Evolution des proprietes de transport des solutions solides M1−xM′xF2+x (M=Sr,Pb; M′=Sb,Bi) ET M1−xM″xF2+2x (M″=Zr,Th) pour les faibles taux de substitution

A detailed study of the transport properties of the solid solutions M_1?xM′_xF_2+x (M=Sr, Pb; M′=Sb, Bi) and M_1?xM″_xF_2+2x (M″=Zr, Th) has been carried out for x<0.10. Contrary to solid solutions of strontium, solid solutions of lead show for a very small value of x (x = 0.10 forPb_1?xM′_xF_2+x, x = 0.005 for Pb_1?xM″'_xF_2+2x) a minimum of conductivity associated with a maximum of activation energy. Hypotheses are proposed to explain the results.     

The first-order Raman scattering of Cd1−xPbxF2 mixed crystals

The first-order Raman spectrum of Cd_1?xPb_xF₂ crystals has been measured at room temperature and 100 K. The data clearly indicate the “two-mode” behaviour of the Raman spectrum. It is shown that the disorder contributes mostly to the linewidth broadening in the 0.3 < x < 0.7 composition range.     

Analyzing Power in the Reaction p + p └ → π 0 + X in the polarized-target fragmentation region at an energy of 50 GeV

The results obtained by measuring, at the U-70 accelerator in Protvino, the single-spin asymmetry A _N in the reaction p + p _└ → π⁰ + X at a beam energy of 50 GeV in the Feynman variable range of ?0.6 < x _F < ?0.1 are presented. The asymmetry A _N is close to zero at small |x _F | and grows in magnitude with |x _F |, reaching 6.4% in the region of |x _F | > 0.25. The results of these measurements agree with data of the E704 experiment on the asymmetry of π ₀ mesons at the Fermi National Accelerator Laboratory in the region of polarized-beam fragmentation and with the results of measurements in the region of polarized-target fragmentation that were performed in Protvino by using a 40-GeV π ^?-meson beam and a 70-GeV proton beam.     

Conductivity enhancement in fluorite-structured Ba1−xLaxF2+x solid solutions

The ionic conductivity of single crystals of the fluorite-structured solid solutions Ba_1?xLa_xF_2+x(10^?3 <×<0.45) has been studied as a function of temperature and composition in the range 300–900 K. Three regions can be discerned in the concentration dependence of the ionic conductivity: a dilute concentration region (x<10^?3), where classic relations between solute content and ionic conductivity hold; an intermediate concentration region (10^?3<x?5×10^?2), where large changes occur in the conductivity activation enthalpy and the magnitude of the conductivity; and a concentrated solid solution region (x?5×10^?2) characterized by enhanced ionic motion. In the dilute region the migration enthalpy for interstitial fluoride ions is determined to be 0.714 eV, while a value of 0.39 eV is found for the (La_BaF_i)^X association enthalpy. The defect chemistry in the intermediate concentration region is shown to be controlled by a superlinear increase of the concentration of mobile defects, while in the concentrated solid solution region a composition-independent amount of ≈1 mole% of interstitial fluoride ions with enhanced mobility, carry the current.     

Magnetic phase diagram of GdAg1−xZnx

The magnetic phase diagram of GdAg_1?xZn_x, an intermetallic solid solution of an antiferromagnet (GdAg: T_N = 136 K) and a ferromagnet (GdZn: T_C = 269 K), has been elaborated from magnetization measurements. The antiferromagnetic phase boundary T_N(x) first passes a broad maximum meeting the ferromagnetic phase boundary T_C(x) at x₁ = 0.575 and T₁ = 72 K, where four phases coexist. On approaching (x₁, T₁) along T_N(x) the magnetization phenomena vanish. At x₁ the phase transition still has ferromagnetic appearance but proceeds into a state without spontaneous magnetic moment. Two different ferromagnetic phases (F₁, F₂) and one ferrimagnetic phase (F₃) occur in the composition intervals 0.69 < x₁ <1, and 0.61 <x₂ < 0.69 and 0.51 < x₃ < 0.61. All phase transitions seem to be of second order except th e F₁?F₂ one at x = 0.69 which is of first order. This phase line meets the paramagnetic to ferromagnetic phase boundary T_C(x) in a multicritical point with the coordinates x_m = 0.69, T_m = 123 K.Six further mixed magnetic phases, M_{1, 2, ..., 6}, are observed between x = 0.33 and 0.6 below the antiferromagnetic branch and exhibit irreversible thermodynamic properties, such as hysteresis, below about 40 K.Assuming local magnetic interactions only between nearest and next-nearest Gd neighbours, the T_N(x) and T_C(x) phase boundaries can be described fairly well by a simple model calculation using different exchange parameters for a few relevant distributions of Ag and Zn atoms.     

