Pressure Dependence of the Metal-Insulator and Superconducting Phase Transitions in (TMTSF)2 Reo4

Measurements of the pressure and temperature dependence of the a-axis resistivity of (TMTSF) ₂ReO₄, are presented. The metal-insulator transition seen in this material at the remarkably high temperature of ～180 K at ambient pressure and which is associated with an ordering of the ReO₄, anions is suppressed under pressure. For pressures above ～9.5 kbar we observe a superconducting transition near 1.3 K. There is a narrow intermediate pressure regime about 2.5 kbar in width in which both superconductivity and effects of anion ordering are observed. In this regime (i) a superconducting transition is seen near 1.3 K even though ρ just above the transition can be up to 10-100 times greater than ρ(300 K), and (ii) there is an extraordinarily large hysteresis in p below ～ 100 K with the possibility of varying the resistance of the low temperature state by several orders of magnitude by appropriate temperature cycling. These results establish the first order character of the transition. We suggest that at high pressures the anions remain frozen in a metastable disordered state to low temperatures.     

Superconductivity in the Organic Charge Transfer Salts: (TMTSF)2X and (TMTTF)2X

Abstract

We report pressure dependent studies of the a-axis resistivity as a function of temperature for several members of the isostructural families of organic charge transfer salts, (TMTSF)₂X and (TMTTF) ₂X. For a typical (TMTSF)₂X material the low temperature metal-insulator transition seen at 1 bar is suppressed above some critical pressure, P_c, where a superconducting transition is observed near 1 K. We find a correlation between P_c and the ambient pressure c lattice parameter which reflects the anion size. The (TMTTF) _cX salts exhibit very different ambient pressure behaviour but we find that with the application of sufficiently high pressures (～30 kbar) their behaviour resembles that seen in the (TMTSF)₂X family but at lower pressures. In particular we find evidence of a possible superconducting transition near 4 K in (TMTTF)₂Br at 25 kbar. At this pressure the conductivity near 4 K is extremely high with a value approaching 10⁶ (Ωcm)^?1 and the resistivity ratio is about 400.     

Low-Temperature Electron Spin Resonance in (TMTSF)2PF6 in the High Pressure Metallic Phase

Abstract

The electron spin resonance of (TMTSF)₂PF₆ has been observed at low fields (H_o < 110 Oe) in the high pressure, metallic phase (p > 6.5 kbar) in the temperature range 1-4^?K. The anisotropy in the g value is similar to that observed at ambient pressure above the metal-insulator transition. The linewidth is very narrow and the spin susceptibility strongly decreases as the superconducting transition is approached from above. We interpret this as evidence for singlet-paired superconductivity. Superconductivity is observed at 1.1 K and the critical field has angular dependence in the be plane. These observations lead us to conclude that (TMTSF)₂PF₆ is a singlet paired superconductor.     

Magnetovolume effects and effect of pressure on the temperature dependence of sublattice magnetization in Ho(Co<Subscript>0.9</Subscript>Ga<Subscript>0.1</Subscript>)<Subscript>2</Subscript> compounds

The temperature dependence of the magnetic moments of cobalt and holmium ions in the temperature range of 5–300 K at pressures of P = 0 and 5 kbar was determined based on neutron diffraction data on Ho(Co_0.9Ga_0.1)₂ intermetallide. The temperature dependence of the lattice parameter was established, and the spontaneous bulk magnetostriction was determined. These quantities were calculated using the exchange striction model of a ferrimagnet, and good agreement with the experiment was obtained. The parameters of the exchange interaction between pairs of atoms of this compound and the magnetoelastic coupling constant were estimated. An original interpretation of the nature of the first-order magnetic phase transition in HoCo₂ is proposed.     

Pressure and temperature dependence of the electrical resistivity of bulk Al23 Te77 glass

Electrical resistivity of bulk amorphous Al₂₃T₇₇ samples has been studied as a function of pressure (up to 80 kbar) and temperature (down to 77 K). At atmospheric pressure the temperature dependence of resistivity obeys the relation ? = π₀ exp(δE/RT) with two activation energies. In the temperature range 300 K ? T > 234 K the activation energy is 0.58 eV and for 234 >T ? 185 K the value is δE = 0.30 ev. The activation energy has been measured as a function of pressure. The electrical resistivity decreases exponentially with the increase of pressure and at 70 kbar pressure the electrical behaviour of the sample shows a metallic nature with a positive temperature coefficient. The high pressure phase of the sample is found to be a crystalline hexagonal phase.     

