Cu nuclear spin-spin relaxation in YBa2Cu3O6.98 and YBa2Cu4O8

We have measured the temperature (T) dependence of the transverse relaxation rate (T _G ^–1 ) of the Cu(1) nuclear spin in YBa₂Cu₃O_6.98 (T _c=92 K) and YBa₂Cu₄O₈ (T _c=82 K). From the scaling ratio ofT _G ^–2 (Cu1) toT _G ^–2 (Cu2), we have estimated the strength of a covalent bonding between the CuO₂ plane and the CuO chain to be B0.38×A _zz. The experimentalT _G ^–1 (Cu1) in YBa₂Cu₄O₈ was of the same order of magnitude as the estimated one fromT _G ^–1 (Cu2). These results appear to indicate that the electrons in the CuO₂ plane fairly spread out of the plane in both compounds.     

Magnetic states of Cu1 sublattice in YBa2Cu3Oy high Tc compounds at different oxygen content

Magnetic states of Cu1 sublattice in YBa₂Cu₃O _y : 1%⁵⁷Fe compounds with 6.09 y6.98 were investigated by⁵⁷Fe Mössbauer spectroscopy at 1.68T300 K. It has been found that, upon reducingy, the magnetic transition temperatureT _ml changes from 3.3 to 12 K aroundy6.4 where the superconductivity disappears. The magnetic phase diagram for the Cu1 sublattice is plotted.     

Shape memory behaviour of annealed Ti48.5Ni(51.5− x )Cu x (x = 6.2–33.5) thin films

The shape memory behaviour of (Ni,Cu)-rich Ti–Ni–Cu thin films (Ti_48.9Ni_44.9Cu_6.2, Ti_48.5Ni₄₀Cu_11.5, Ti_48.6Ni_35.9Cu_15.5, Ti_48.3Ni_28.4Cu_23.3, Ti_48.3Ni_23.9Cu_27.8 and Ti_48.5Ni₁₈Cu_33.5) annealed at 773, 873 and 973 K for 1 h was investigated. The films with 6.2, 11.5–15.5 and 23.3–33.5 at% Cu showed a single-stage deformation due to a B2 ? B19′ transformation, a two-stage deformation due to the B2 ? B19 ? B19′ transformation and a single-stage deformation due to the B2 ? B19′ transformation, respectively. The martensitic transformation start temperature (M _s) increased with increasing Cu content and then levelled off for more than 15 at% Cu, indicating a high Ms temperature of 345 K. Temperature hystereses were almost 15 K for all films with more than 10 at% Cu. The critical stress for slip increased with increasing Cu content and increased significantly for the Ti_48.5Ni₁₈Cu_33.5 film, whereas the maximum recoverable strain significantly decreased for the Ti_48.5Ni₁₈Cu_33.5 film. With decreasing annealing temperature, the critical stress for slip increased, but the M _s temperature decreased. It was found that films with 11.5 at% Cu or more, annealed at 873 K, showed a high martensitic transformation temperature and a high critical stress for slip.     

Weak link problem and intragrain current density in polycrystalline Bi1Ca1Sr1Cu2Ox and Tl2Ca2Ba2Cu3O10

Polycrystalline sintered specimen were investigated by means of ac susceptibility and inductive critical current measurements. Main objects are whether the new highT _c oxides have a weakly coupled intergranular structure and to get information about the intragrain critical current density. The Tl₂Ca₂Ba₂Cu₃O₁₀ specimen shows a connective nature similar to YBa₂Cu₃O₇ with low intergrain currents (100 A/cm² at 100K,B=0 T) and high intragrain ones (4.5·10⁵ A/cm² at 100K,B=0 T). The investigation of the Bi₁Ca₁Sr₁Cu₂O_x specimen becomes complex due to the presence of two superconducting phases and the low intragrain critical current density of the lowerT _c phase.     