Single crystals of LnFeAsO1−xFx (Ln = La,Pr, Nd,Sm, Gd) and Ba1−xRbxFe2As2: Growth,structure and superconducting properties

A review of our investigations on single crystals of LnFeAsO_1?xF_x (Ln = La, Pr, Nd, Sm, Gd) and Ba_1?xRb_xFe₂As₂ is presented. A high-pressure technique has been applied for the growth of LnFeAsO_1?xF_x crystals, while Ba_1?xRb_xFe₂As₂ crystals were grown using a quartz ampoule method. Single crystals were used for electrical transport, structure, magnetic torque and spectroscopic studies. Investigations of the crystal structure confirmed high structural perfection and show incomplete occupation of the (O, F) position in superconducting LnFeAsO_1?xF_x crystals. Resistivity measurements on LnFeAsO_1?xF_x crystals show a significant broadening of the transition in high magnetic fields, whereas the resistive transition in Ba_1?xRb_xFe₂As₂ simply shifts to lower temperature. The critical current density for both compounds is relatively high and exceeds 2 × 10⁹ A/m² at 15 K in 7 T. The anisotropy of magnetic penetration depth, measured on LnFeAsO_1?xF_x crystals by torque magnetometry is temperature dependent and apparently larger than the anisotropy of the upper critical field. Ba_1?xRb_xFe₂As₂ crystals are electronically significantly less anisotropic. Point-Contact Andreev-Reflection spectroscopy indicates the existence of two energy gaps in LnFeAsO_1?xF_x. Scanning Tunneling Spectroscopy reveals in addition to a superconducting gap, also some feature at high energy (～20 meV).     

Pressure studies of (La, Sm)FeAsO1−xFx and LaFePO

Pressure dependence on superconducting transition temperature (T_c) was examined for iron-based superconductor LaFeAsO_1?xF_x, SmFeAsO_1?xF_x and LaFePO. The T_c’s increase largely for LaFePO and LaFeAsO_1?xF_x with a small increase of pressure. The electrical resistivity measurements reveal the pressure-induced superconductivity in undoped LaFeAsO and SmFeAsO. X-ray diffraction measurements were also performed under high pressure up to 10 GPa for LaFePO and LaFeAsO_1?xF_x system, where the anisotropic decrease of the lattice constants was observed with applying pressure.     

Ionic conductivity in tysonite-type solid solutions La1−xBaxF3−x

The ionic conductivity of single crystals of tysonite-type solid solutions La_1?xBa_xF_3?x(0?x?0.095) has been studied parallel and perpendicular to the crystallographic c axis in the temperature range 293–1300 K. Three regions can be discerned in the compositional dependence of the ionic conductivity: (i) the “pure” crystal, in which at room temperature no exchange occurs between different types of anion sites in the tysonite structure; (ii) an intermediate region(0 < x < 7 × 10^-2) which reveals changes in both the conductivity activation enthalpy and the magnitude of the conductivity; (iii) a concentrated solid-solution region (x > 7 × 10^-2), where fluoride ions interchange easily among the different anion sublattices. Diffusion coefficients calculated from ionic conductivity results, are in good agreement with those calculated from ¹⁹F NMR measurements. Using the present data, along with ¹⁹F NMR data, dielectric relaxation data and structural considerations, mechanisms governing the ionic conductivity are proposed.     