New (TMTSF)2X Derivatives: A Change in the Selenium Network Dimensionality Derived From the Molecular and Crystal Structures of (TMTSF)2(Fso3) [T=298K, 123K] and (TMTSF)2(Bro4) T=298K

Abstract

We report the first crystallographic analysis, as a function of temperature, of a TMTSF derivative. Both (TMTSF)₂(FSO₃) and (TMTSF)₂(BrO₄) are isostructural (triclinic, with space group PI) with superconducting (TMTSF)₂(ClO₄). (TMTSF)₂(FSO₃) undergoes a metal-to-insulator transition at 86-90K as observed by microwave conductivity, D.C. conductivity, and magnetic susceptibility. The crystal structure contains 2-dimensional sheets of short Se-Se contacts in the molecular stacking direction and perpendicular to the stacking direction. The temperature dependent variations in these contact distances appear to be of special importance in determining the conduction properties of these materials, and are observed to change in a surprising manner when (TMTSF)₂(FSO₃) is cooled (298 → 123K). The homoatomic Se separations within each TMTSF molecule appear to increase slightly, but not significantly. At the same time the entire 2-dimensional sheet of intermolecular (intra- and interstack) Se-Se contacts between TMTSF molecules contract quite anisotropically, which results in an increase in “dimensionality” of the Se-Se network. Hence, an increase in electrical conduction, in the absence of insulating phenomena, over the temperature range 298 → 123K is not surprising. The intermolecular Se-Se contact distances in (TMTSF)₂(BrO₄) are significantly longer than in (TMTSF)₂(FSO₃) which suggests that the room temperature electrical conductivity of the (BrO₄)^? salt may be diminished compared to the (FSO₃)^? analogue.     

Growth,structure, and superconducting properties of Bi2Sr2Ca2Cu3O10 and (Bi,Pb)2Sr2Ca2Cu3O10‐y crystals

Large and high‐quality single crystals of both Pb‐free and Pb‐doped high temperature superconducting compounds (Bi_1‐xPb_x)₂Sr₂Ca₂Cu₃O_10‐y (x = 0 and 0.3) were grown by means of a newly developed “Vapour‐Assisted Travelling Floating Zone” technique (VA‐TSFZ). This modified zone‐melting technique was realised in an image furnace and allowed for the first time to grow Pb‐doped crystals by compensating for the Pb losses occurring at high temperature. Crystals up to 3×2×0.1 mm³ were successfully grown. Post‐annealing under high pressure of O₂ (up to 10 MPa at T = 500°C) was undertaken to enhance T_c and improve the homogeneity of the crystals. Structural characterisation was performed by single‐crystal X‐ray diffraction (XRD) and the structure of the 3‐layer Bi‐based superconducting compound was refined for the first time. Structure refinement showed an incommensurate superlattice in the Pb‐free crystals. The space group is orthorhombic, A2aa, with cell parameters a = 27.105(4) Å, b = 5.4133(6) Å and c = 37.009(7) Å. Superconducting studies were carried out by A.C. and D.C. magnetic measurements. Very sharp superconducting transitions were obtained in both kinds of crystals (ΔT_c ≤ 1 K). In optimally doped Pb‐free crystals, critical temperatures up to 111 K were measured. Magnetic critical current densities of 2�10⁵ A/cm² were measured at T = 30 K and μ₀H = 0 T. A weak second peak in the magnetisation loops was observed in the temperature range 40‐50 K above which the vortex lattice becomes entangled. We have measured a portion of the irreversibility line (0.1‐5 Tesla) and fitted the expression for the melting of a vortex glass in a 2D fluctuation regime to the experimental data. Measurements of the lower critical field allowed to obtain the dependence of the penetration depth on temperature: the linear dependence of λ(T) for T < 30 K is consistent with d‐wave superconductivity in Bi‐2223. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of high pressure on crystallization of splat-cooled V2O5

Crystallization of splat-cooled V₂O₅ under high pressure was examined. By X-ray diffraction and thermal analysis, it is shown that the non-crystalline V₂O₅ crystallizes dramatically up to about 6 kb. Crystallization temperature increases with increasing pressure under this pressure range.At higher pressure (20–60 kbar), crystallization occurs gradually and the crystallization temperature has a slight tendency to decrease with increasing pressure.     