Crystallographic study of tetragonal,superconducting YBa2(Cu0.93Fe0.05)3O7

Single crystal- and powder X-ray diffraction, powder neutron diffraction at room temperature and 3 K, high resolution electron microscopy and electron diffraction were used to study the crystal- and defect-structure of YBa₂(Cu_0.93Fe_0.05)₃O₇. Crystals of this compound are superconducting (T _c 80 K) and appeart to be tetragonal down to at least 3 K. The structure resembles that of the undoped YBa₂Cu₃O₇ phase with the oxygen content being very close to 7.0 and the Fe atoms preferentially occupying the Cu(1) site. A copper deficiency is shown to be present on this site too, leading to the approximate formula YBa₂(Cu_0.97Fe_0.03)₂(Cu_0.86Fe_0.10.04)O₇. High resolution electron microscopy reveals the existence of orthorhombic micro-domains, 20–30 Å in diameter, probably due to short range ordering of oxygen atoms on the O(1) site. In view of these results the structure has to be regarded as being tetragonal only in a statistical sense.     

Coexistence of superconductivity and magnetic order in YBa2Cu4O8

⁵⁷Fe Mössbauer spectroscopy, magnetic susceptibility and powder x-ray-diffraction measurements were used to study superconductivity and magnetic order in YBa₂(Cu_1?xFe_x)₄O_8+δ. T_c is decreasing with x, disappearing for x>x_c≈0.04. For xc iron substitutes Cu, predominantly in the Cu(1) site exhibiting a single quadrupole Mössbauer spectrum at 90 K. For x>x_c magnetic order is observed in the Cu(2) site, T_N=380 (5) K for x=0.1 and H_eff (Cu(2), 4.2 K)=510(2) kOe. However, the most surprising discovery is that for x=0.025, for which T_c=27(2) K, the Fe in the Cu(1) site orders magnetically at T_N=30(2) K and H_eff (Cu(1), 4.2 K)=461(2) kOe. The coexistence and competition between superconductivity and magnetic order in the Cu(1) and Cu(2) sites in YBa₂Cu₄O₈ are discussed in terms of the previously observed phase diagrams for Y_1?xPr_xBa₂(Cu_1?yFe_y)₃O_z.     

Study of local environment of Cu atoms in Fe73.5Cu1Nb3Si13.5B9 alloy with different annealing temperature

The local environment of Cu atoms in Fe73.5Cu1Nb3Si13.5B9 alloy was investigated by extended X-ray absorption fine structure(EXAFS).Cu clusters began to order when the annealing temperature was around 733 K from the results of the Fourier transform curves.The fitting results showed that the first shell of the near fcc(face-centered cubic)Cu clusters only contained Cu atoms.The coordination number increased with the annealing temperature.Subsequently,the occupancy rate increased from 33.3%(annealed at 733 K)to 100% (annealed at 853 K).This local structural change of Cu atoms could probably affect the distribution of the bcc(body-centered cubic)α-Fe in Fe73.5Cu1Nb3Si13.5B9 alloy.     

High‐temperature thermoelectric properties of Cu2In4Te7

Cu₂Ga₄Te₇ has recently been reported to have a relatively high thermoelectric (TE) figure of merit (ZT). However, the TE properties of Cu₂In₄Te₇, which has the same defect zinc‐blende structure as Cu₂Ga₄Te₇, have been hardly investigated. Here, we demonstrate that Cu₂In₄Te₇ has relatively high ZT values that are similar to those of Cu₂Ga₄Te₇. High‐density polycrystalline bulk samples of Cu₂In₄Te₇ were prepared and their electrical resistivity (?), Seebeck coefficient (S), and thermal conductivity (κ) were measured. Cu₂In₄Te₇ has a maximum ZT of 0.3 at 700 K, with ?, S, and κ values of 62.1 × 10^–5 Ω m, 394 μV K^–1, and 0.61 W m^–1 K^–1, respectively. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Oleylamine‐Assisted Phase‐Selective Synthesis of Cu2−xS Nanocrystals and the Mechanism of Phase Control

