Evidence for impurity phase superconductivity in EuMo6S8 under pressure

Magnetization measurements in a static field as a function of temperature (2.5–20K) and pressure to 14 kbar are reported for a series of well characterized samples of EuMo_6+xS_8?y. From these d.c. magnetization data, we find no evidence for bulk superconductivity in any of our samples, although some of them exhibit a strong diamagnetic anomaly in the a.c. susceptibility under pressure, similar to that reported in the literature. An explanation for this anomaly is presented in terms of the presence of a granular superconducting impurity on the grain boundaries of the Chevrel phase compound EuMo₆S₈.     

Low temperature structural distortion in the high Tc Chevrel-phase superconductors PbMo6S8 and SnMo6S8

High-resolution powder neutron diffraction data reveal that, at temperatures below 100 K, oxygen-free, high-T_c samples of PbMo₆S₈ and SnMo₆S₈ exhibit a small structural distortion from the R$\text{3}$ rhombohedral space group. The data cannot be refined in a simple P$\text{1}$ triclinic space group as previously reported for EuMo₆S₈ and BaMo₆S₈. Thus, a supercell ordering is suggested.     

Charge transfer and valence electron concentration in Chevrel phases

Single crystal X-ray diffraction measurements on M_xMo₃S₄ compounds (M = Cu, Ag, Sn, In) yield evidence for the existence of a charge transfer from the interstitial element M to the Mo₆S₈ building blocks. The importance of this transfer was estimated from the contraction of the Mo₆ octahedron as a function of the valency and the concentration of the cations. It is suggested that this effect stabilises the structure and has a strong influence on the superconducting transition temperature. Bonding is discussed using a simple valence bond model which is based on the electron requirement of the Mo₆ octahedron to form 12 covalent bonds.     

Double magnetic entropy change peaks and high refrigerant capacity in Gd1-xHoxNi compounds in the melt-spun form

Gd_1-xHo_xNi melt-spun ribbons were fabricated by a single-roller melt spinning method. All the compounds crystallize in an orthorhombic CrB-type structure. The Curie temperature (T_C) was tuned between 46 and 99 K by varying the concentration of Gd and Ho. A spin reorientation (SRO) transition is observed around 13 K. Different from T_C, the SRO transition temperature is almost invariable for all compounds. Two peaks of magnetic entropy change (ΔS_M) were found. One at the higher temperature range was originated from the paramagnet-ferromagnet phase transition and the other at the lower temperature range was caused by the SRO transition. The maximum of ΔS_M around T_C is almost same. The other maximum of ΔS_M around SRO transition, however, had significantly positive relationship with x. It reached a maximum about 8.2 J kg⁻¹ K⁻¹ for x = 0.8. Thus double large ΔS_M peaks were obtained in Gd_1-xHo_xNi melt-spun ribbons with the high Ho concentration. And the refrigerant capacity power reached a maximum of 622 J kg⁻¹ for x = 0.6. Gd_1-xHo_xNi ribbons could be good candidate for magnetic refrigerant working in the low temperature especially near the liquid nitrogen temperature range.     

On the lattice instabilities in Chevrel phases

X-Ray diffraction measurements on single crystals of rhombohedral M_xMo₆S₈ compounds (M = Cu, Ag, In, Sn, Gd, La), yield evidence for a systematic delocalisation of the cation M from the inversion centre. The delocalisation is proportional to the rhombohedral angle, but is not a simple function of the ionic radii as tabulated for M. It is suggested that this effect is temperature dependent and responsible for the occurence of lattice instabilities in the Chevrel phases. A possible correlation between delocalisation and superconductivity is discussed.     

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.     

Field induced sign reversal of magnetocaloric effect in Gd2In

We report the magnetocaloric effect in the metamagnetic compound Gd₂In obtained from magnetization measurement. Gd₂In was previously reported to have two magnetic transitions: (i) a paramagnetic to ferromagnetic transition below 190 K and (ii) a ferromagnetic to an antiferromagnetic state below 105 K. The low temperature antiferromagnetic state is unstable under an applied magnetic field and undergoes metamagnetic transition to a ferromagnetic like state. We observe conventional positive magnetocaloric effect (the magnetic entropy change, ΔS_M<0) around 190 K at all applied fields. The magnetocaloric effect is found to be inverse (negative) at low fields around 105 K (ΔS_M>0), however it turns positive at higher fields (ΔS_M<0). The observed anomaly is found to be related to the field induced transition which drives the system from an antiferromagnetic to a ferromagnetic state.     