A survey of the elastic properties of some semiconducting glasses under pressure

We have measured both shear and longitudinal velocities for 10 MHz sound in amorphous As₂S₃, As₂Se₃, As₂Ge₂SeTe, As₂Ge₃Te₁₅ and Cd₆GeTe and Cd₆Ge₃As₁₁ over the pressure range 0–8 kbar and the temperature range 25–100°C. A variety of elastic constants has been computed. Those glasses with larger values of the connectedness were stiffer and showed less pressure effect.     

Hexagonal frustrated RMnO3 manganites (R = Y, Lu) under high pressure

The crystalline and magnetic structures of YMnO₃ and LuMnO₃ hexagonal manganites under pressures of 0–6 GPa and in the temperature range 10–295 K have been investigated by neutron diffraction. Application of pressure leads to a significant decrease in the ordered magnetic moment of Mn ions (at T = 10 K) from 3.27 (0 GPa) to 1.52 μ_B (5 GPa) for YMnO₃ and from 2.48 (0 GPa) to 1.98 μ_B (6 GPa) for LuMnO₃. Under high pressures, spin reorientation of Mn magnetic moments and a change in the symmetry of the antiferromagnetic structure are observed in YMnO₃. The relationship between the triangular lattice distortion parameter and the symmetry of the triangular antiferromagnetic state of RMnO₃ hexagonal manganites is discussed.     

Photoconductivity of rare-earth-doped (CdSe,ZnS)

Photoconductivity rise and decay curves of (CdSe, ZnS) doped with La and Dy separately are investigated as a function of ambient temperature and pressure, electrode material and cell thickness. Using a number of metal electrodes Fe is found to give maximum I_PC/I_DC ratio for (CdSe, ZnS): La and Cu for (CdSe, ZnS): Dy. Due to change in temperature, maximum I_DC and I_PC are found to 70 °C. A possible mechanism is proposed for thermal and photo-excitations in terms of these results. At lower ambient pressure the photocurrent is found to be low. Cell thickness effect also shows changes in I_PC.     

Reverse metal-non-metal transition in semiconducting melts

Electrical conductivity, σ(T), and thermopower, α(T), measurements were performed for liquid TlAsSe₂, CuTlSe₂, Cu_0.2(CuAsSe₂)_0.8, Cu_0.4(CuAsSe₂)_0.6, and Cu_0.6(CuAsSe₂)_0.4 alloys in a wide temperature range (700<T<1800 K) under ambient pressures of argon gas (up to 25 MPa). A reverse metal-non-metal high temperature transition is observed when temperature increases to about 1500 K. A mechanism involving the opening of a pseudogap is proposed. The mechanism suggests formation of both a mobility edge responsible for the electrical conductivity behavior, and a density of states edge that is responsible for the thermopower behavior.     

Superconducting Properties in Metallic Phase of NbS3

Metallic phase of NbS₃ was synthesized by heating the crystal of semiconducting NbS₃. Metallic NbS₃ undergoes superconducting transition around 2 K. The analysis of the angular dependence of the upper critical magnetic field suggests that the effect of filmy or fibrous morphology plays an important role in the superconducting properties.     

Voltage‐current characteristics of Bi‐2223 superconducting tape near Tc under γ irradiation

Voltage‐current characteristics at four different applied magnetic fields (7, 20, 30, and 40 mT) of Bi₂Sr₂Ca₂Cu₃O_x superconducting tape were measured in the temperature range from 100 to 115 K. They were also measured at zero magnetic field before and after γ irradiations up to 10 MRad at different temperatures just below the critical temperature. The data were fitted to a power law expression V = I ^β(T) in which the exponential parameter β under 20 mT field and after irradiation is found to fluctuate around three and then drops to unity near the critical temperature which may be interpreted as a sign of Kosterlitz‐Thouless transition. The electrical properties of the tape were found to be very sensitive to γ irradiation where most of the changes take place in low γ doses. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study of the structure of PyHReO4 under high pressure