Environmentally friendly Cu_2?x S compounds exist in many different mixed phases in nature, while their nanoscale counterparts can be pure phase with interesting localized surface plasmon resonance properties. Because of the complexity of composition and phase, controllable synthesis of Cu_2?x S nanocrystals becomes an important scientific issue in colloidal chemistry. In this work, a hot‐injection method is developed to synthesize Cu_2?x S nanocrystals by injecting a sulfur precursor into a copper precursor using oleylamine and octadecene as solvents. By varying the reaction parameters (temperature, volume ratio of oleylamine/octadecene, molar ratio of Cu/S in the precursors), hexagonal CuS, monoclinic Cu_1.75S, and rhombohedral Cu_1.8S, nanocrystals can be selectively synthesized, providing a platform to illustrate the mechanism of crystal phase control. The crystal phase control of Cu_2?x S nanocrystals is oleylamine‐determined by controlling the molar ratio of Cu/S in the reaction precursors as well as the ratio of Cu_2?x S clusters/Cu⁺ in the subsequent reaction. More importantly, temperature plays an important role in varying the molar ratio of Cu/S and Cu_2?x S clusters/Cu⁺ in the reaction system, which significantly influences the crystal phase of the resulting Cu_2?x S nanocrystals. The understanding into crystal control provides a guideline to realize reproducible phase‐selective synthesis and obtain well‐defined high‐quality materials with precise control.     

A reaction cell for time‐resolved in situ XAS studies during wet chemical synthesis: the Cu2(OH)3Cl case

The use of in situ time‐resolved dispersive X‐ray absorption spectroscopy (DXAS) to monitor the formation of Cu₂(OH)₃Cl particles in an aqueous solution is reported. The measurements were performed using a dedicated reaction cell, which enabled the evolution of the Cu K‐edge X‐ray absorption near‐edge spectroscopy to be followed during mild chemical synthesis. The formed Cu₂(OH)₃Cl particles were also characterized by synchrotron‐radiation‐excited X‐ray photoelectron spectroscopy, X‐ray diffraction and scanning electron microscopy. The influence of polyvinylpyrrolidone (PVP) on the electronic and structural properties of the formed particles was investigated. The results indicate clearly the formation of Cu₂(OH)₃Cl, with or without the use of PVP, which presents very similar crystalline structures in the long‐range order. However, depending on the reaction, dramatic differences were observed by in situ DXAS in the vicinities of the Cu atoms.     

Phase transition and high temperature thermoelectric properties of copper selenide Cu2-x Se （0 ≤ x ≤ 0.25）

With good electrical properties and an inherently complex crystal structure, Cu_2-xSe is a potential “phonon glass electron crystal” thermoelectric material that has previously not attracted much interest. In this study, Cu_2-xSe (0 ≤ x ≤ 0.25) compounds were synthesized by a melting-quenching method, and then sintered by spark plasma sintering to obtain bulk material. The effect of Cu content on the phase transition and thermoelectric properties of Cu_2-xSe were investigated in the temperature range of 300 K—750 K. The results of X-ray diffraction at room temperature show that Cu_2-xSe compounds possess a cubic structure with a space group of Fm3m (#225) when 0.15 < x le 0.25, whereas they adopt a composite of monoclinic and cubic phases when 0 ≤ x ≤ 0.15. The thermoelectric property measurements show that with increasing Cu content, the electrical conductivity decreases, the Seebeck coefficient increases and the thermal conductivity decreases. Due to the relatively good power factor and low thermal conductivity, the nearly stoichiometric Cu₂Se compound achieves the highest ZT of 0.38 at 750 K. It is expected that the thermoelectric performance can be further optimized by doping appropriate elements and/or via a nanostructuring approach.     