Pressure effect on magnetic properties of RCo12B6 (R=Y,Ce) compounds

The effect of pressure on magnetic properties of YCo₁₂B₆ and CeCo₁₂B₆ was studied in temperature range 5–300 K at pressures up to 9 kbar. The Curie temperature T_C and spontaneous magnetization M_S decrease with pressure for both compounds. The decrease can be attributed mostly to the volume dependence of both, the Co magnetic moment and the exchange interactions. The hybridization of the p–d states as a consequence of small distances between the Co and B atoms can be one reason of the relatively low pressure effects (ΔT_C/Δp=?0.39±0.02 K/kbar, d ln M_S/dp=?0.0013±0.0002 kbar^?1) in YCo₁₂B₆. Higher volume sensitivity of magnetic properties of CeCo₁₂B₆ in comparison with YCo₁₂B₆ can be attributed to the pressure induced changes of the Ce f- and Co d-states.     

Superconducting thin films of MxMo6S8 type

Thin films of M_xMo₆S₈, where M=Pb, Sn, Sn-Al and Cu, known as the Chevrel phases have been prepared by d.c. getter sputtering method and the optimal conditions of their preparation have been determined. The transition temperatures reached: 10.16, 13.66, 11.74 and 12.86 K for thin films with M=Cu, Sn, Sn-Al and Pb respectively. The highest critical fields H_c²(0) of 428 kG were obtained for Pb compounds.     

Electronic structure,spin polarization and high critical fields in Chevrel compounds

Results are presented of an extensive theoretical study of the origin of high field superconductivity and/or magnetism in a number of Chevrel phase ternary compounds, MMo₆X₈ (with M=Sn, Eu, Gd and X=S and/or Se) based on self-consistent linear muffin-tin orbital (LMTO) energy band calculations using the local density approach (Hedin et al. exchange correlation) for the paramagnetic structures and local spin density formalism (Gunnarsson and Lundqvist) for the ferromagnetic structures. All electrons and all 15 atoms/cell are included with the core electrons (including the 4f's) recalculated in each iteration in a fully relativistic representation and the conduction electrons treated semirelativistically (all relativistic terms except spin-orbit). Superconductivity is found to be due to the high Mo d-band density of states (DOS) at E_F resulting from the unusual large charge transfer of Mo electrons to the chalcogen sites. There is also a large charge transfer from the metal site to the cluster (≈2 electrons in Sn and Eu) giving essentially no occupied conduction bands, for example, at the Eu site and a divalent ion isomer shift in very good agreement with the experiments of Dunlap et al. The conduction-electron DOS at the Eu site is found to be reduced by an order of magnitude from its metallic state value - in close agreement with their spin - lattice relaxation rate measurements. This low conduction-electron DOS yields very weak coupling of the 4f electrons to the conduction electrons and only a very weak Ruderman-Kittel-Kasuya-Yosida magnetic interaction showing why all the Chevrel rare-earth compounds - except Ce and Eu - are superconducting despite their having large local magnetic moments. The unusually high upper critical fields, H_c2, in these materials is found to be due to the unusully flat energy bands near F_F. The ferromagnetic (spin polarized) results for the Eu- and Gd-compounds show a net small but positive magnetic moment on the metal site and a small but negative induced spin magnetic moment on the Mo site in the Eu compound. Fermi-contact contributions to the hyperfine field are calculated and found to be in good agreement with the Eu Mössbauer results and the negative NMR Knights shift results of Fradin et al. These results demonstrate theoretically for the first time the validity of the Fischer et al. and Fradin et al. conclusion that the Jaccarino-Peter mechanism is responsible for the large increase in the H_c2 when large concentrations of Eu magnetic impurities are substituted in SnMo₆S₈. Finally, calculated Stoner factors for the paramegnetic phase and spin magnetization densities for the ferromagnetic phase are used to discuss qualitatively the origin of the different behavior observed for GdMo₆S₈ and EuMo₆S₈.     

Spontaneous compactification in generalized Candelas-Weinberg models

In their recent work on the dimensional reduction, Candelas and Weinberg considered a model which is compactified into a direct product space of the Minkowski space (M₄) and an N-dimensional sphere (S_N). In the present paper we investigate generalized models of their type which are compactified into M₄ × S_M × S_N and M₄ × S_M × CP₂. The compactification is caused by the quantum loop effect due to a large number of matter fields. The conditions for the vacuum stability are studied. Numerical computation of the loop effect is undertaken, and it is shown that some of the models of the type M₄ × S_M × S_N admit a stable solution which has finite circumferences of both of the extra spaces and positive coupling constants of the Einstein-Yang-Mills theory in four dimensions.     