The structure of deuterated pyridinium perrhenate (d₅PyH)ReO₄ (C₅D₅NHReO₄) is studied by X-ray diffraction at room temperature and pressures up to 3.5 GPa and by neutron diffraction in the temperature range 10–293 K and at pressures up to 2.0 GPa. Under normal conditions, this compound belongs to the orthorhombic space group Cmc2₁ (ferroelectric phase II). At room temperature and pressures above P > 0.7 GPa, a transition to an orthorhombic phase (paraelectric phase II) is observed. This paraelectric phase is described by the space group Cmcm. At a pressure as high as P = 2.0 GPa, phase I remains stable at temperatures down to 10 K. This fact indicates that the high pressure suppresses the ferroelectric state in deuterated pyridinium perrhenate (d₅PyH)ReO₄.     

Neutron diffraction investigation of the atomic and magnetic structures of MnAs at high pressures

The atomic and magnetic structures of the MnAs compound are investigated using neutron diffraction at high pressures up to 38 kbar in the temperature range 15–300 K. It is found that, as the temperature decreases under high pressure, the MnAs compound undergoes a spin-reorientation transition from the ferromagnetic orthorhombic phase to a new phase whose magnetic moment has both the ferromagnetic and antiferromagnetic components. The structural and magnetic parameters of the high-pressure phases of the MnAs compound are determined.     

Structural phase transition in crystals of the molecular conductor α′-(BDH-TTP)<Subscript>6</Subscript>[Hg(SCN)<Subscript>3</Subscript>][Hg(SCN)<Subscript>4</Subscript>]

Single crystals of the organic conductor α′-(BDH-TTP)₆[Hg(SCN)₃][Hg(SCN)₄] are studied by low-temperature X-ray diffraction at 100–300 K. It is shown that, in the temperature range 250–200 K, the compound undergoes a phase transition, which is accompanied by the appearance of superstructure reflections and a rapid increase in their intensity due to the partial anion and cation ordering. The superstructure is observed down to a temperature of 100 K, at which the set of diffraction data is collected. The temperature dependence of the electrical resistance exhibits a minimum in the range of the structural transition temperature. Under a pressure of up to 10 kbar, the general behavior of the dependence remains unchanged and only the minimum is shifted toward the low-temperature range. The phase transition is completely reversible.     

Superconducting properties of an NbN–SiO2 disordered system obtained by ammonolysis of NbN–SiO2 sol–gel derived coatings

Studies in superconducting properties of NbN–SiO₂ films are reported. The films were obtained through nitridation of sol–gel derived Nb₂O₅–SiO₂ coatings at 1200 °C, a process leading to the formation of disordered structures with NbN metallic grains dispersed in the insulating SiO₂ matrix. Electrical resistivity was measured with the conventional four-terminal method in the temperature range from 5 to 280 K. The samples’ superconducting properties, examined with magnetically modulated microwave absorption (MMMA), depend on the NbN/SiO₂ molar ratio and the film’s thickness.     

Effect of hydrostatic pressure on the elastic moduli of As2S3 and As2Se3 glasses at 195 and 296 K

Velocities of 30 MHz longitudinal and shear ultrasonic waves have been measured in As₂S₃ and As₂Se₃ glasses as a function of hydrostatic pressure up to 1.5 kbar at 195 K and 3 kbar at 296 K. The elastic stiffness moduli are found to have relatively large, positive, pressure dependences which are about the same at both temperatures for both glasses. This behavior is attributed to the weakness of bonding between layers comprised of AsS₃ and AsS₃ pyramids.Inspection of data for a variety of glasses reveals a correlation between the value of C_L/3C_T and whether the elastic moduli are increased or decreased by pressure. (C_L is the longitudinal modulus and C_T the shear modulus.)Using the pressure dependences of the elastic moduli obtained in the present work, it is found that volume change is responsible for most of the temperature dependences of the moduli. In addition elastic gammas are obtained which are consistent with thermal Grüneisen gammas at 12 K. The pressure dependence of the volume of As₂S₃ glass at 296 K is calculated using the present results in the Murnagham equation. Agreement with volumetric data of Weir is obtained.