Magnetic properties and antiferromagnetic Cu ordering in Pr2CuO4

Bulk-magnetisation measurements and neutron-scattering experiments were performed both on a polycrystalline sample and on a single-crystal of Pr₂CuO₄ in the temperature range from 1.5 to 300 K. Pr₂CuO₄ crystallizes with theT (Nd₂CuO₄)-type structure. We observed antiferromagnetic ordering of the Cu moments belowT _N =(190±2) K in a single crystal and belowT _N =(250±10)K in powder material. The magnetic unit cell dimensions area _m =2a _o ,c _m =c _o ;the Cu moments are oriented in the basal plane with a magnetic saturation moment of _Cu=(0.45±0.12) _B . Pr³⁺ does not order magnetically above 1.5K due to its crystal-field induced singlet ground state as verified by inelastic neutron scattering.     

A high temperature Mössbauer effect study of iron-doped YBa2Cu3O7 superconductor

Superconducting YBa₂Cu_2.955Fe_0.045O₇ has been studied at temperatures between 300 and 1000 K. Spectra were recorded on a sample which was sealed as a pellet pressed with boron nitride. An atmosphere of oxygen was maintained in the sample region at all times. At temperatures up to 900 K, we observed the four iron sites A, (Cu(1) chain-site; square planar oxygen coordination with O(5) vacancy on thea-axis), B, (Cu(2) plane-site; square pyramidal oxygen coordination), C, (Cu(1) chain-site; square pyramidal oxygen coordination with O(5) site occupied) and D, (Cu(1) chain-site; quasi-tetrahedral oxygen coordination with O(4) vacancy along theb-axis). At temperatures up to 700 K, the relative area of the B and C sites remained nearly constant as the temperature was increased. However, the area of the A site decreased while, the D site area increased with increasing temperature. At all times, the total area of sites A and D remained constant, thereby indicating the possibility of oxygen atom hopping in thea-b plane. The quadrupole splitting of each site, except the B site, decreased linearly with increasing temperature.Research supported in part by the Old Dominion University Undergraduate Research Program.     

Room-temperature ferromagnetism of Cu ion-implanted Ga-doped ZnO

1 MeV Cu²⁺ ions have been implanted into un-doped ZnO and Ga-doped ZnO films with a dose of 1 × 10¹⁷ ions/cm² at room-temperature. Cu ion-implanted Ga-doped ZnO had ferromagnetism at room-temperature and the saturation magnetization of this sample was estimated to be 0.12 μ_B per Cu, while the Cu ion-implanted un-doped ZnO did not show ferromagnetic behavior. Near-edge X-ray fine structure (NEXAFS) spectroscopy revealed that a partial amount of implanted Cu ions existed as Cu²⁺ (d⁹) state in Ga-doped ZnO film. On the other hand, almost Cu atoms existed as Cu¹⁺ (d¹⁰) state in un-doped ZnO film. However, the subsequent annealing at temperature above 800 °C on this ferromagnetic sample induced the annihilation of ferromagnetism due to the formation of non-ferromagnetic Cu₂O phase.     

57Fe mössbauer study of high-T c Y−Ba−Cu oxide superconductors

⁵⁷Fe Mössbauer measurements have been performed for Fe-doped YBa₂ (Cu_1-x Fe_x)₃O_7-v (x=0.005–0.10) superconducting oxides. Fe atoms mainly substitute at Cul chain sites and the fraction of Fe at Cu2 plane sites is discussed thermodynamically. The spin direction of Fe at Cu2 was determined to be normal to thec-axis using an oxygen deficient specimen having a strong texture along thec-axis. A magnetically broadened spectrum at 4.2 K for Fe at Cul is compared with a simulated one which takes the distribution of hyperfine fields into account.     

The electronic structure of ordered Cu3Au(001)

The electronic structure of the (001) face of ordered Cu₃Au was studied using synchrotron radiation at BESSY, in the photon energy range 22–80 eV. The Cu 3d-derived bands in Cu₃Au look like the foldedd-bands of fcc Cu metal. Three Au 5d-derived bands were observed at 5.0, 6.1 and 7.0 eV below the Fermi level, which showed no dispersion with change in photon energy. The Cu 3d- and the Au 5d-derived bands are found to be separated in energy. We have calculated self-consistent energy bands along the (001) direction using the fully relativistic LMTO method. Comparison of these bands with those experimentally determined shows good agreement. From the calculated bands along –X the direction dependent densities of states were determined, which give a consistent account for the non-dispersive Au-bands.     