The thermoelectric power in AgxTiS2 and AgxNiPS3. Part II. The ionic component of the thermoelectric power

The EMF of the isothermal cells: Ag/AgI/Ag_xTiS₂: 0<x<1, T=150–200°C/Ag_xNiPS₃: 0<x<3, T=150–350°C has been measured. From the EMF-x curves the existence ranges of the 2-phase (stage I and II) regions ?0.16<x<0.32 for the Ag/Ag_xTiS₂ system at 190°C; 0.20 < x < 0.50 and 1 < x < 2 for the Ag/Ag_xNiPS₃ system at 400°C - have been determined. The results are sustained by X-ray diffraction and electrical conductivity measurements. From the EMF-T curves the partial enthalpy (ΔH?_Ag) and entropy (ΔS?_Ag) of dissolution of silver in the Ag_xSSE (solid solution electrode) materials were obtained. In the case of Ag_xTiS₂, ΔH?_Ag has a low absolute value, while ΔS?_Ag is distinctly positive. The EMF of the Ag/Ag_xNiPS₃ system also has a positive temperature coefficient. Furthermore, the ionic component of the thermoelectric power, ΔE/ΔT, of the thermogalvanic cells: Ag/AgI/Ag_xSSE/AgI/Ag Ag_xTiS₂: 0 < x < 1, T = 150–200°C( T ) (T+ΔT) Ag_xNiPS₃: 0 < x < 1, T= 150–350°C has been measured. The kinetically important heat of transport of silver ions in the Ag_xSSE materials has been determined in two ways: first from the dependence of the ionic Seebeck coefficient (?_Ag+) on reciprocal temperature; and second from direct calculation, using the data for ?_Ag+ and ΔS?_Ag. The heat of transport is much smaller than the activation enthalpy for Ag⁺-conduction, indicating a high ionic polaron binding energy in these materials.     

Electronic conductivity in La1−xBaxF3−x crystals

The electronic conductivities of solid solutions La_1?xBa_xF_3?x (0 ? x ? 0.0952) were investigated up to 533 K using the Hebb-Wagner dc polarization technique. The electrochemical cell (-)La|La_1?xBa_xF_3?x|Pt(+) has been utilized with Pt as the ion-blocking electrode. Under steady-state conditions the La_1?xBa_xF_3?x solid solutions exhibit electronic conductivity. The electronic conductivity vanishes in pure LaF₃. Together with ac conductivity measurements it appears that the ionic transference number for La_1?xBa_xF_3?x (0 ? x ? 0.0952) is essentially unity over the temperature range studied.     

Photoemission study of Pd Zr and Cu Zr alloys

The XPS valence bands and core levels of the alloys Pd_1?xZr_x (0<x<1) and Cu_1?xZr_x (0<x<1) have been measured. The alloys prepared by coevaporation are crystalline — but their valence band spectra are close to those of the metallic glasses of the same compositions. The large valence band and core level shifts observed for Pd can be explained by a simple theory, not necessitating the postulation of a new type of bonding in these systems.     

The classification of superconductors using muon spin rotation

In this paper we explore the role of muon spin rotation (μSR) techniques in the characterization and classification of superconducting materials. In particular we focus upon the Uemura classification scheme which considers the correlation between the superconducting transition temperature,T _c, and the effective Fermi temperature,T _F, determined from μSR measurements of the penetration depth. Within this scheme strongly correlated “exotic” superconductors, i.e, hightT _C cuprates, heavy fermions, Chevrel phases and the organic superconductors, form a common but distinct group, characterized by a universal scaling ofT _C withT _F such that 1/100 <T _C/T _F<1/10. For conventional BCS superconductorsT _C/T _F<1/1000. The results of new μSR measurements of the penetration depth in superconducting Y(Ni_1?x Co _x )₂B₂C and YB₆ are also presented. In Y(Ni_1?x Co _x )₂B₂C the decrease ofT _C with increasing Co concentration is linked to a marked decrease in the carrier density from 2.9·10²⁸ m^?3 atx=0 to 0.6·10²⁸ m^?3, atx=0.1, while the carrier mass enhancement remains almost constant at approximately 10. For YB₆ we find evidence of a modest enhancement of the carrier mass (m ^*/m=3), and a relatively low carrier density of 0.24·10²⁸ m^?3. These results are discussed within the Uemura classification scheme. It is found that neither Y(Ni_1?x Co _x )₂B₂C withT _c/T _F>>1/250 nor YB₆ withT _C/T _F>>1/340 can be definitively classified as either “exttic” or “conventional”, but instead the compounds display behavior which interpolates between the two regimes.     

