Superconductivity and crystal structure of ternary CuxMo3S4 compounds with 0 ≤ x ≤ 1 prepared by anodic oxidation of Cu1.0Mo3S4

Superconductivity and crystal structure data are reported for a series of ternary Cu_xMo₃S₄ samples with 0 ≤ x ≤ 1 which were prepared by anodic oxidation of Cu_1.0Mo₃S₄. A phase with the composition Cu_0.5Mo₃S₄ was found to have rhombohedral lattice parameters $\text{a}{}_{\mathrm{R}}\text{= 6.447(5)}\text{A}\text{?}$ and α_R = 93.74(4) ° and a superconducting critical temperature T_c = 5.8 K. The dependence of T_c on pressure for Cu_0.5Mo₃S₄ has been measured between 0 and 19 kbar.     

Synthesis and physical properties of new superconducting Chevrel phases HgxMo6S8

New ternary molybdenum chalcogenides Hg_xMo₆S₈ (0 < x < 1) have been synthesized and investigated for their structural, magnetic, and superconducting behavior. These new phases prepared at low temperature by reaction of mercury with Mo₆S₈ (obtained from oxidation of Cu₂Mo₆S₈ by iodine) have been characterized by x-ray diffraction, static Faraday susceptibility, and superconducting transition temperature studies. HgMo₆S₈ crystallizes in the rhombohedral space group $\text{R}\text{3 (}\text{a}{}_{\mathrm{r}}\text{= 6.51}\text{A}\text{?}\text{, α}{}_{\mathrm{<mtext>r</mtext>}}\text{= 92.53°)}$, has a paramagnetic, temperature dependent susceptibility, and superconducts at 8.1K. As the mercury content decreases, a continuous decrease in T_c from 8.1K to 1.7K for x=0 (Mo₆S₈) is observed.     

Stoichiometry of the chevrel phase SnMo6S8

The phase field of the Chevrel phase Sn_xMo_yS₈ was investigated by metallographic methods. A shift of the phase field away from the “ideal” compound SnMo₆S₈ towards the molybdenum-rich side of the phase diagram was observed. The degree of off-stoichiometry could not yet be determined, however, the c/a ratio of the hexagonal lattice parameters can be used to characterize the samples. Measurements of the superconducting transition temperature indicate two superconducting “phases”, which differ in the c/a ratio of the lattice parameters. While phase A showed a linear variation of T^a_c with c/a in the region from 11.0 to 13.0 K phase B was independent of the c/a ratio with a T^b_c = 10.8 ± 0.2 K.     

Hysteresis and γ-recoil effects in the superconducting compounds HfxZr1−xV2

The anisotropy of the 133–182 keV γ-γ cascade in¹⁸¹Ta measured as a function of temperature between 70K and 298K shows lattice instability, the phenomenon of hysteresis in the vicinity of the lattice transformation temperature (T_L) and a temperature dependent electric field gradient (EFG) at the cubic Hf sites in the superconducting cubic Laves phase (C15) compounds Hf_1?xZr_xV₂ (x=0.0, 0.25 and 0.75). These observations are qualitatively understood by assuming the presence of γ-recoil effects and microdomains fluctuating between the high temperature (T>T_L) and the low temperature (T < T_L) phases of these compounds.     

Metal atom incorporation studies on AxMo6S8 Chevrel phases

Group IIIa metals and Nb, Hg and Pb containing A_xMo₆S₈ Chevrel phases have been synthesized by low temperature reaction (420–430°C) frorn A metal and Mo₆S₈. Some of these phases are hitherto unknown. Electrolysis method of preparation of A_xMo₆S₈ reported by Schöllhorn does not yield the desired phases when A = Pb or Ag. Stoichiometry, thermal stability, electrical and superconducting properties of the compounds have been examined. In the Pb_xMo₆S₈ system, a series of phases with varying x have been prepared and studied. Group IIIa metal and Nb-compounds are found to be semiconductors with low energies of activation exhibiting p-type behavior in the range 77–300 K. Hg-phase behaves as a metal or a degenerate semiconductor and does not become superconducting above 4.2 K. X-Ray, resistivity and T_c studies show that for x ? 0.8 in Pb_xMo₆S₈, the compounds behave more like Mo₆S₈ and only for x ? 1.0 or (PbBi)_1.0, the inherent behavior of the ternary Chevrel phase is exhibited. Seebeck coefficients are small and positive for Mo₆S₈, Cu and Pb-containing phases in the range 77–300 K. The results are discussed in the light of available band structure of these materials.     