Correlations between structure and the superconducting transition temperature in Chevrel phase molybdenum chalcogenides

The superconducting transition temperatures for Chevrel phase materials, M_xMo₆X₈(M=Pb, Sn, rare eart …, X = S, Se, Te) show wide variability even for a single phase, e.g. PbMo₆S₈ with reported T_c's of 9.8–14.7 K. The T_c is shown to be a linear function of the hexagonal crystallographic $\text{c}\text{a}$ ratio when materials are grouped according to the formal charge on the ternary element M. This correlation is discussed in terms of the electron-phonon coupling and electronic density of states.     

Metal-insulator transition in the spinel-type Cu(Ir1−xCrx)2S4 system

A normal thiospinel CuIr₂S₄ exhibits a temperature-induced metal-insulator (M-I) transition around 230 K with structural transformation, showing hysteresis on heating and cooling. On the other hand, CuCr₂S₄ has the same normal spinel structure without the structural transformation. CuCr₂S₄ has been found to be metallic and ferromagnetic with the Curie temperature T_c~377 K. In order to see the effect of substituting Cr for Ir on the M-I transition, we have carried out a systematic experimental study of electrical and magnetic properties of Cu(Ir_1−xCr_x)₂S₄. The M-I transition temperature shifts to lower temperature with increasing Cr-concentration x and this transition is not detected above x~0.05. The ferromagnetic transition temperature decreases as x is decreased and the transition does not occur below x~0.20.     

Superparamagnetism and spin-glass like state for the MnFe2O4 nano-particles synthesized by the thermal decomposition method

MnFe₂O₄ nano-particles with an average size of about 7 nm were synthesized by the thermal decomposition method. Based on the magnetic hysteresis loops measured at different temperatures the temperature-dependent saturation magnetization (M_S) and coercivity (H_C) are determined. It is shown that above 20 K the temperature-dependence of the M_S and H_C indicates the magnetic behaviors in the single-domain nano-particles, while below 20 K, the change of the M_S and H_C indicates the freezing of the spin-glass like state on the surfaces. By measuring the magnetization–temperature (M–T) curves under the zero-field-cooling (ZFC) and field-cooling procedures at different applied fields, superparamagnetism behavior is also studied. Even though in the ZFC M–T curves peaks can be observed below 160 K, superparamagnetism does not appear until the temperature goes above 300 K, which is related with the strong inter-particle interaction.     

Encapsulation of atomic hydrogen into silsesquioxane cages and ESR of encapsulated hydrogen atoms

Hydrogen atoms are encapsulated in octasilsesquioxane, R(SiO_1.5)₈, by irradiation with γ-rays at room temperature. In deca- and dodecasilsesquioxane, hydrogen atoms are encapsulated by irradiation at 77 K. The thermal decay of the encapsulated hydrogen is well described by a single-exponential function. The excitation energies of the decay are 110–117, 50.4, and 55.6 kJ/mol for the hydrogen atoms in Q₈M₈, Q₁₀M₁₀, and Q₁₂M₁₂, respectively. Theg-values and hyperfine splitting (hfs) constants of the hydrogen atoms in R(SiO_1.5)₈ are dependent on the substituents in the corners of the polyhedra, R. Theg-values are independent of the temperatures, while the hfs constants increase as the temperature decreases. Theg-values of the hydrogen atoms in a large encapsulating cavity decrease with increasing cavity size and approach 2.0023. The temperature dependence of the hfs constants for the hydrogen atoms in Q₁₀M₁₀ or Q₁₂M₁₂ suggests that the hydrogen atoms are localized within the encapsulating cages at low temperatures.     