Microstructure of annealed Ti48.5Ni(51.5– x )Cu x (x = 6.2–33.5) thin films

(Ni, Cu)-rich Ti–Ni–Cu amorphous films with a Cu content of 6.2–33.5 at. % formed by sputtering were annealed at 773, 873 and 973 K for 1 h and their microstructures investigated. Two types of precipitate were observed in the annealed films: a Ti(NiCu)₂ phase for the Ti_48.5Ni₄₀Cu_11.5, Ti_48.6Ni_35.9Cu_15.5, Ti_48.3Ni_28.4Cu_23.3 and Ti_48.3Ni_23.9Cu_27.8 films, plus a TiCu phase for the Ti_48.5Ni₁₈Cu_33.5 films. These precipitates were found to have coherency with the B2 matrix in the films annealed at 773 K and were densely distributed within the grains. However, in the films annealed at 873 K, their size increased 10-fold and their density decreased. Annealing at 973 K promoted grain-boundary precipitation and, accordingly, the density of the precipitates in the grain interiors decreased. On the other hand, the annealed Ti_48.9Ni_44.9Cu_6.2 films showed no precipitates in their grain interiors, but the number of grain-boundary precipitates increased with increasing annealing temperature. It was also found that grain size decreased with increasing Cu content and was significantly decreased for the Ti_48.5Ni₁₈Cu_33.5 films.     

Identification of Cu(I) and Cu(II) oxides by electron spectroscopic methods: AES,ELS and UPS investigations

The externally prepared black-coloured copper oxide (T? 700 K, P_O2 ? 100 torr) on a Cu(100) surface is identified by electron spectroscopy as CuO. Compared to the red-coloured Cu(I) oxide (in situ oxidation at T ? 400 K, P_O2 ? 0.5 torr, ～ 10⁹ L), the He(I)- excited photoemisson from CuO reveals characteristic shake-up satellites 10–12 eV below E_F and a broadened emission from overlapping oxygen-induced 2p and Cu 3d states. From the AES and ELS results, in correlation with the data from core electron spectroscopy, chemical shifts of Cu 2p, Cu 3s and Cu 3p in CuO to higher binding energy and decreases in binding energy of the oxygen-induced states were deduced. The unoccupied electron states of Cu at 5 and 7.5 eV above E_F — postulated from the ELS results — are preserved in Cu₂O and CuO compounds. Annealing of the Cu(II) oxide at 670 K is accompanied by decomposition into Cu₂O due to the solid-state reaction following the scheme: 2CuO → 1/2 O₂ + Cu₂O.     

Characterization of Cu additive FePt-C granular films

FePt-C granular films doped with different Cu atomic fractions (x_Cu) were fabricated using facing-target sputtering at room temperature and subsequently annealed at 650 °C. Structural analyses reveal that the as-deposited films are in amorphous state. Appropriate Cu addition (x_Cu = 14) can improve the ordering of L1₀ FePt phase, and excessive Cu doping destroys the formation of ordered L1₀ phase with the appearance of Fe₃C and CuPt phases. Besides, preferential graphitization of amorphous carbon (a-C) occurs near large metal particles upon annealing. Annealing turns the as-deposited superparamagnetic films into ferromagnetic associated with coercivity peaks at x_Cu = 14, drops from ∼11.2 kOe at 5 K to ∼7.2 kOe at 300 K in a 50 kOe field.     

Zero-field μSR study of ErBa2Cu3Ox for various oxygen contentx

Results from zero-field μSR experiments are presented, performed on the high-T _c compounds ErBa₂Cu₃O_x for various oxygen contentx with 6≤x≤7 at temperatures between 40 mK and 300 K. The aim was to study the magnetic ordering behavior of the Cu moments and the Er moments, and its interplay with superconductivity.