Positron annihilation studies in high-Tc superconductors RBa2Cu3Oy,R: La,Nd, Sm,Eu, Gd,Dy, Ho,Y, Er

Positron lifetime and Doppler broadening of the annihilation line measurements have been performed at room temperature in high-T_c superconductors RBa₂Cu₃O_y, where R: La, Nd, Sm, Eu, Gd, Dy, Ho, Y, Er and 6.9 < y ≤ 7. Doppler broadening of the annihilation line measurements have also been performed in high-T_c superconducting samples R RBa₂Cu₃O_y, where R: Nd, Sm, Eu, Ho, Y, Er as a function of temperature between 14 K and 293 K. It was observed that the positron lifetime and the S parameter values at room temperature have no obvious trend in their variation from the yttrium substitution by a rare-earth element. It was also observed that the temperature dependence of the positron annihilation parameters is similar in the high-T_c superconducting samples.     

Low temperature normal state resistance of ternary molybdenum sulfides

The resistance varies as T² over the range of T from T_c to nearly 40 K, in sintered, sputtered and evaporated thin film Cu_xMo₆S₈, and in sputtered PbMo₆S₈ films. In sintered PbMo₆S₈ the resistance varies as T. These results can neither be explained by existing theory for PbMo₆S₈, nor by a Mo₂S₃ phase argument.     

Anomalous states of the structure of (NH4)2SO4 crystals in the temperature range 4.2–300 K

Crystals of the (NH₄)₂SO₄ ammonium sulfate are studied using x-ray diffractometry. It is revealed that the temperature dependence of the lattice parameters exhibits an anomalous behavior, namely, a global hysteresis, and an anomalous increase in the lattice parameter a and the unit cell volume at temperatures below the ferroelectric phase transition point (T _c=223 K). The series of superstructure reflections observed corresponds to an incommensurate composite structure. Analysis of the temperature behavior of the mismatch parameters for the matrix (host) and superstructure (guest) lattices demonstrates that the (NH₄)₂SO₄ compound undergoes a number of phase transitions, including a transition to a three-dimensionally incommensurate composite phase and transitions to commensurate (along one of the crystallographic directions) composite phases.     

Correlation between the superconducting and normal state properties of amorphous molybdenum - silicon alloys

Measurements on amorphous Mo_1?xSi_x (0.27 ≤ × ≤ 0.77) show that with increasing x the superconducting transition temperature, T_c, decreases linearly with x for x ≤ x₀ ≡ 0.63 ± 0.05. The superconducting transition width and normal state resistivity increase rapidly with increasing x as x approaches x₀. For x > x₀, T_c drops below 1.5K. Transmission electron diffraction measurements (0.65 ≤ × ≤ 0.75) detect the presence of a second amorphous phase which resembles a-Si only for samples with x ? 0.75. The behavior near x₀ could be attributed to the onset of an electronic transition involving the conversion of metallically bonded Si to covalently bonded Si.     

正交和四方YBa2Cu3O7-x的热膨胀系数

用电容法测量了正交和四方YBa₂Cu₃O_7-x的热膨胀系数与温度的关系。结果表明,正交样品在205K附近,四方样品在92—130K之间热膨胀系数有异常。估计前者可能与晶格的不稳定性有关,说明具有较强的电-声子相互作用,后者可能与结构转变有关,因此破坏了高温超导电性。同时也发现正交样品在92K热膨胀系数有微小跳跃。由此估计了压力效应 关键词：     

Yb-Ba-Cu(O,F)体系超导电性、点阵常数和热学特性的研究

本文叙述了Yb-Ba-Cu(O,F)体系超导体的制备,点阵常数、单胞体积以及T_c随F加入量和O含量的变化。实验结果表明,在YbBa₂Cu₃O_7-x-δF_2x(0≤x≤1)体系中,O含量越低,T_c越高,点阵常数和单胞体积就越大。晶体结构分析结果证明点阵常数a与b的差值愈大的正交相结构,其超导性能愈好,表明一维Cu-O链结构对高T_c超导机制有重要作用。 关键词：     

Superconductivity in the pseudo-binary A-15 compounds Mo3Os1−χRuχ and Mo3Ir1−χRuχ

Superconducting transition temperatures (T_c) and room temperature lattice parameters (α_o) are reported for the A-15 pseudo-binary systems Mo₃Ir_1−χRu_χ and Mo₃Os_1−χRu_χ (0 ≤ x ≤ 0.8). If Mo₃Ru could be synthesized in the A-15 structure, its T_c and α_o are predicted to be 10–11°K and 4.95 Å, respectively.     