Magnetic properties of GdCo12B6 compound under high pressures

The effects of hydrostatic pressure up to 10 kbar on Curie temperature T_C, compensation temperature T_COMP and spontaneous magnetization M_S of ferrimagnetic GdCo₁₂B₆ compound have been studied. Two antiferromagnetically coupled sublattices that are carrying magnetization of typically 0.42 μ_B/Co atom and 7 μ_B/Gd cancel out at compensation temperature at about 50 K and magnetic ordering temperature T_C=163±2 K. The volume dependence of intrinsic magnetic properties of the GdCo₁₂B₆ compound has been determined by studying it under hydrostatic pressure. The observed increase of M_S with pressure (dM_S/dp=+0.005 μ_B kbar^?1 at 5 K) is attributed predominantly to the pressure induced decrease of Co magnetic moments. The crucial role of Co in this behavior is confirmed by the change of sign of the pressure slope at temperatures above T_COMP and by the fact that the estimated decrease of m_Co is also quite comparable with pressure induced decrease of M_S in YCo₁₂B₆ (dM_S/dp=?0.007 μ_B kbar^?1). The decrease of m_Co is also responsible for the increase of T_COMP with pressure (dT_COMP/dp=+0.06 K kbar^?1). The decrease of T_C with pressure (dT_C/dp=?0.55 K kbar^?1) is comparable to the decrease observed on RCo₁₂B₆ compounds with non-magnetic R and can be attributed to the volume dependence of Co–Co exchange interactions. The remarkable role of the hybridization as a consequence of small distances between Co and B atoms could be a background of this rather unexpected volume stability of magnetic properties.     

Raman scattering in stage 1 europium intercalated graphite

The Raman spectrum of stage 1 europium intercalated graphite, EuC₆, has been recorded at room temperature. EuC₆ has a p(√3 × √3)R30° in-plane superlattice structure, the same as that of LiC₆. The c-axis stacking sequences of EuC₆ and LiC₆ are different. The Raman spectrum of EuC₆ exhibits a broad asymmetric Fano resonance peak at 1500 ± 5 cm^-1, similar to that observed in MC₈ (M = K, RbandCs). However, there is no evidence of any spectral feature around 580 cm^-1 as what has been observed in MC₈. Considering the Raman features of various graphite intercalation compounds in light of their superlattice structures, we suggest that: (1) The feature around 580 cm^-1 is a characteristic associated only with the MC₈p(2 × 2)R0° in-plane superlattice structure. It should originate from the M point phonons of pristine graphite, which become Raman active as predicted by phonon band structure calculations. (2) The continuous background in the spectra of EuC₆ and MC₈, which results in the Fano resonance peak at 1500 cm^-1, is associated with the staggered stacking sequence. Stacking faults are easy to occur in crystals with staggered stacking sequences, but not in crystals with complete elliptical sequences. Therefore, a disorder induced continuum is observed in the Raman spectra of EuC₆ and MC₈, but not in that of LiC₆.     

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.     

Study of the field dependence of the magnetocaloric effect in Nd1.25Fe11Ti: A multiphase magnetic system

The field dependence of magnetic entropy change ΔS_M(T,H) has been studied in the crystalline sample Nd_1.25Fe₁₁Ti, a multiphase system constituted by three phases: Fe₁₇Nd₂, Fe₇Nd and Fe₁₁TiNd. The magnetic entropy change has been calculated from the numerical derivative of magnetization curves M(T,H) with respect to temperature and subsequent integration in field. To determine the field dependence of the experimental ΔS_M, a local exponent n(T,H) can be calculated from the logarithmic derivative of the magnetic entropy change vs. field. In contrast with the results for single phase materials, where n at the Curie temperature T_C is field independent, it is shown that for a multiphase system n evolves with field both at the Curie temperature of the system and the Curie temperatures of the constituent phases. This is in agreement with numerical simulations using the Arrott-Noakes equation of state.     

Field-induced structural transition and the related magnetic entropy change in Ni43Mn43Co3Sn11 alloy

Magnetic properties and magnetic entropy change ΔS were investigated in Heusler alloy Ni₄₃Mn₄₃Co₃Sn₁₁. With decreasing temperature this alloy undergoes a martensitic structural transition at T_M=188 K. The incorporation of Co atoms enhances ferromagnetic exchange for parent phases. Austenitic phase with cubic structure shows strong ferromagnetic behaviors with Curie temperature T_C^A at 346 K, while martensitic phase shows weak ferromagnetic properties. An external magnetic field can shift T_M to a lower temperature at a rate of 4.4 K/T, and a field-induced structural transition from martensitic to austenitic state takes place at temperatures near but below T_M. As a result, a great magnetic entropy change with positive sign appears. The size of ΔS reaches 33 J/kg K under 5 T magnetic field. More important is that the ΔS displays a table-like peak under 5 T, which is favorable for Ericsson-type refrigerators.