\left( {NQR} \right)} {W\left( {\vec H\left\| {\vec c} \right.} \right)}}} \right. \kern-0em} {W\left( {\vec H\left\| {\vec c} \right.} \right)}}\) is thus observed around 80 K, either in LASCO or in YBCO, again indicating that the transition could be driven by a mechanism not directly involving the spin dynamic properties. To study the role of the fluxions belowT _c ⁸⁹Y NMR shifts and spectra in oriented powders of YBCO are analyzed. Information on the spin susceptibility and on the structure of the vortex lattice is obtained. In addition, from the temperature behavior of the linewidth a motional narrowing related to flux melting is evidenced. The effective correlation time for the vortex motion is derived and it is discussed why μ⁺SR cannot detect it in view of the different rigid-lattice line broadening.     

Possible mechanism of superconductivity in the CuO-Cu interface

Apparently, a two-dimensional CuO lattice is formed on the surface of copper oxide in the CuO-Cu interface. This lattice consists of Cu²⁺ and O^1? ions, which form a narrow, partially filled two-dimensional band. In this case, local electron pairs (LEPs) can form in the oxygen subsystem as a result of the fulfillment of the Shubin-Vonsovskii conditions. A crude estimate of the formation temperature of LEPs gives T* ～ 10 4 K. At the concentration in the interface layer n～1.6×10²⁰ cm^?3 and the effective mass of carriers m* ～ m _e, the onset temperature of Bose-Einstein condensation may take a value of T _c ～ 1000 K. The estimate obtained for the temperature T _c corresponds to the experimental value by an order of magnitude.