NMR study of Chevrel phase superconductor

The nuclear spin lattice relaxation time, T₁, the Knight shift and the spin echo decay time, T₂, of ²⁰⁷Pb and ⁷⁷Se were measured in Pb_1.125Mo₆Se_7.5 and Pb_1.125Mo₆S_7.5 at He temperatures. The temperature dependence of T₁ shows the existence of the energy gap of 3.5kT_c at both sites of Pb and Se. The Knight shift dose not change with temperature even below T_c. A remarkable decrease of T₂ below T_c is observed, which is opposite to the case in usual type II superconductor.     

Superconductivity with transition temperature up to 80 K for TbSr2Cu2.7Mo0.3O7+δ

A Tb-123 phase with the composition, TbSr₂Cu_2.7Mo_0.3O_7+δ, has been synthesized in single-phase form by the solid-state reaction route. Its phase purity has been confirmed from neutron powder diffraction studies. The as-synthesized Tb-123 sample does not show superconductivity down to 5 K. On the other hand, an unusually high antiferromagnetic ordering temperature (T_N) of around 7 K is seen for the Tb moments. After 120-atm-O₂ post-annealing, bulk superconductivity is achieved in this compound with a superconducting transition temperature (T_c) of about 30 K, without any significant effect on T_N. To achieve higher oxygen content and higher T_c, the as-synthesized sample was subjected to high-pressure oxygenation, carried out in a closed cell, at 5 GPa and 400 °C in the presence of AgO as an excess-oxygen source. This sample exhibited superconductivity onset at around 80 K with a Meissner fraction larger than 10% at 5 K. Our observation of superconductivity at 80 K is the highest T_c to-date for the Tb-123 type compounds.     

The influence of magnetic and structural heterogeneity on thermopower,magnetothermopower, electrical resistivity,and magnetoresistivity of Nd<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganite

The thermopower, S, magnetothermopower, ΔS/S, resistivity, ρ, and magnetoresistivity, Δρ/ρ, depending on the temperature T and magnetic field H, have been studied in an Nd_0.5Sr_0.5MnO₃ single crystal consisting of three types of clusters: an antiferromagnetic CE-type with charge-orbital ordering (below the Neel temperature T_NCE ~ 145 K) and an A-type with T_NA ~ 220 K; a ferromagnetic at 234 ≤ T ≤ 252 K, and a ferromagnetic metal phase below the Curie temperature T_C = 248 K. The thermopower was found to be negative, indicating the dominance of the electronic type of conductivity. In the S(T) curves, a sharp minimum is observed in the temperature range of 100 K ≤ T ≤ 133 K, close to T_NCE, where the absolute S value attains 53 μV/K. With a further increase in temperature, the absolute S value decreases rapidly; at 200 K it is equal to 7 μV/K. It then slightly increases, reaching its maximum value of 15 μV/K at a temperature of 254 K, which is close to T_C. The absolute thermopower decreased under the influence of the magnetic field; i.e., a negative magnetothermopower occurs. In {ΔS/S}(T) curves, a sharp minimum is observed at T = 130 K close to T_NCE, where the magnetothermopower reaches a huge value of ~45% at H = 13.23 kOe. A broad minimum in the {ΔS/S}(T) curves is observed near the Curie temperature and its value is also high, viz., ~15% in the maximum measuring magnetic field of 13.23 kOe. The extremely high magnetothermopower values mean that the charge-orbital ordered nanoclusters or ferron type make the main contribution to the thermopower of the entire sample. The behavior of the ρ(T) and {Δρ/ρ}(T) curves is similar to that of the S(T) and {ΔS/S}(T) dependencies, which is in agreement with this conclusion.     

Superconductivity in the ‘triple-fluorite-layer’ copper oxides (Cu,M)-1232 (M=Mo, W, Re, Pb)

Here two new high-T_c superconductors are reported of the (Cu,M)-1232 structure containing a fluorite-structured (Ce,Y)-O₂-(Ce,Y)-O₂-(Ce,Y) triple-layer block between two adjacent superconductive CuO₂ planes. The new superconductors were found through substitution studies at the Mo site in the recently synthesized superconductor, (Cu_0.75Mo_0.25)Sr₂(Ce_0.67Y_0.33)₃Cu₂O_11+δ or (Cu_0.75Mo_0.25)-1232 [Y. Morita, T. Nagai, Y. Matsui, H. Yamauchi, M. Karppinen, Phys. Rev. B 70 (2004) 174515. [10a]]. Essentially single-phase samples of the (Cu_0.75M_0.25)-1232 phase with M=W, Re and Pb were obtained by an ambient-pressure solid-state synthesis method. Through a subsequent high-pressure oxygenation (HPO) treatment carried out at 5 GPa and 500 °C in the presence of Ag₂O₂ as an oxygen source the M=W and Re samples were successfully ‘superconductorized’. Introduction of Pb was found to markedly enhance the speed of the formation of the 1232 phase, but the (Cu,Pb)-1232 samples did not exhibit superconductivity. Among the superconductive (Cu,M)-1232 samples, the highest T_c value of 56 K was achieved for (Cu_0.75Re_0.25)-1232. It is likely that the higher the average valence of cations in the (Cu,M)O_1+δ charge-reservoir is, the more can the phase accommodate excess oxygen upon HPO treatment and the higher is the resulting T_c value.     

Magnetic susceptibility of fine crystalline high-temperature YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.93</Subscript> superconductors. The role of nanoscale structural disordering

Static magnetic susceptibility χ(T) in the normal state (T_c ≤ T ≤ 400 K) and specific heat C(T) near temperature T_c of the transition to the superconducting state are experimentally studied for a series of fine crystalline samples of high-temperature YBa₂Cu₃O_y superconductor, having y and T_c close to optimal but differing in the degree of nanoscale structural disordering. It is shown that under the influence of structural disordering, there is enhancement of anomalous pseudogap behavior of the studied characteristics and a significant increase in the width of the pseudogap.     

Anisotropic thermal expansion of AEFe2As2 (AE = Ba,Sr, Ca) single crystals

We report anisotropic thermal expansion of the parent, AEFe₂As₂ (AE = Ba, Sr, and Ca), compounds. Above the structural/antiferromagnetic phase transition anisotropy of the thermal expansion coefficients is observed, with the coefficient along the a-axis being significantly smaller than the coefficient for the c-axis. The high temperature (200 K ≤ T ≤ 300 K) coefficients themselves have similar values for the compounds studied. The sharp anomalies associated with the structural/antiferromagnetic phase transitions are clearly seen in the thermal expansion measurements. For all three pure compounds, the ‘average’ a-value increases and the c-lattice parameter decreases on warming through the transition, with the smallest change in the lattice parameters observed for SrFe₂As₂. The data are in general agreement with the literature data from X-ray and neutron diffraction experiments.     

Spin gap, phase separation and d-wave pairing as revealed by electron spin-lattice relaxation in 123 and 124 YBaCuO systems doped with Gd3+

With an original modulation technique, the Gd³⁺ electron spin-lattice relaxation has been investigated in normal and superconducting states of YBa₂Cu₃O_6+x (123) and YBa₂Cu₄O₈ (124) compounds doped with 1% Gd. In the 123 sample withx = 0.9T _c = 90 K), theT ₁ behavior within 50 <T< 200 K reveals the [1 ? tanh²(Δ/2kT)]/T dependence typical of a spin gap opening with Δ ≈ 240 K. Below 50 K, the exponential slowing down ofT ₁ is limited by the Korringa-like behaviorT ₁ T = const); the same Korringa-like law is found in the 123 sample withx = 0.59 (T _c = 56 K) within the total 4.2–200 K temperature range. This is interpreted in terms of microscopic separation of the normal and superconducting phases allowing for the electron spin cross-relaxation between them. In the 124 sample (T _c = 82 K), the Gd³⁺ relaxation rate below 60 K is found to obey a power lawT _n with an exponentn ≈ 3. Such a behavior (previously reported for nuclear spin relaxation) is indicative of the d-wave superconducting pairing. Additional paramagnetic centers characterized by relatively slow spin-lattice relaxation are found in both 123 and 124 systems. A well-pronounced change in theT ₁ temperature dependence atTT* ≈ 180–200 K is observed for these slowly relaxing centers as well as for the conventional, fast-relaxing Gd³⁺ ions, suggesting microscopic phase separation and a change in the relaxation mechanism due to electronic crossover related with the opening of the spin gap. This hypothesis is supported by some “180 K anomalies” previously reported by other authors.     

含Sb的Bi系超导体的研究

Bi-Sr-Ca-Cu-O系中掺入适量的Sb,其高温相(110K相)含量明显多于不掺Sb样品。Sb具有加速高温相形成的作用。对于各义组分为Bi_2-xSb_xSr₂Ca_2.5Cu_3.7O_y的样品,x=0.1最有利于高温相的形成。用液氮中淬火后低温回火的方法,发现在865℃烧结时样品中首先形成的是低温相(80K相),然后再逐渐转变为高温相。T_c值随烧结时间的延 关键词：