Thermal desorption spectra of hydrogen from the bulk: ZrV2Hx

Thermal desorption of hydrogen from the bulk of the system ZrV₂H_x, 0.3 ? x ? 4.27, shows spectra which develop from a single peak, for x < 1, to a spectrum that consists of 3 peaks and a shoulder for x ? 4.27. A model is proposed to explain the origin of these peaks and relates them to a consecutive desorption of the hydrogens from the different interstitial sites, in agreement with neutron diffraction data on the sites' occupancy. However, neutron diffraction indicates that up to x ≈ 2.5 the hydrogens occupy the tetrahedral sites formed by 2 Zr and 2 V, nevertheless our results show that there is a large difference in the bonding energy of these sites for hydrogens with x < 1 and hydrogens with 1 < x < 2.5.     

Dielectric relaxation properties of tysonite-type solid solutions La1−xBaxF3−x

Dielectric relaxation properties of solid solutions La_1?xBa_xF_3?x (x ? 0105) have been studied by thermally stimulated depolanzation current (TSDC)- and a c. dielectric loss (DL) techniques.For x < 30 × 10^?3 the dielectric spectra show a relaxation peak which is ascribed to a simple associate of a substitutional dopant ion and a fluoride ion vacancy (Ba_LaV_F)^x in nearest-neighbour position, the vacancy being confined to the B sublattice For x values of about 1.3 × 10^?2 a relaxation peak appears which is tentatively attributed to a similar type of defect associate with the vacancy now confined to the A sublattice of the tysonite anion array One broad relaxation peak dominates the TSDC and DL spectra over the whole concentration range This peak is due to the relaxation of macroscopic space charge, i e ionic conductivity The low-temperature ion conductivity has been determined for several solid solutions, and extrapolates to the high-temperature conductivity determined previously with impedance spectroscopy Below liquid-nitrogen temperature three relaxations are observed, and ascribed to electronic transitions in cenum impurities. A computer programme has been developed to analyse TSDC relaxation peaks, taking dipole-dipole interactions into account Relaxation parameters and dipole concentrations are presented.     

Suppression of superconductivity in Zn-doped SmFeAsO0.8F0.2 system

A series of SmFe_1?xZn_xAsO_0.8F_0.2 samples with x = 0, 0.05, 0.1, 0.2 and 0.4 have been successfully synthesized using a solid state method. The lattice parameters are found to increase with increasing Zn doping content. The superconductivity has been definitely suppressed by Zn doping at Fe site with the transition temperature T_c being reduced from 52.5 K to 23.3 K for the sample of x = 0.05, and to 18.2 K for the sample of x = 0.1. For the samples with x > 0.1, the superconducting transition vanishes, and, at the meantime, the spin-density-wave anomaly recovers at 140 K. The metal to semiconductor transition is also observed in the SmFe_1?xZn_xAsO_0.8F_0.2 system. The behavior of SmFe_1?xZn_xAsO_0.8F_0.2 is very different from that of R_EFeAsO (R_E = rare earth metal), which reveals a very strong electron correlation in SmFe_1?xZn_xAsO_0.8F_0.2.     

On directly measuring relative Fermi energies of noble metals and their alloys

We present the first evidence of direct measurement of relative Fermi energies in alloys and between pure metals. From applying the “atomic” concept of core hole final state screening, the Auger energy shift of noble metal A equals E_F^A?E_F(x). High resolution Auger shifts in P_1?x^tCu_x,Au_xCu_1?x and Au_xAg_1?x demonstrate experimental verification of this simple relation. We find E_F^CuE_F^Au ? ? 0.2 eV, and E_F^Pt ? E_F^Cu and E_F^Ag ? E_F^Au.     

Electrical conduction in sputtered Si:Al films

The d.c. electrical resistivity ?(x, T) has been measured for a series of granular Si_xAl_1?x sputtered films for 0.25 < x < 0.62 and 4K < T < 300 K. Three separate behaviours are identified in ?(x, T) corresponding to extrinsic activated semiconduction, metallic conduction and electron localisation.     

Bonding in the Doubly Disordered Ba1−x Sn x Cl1+y F1−y Solid Solution

New materials were prepared in the SnF₂/BaCl₂ system by precipitation, and in the SnF₂/BaCl₂/BaF₂ system by direct reactions at high temperature in dry conditions. Stoichiometric BaSn₂Cl₂F₄ and BaSnClF₃?0.8H₂O, and a wide Ba_1?x Sn _x Cl_1+y F_1?y solid solution were prepared for the first time. Elemental analysis, X-ray diffraction and ¹¹⁹Sn Mössbauer spectroscopy were used for the characterization and study of bonding in the new materials. Mössbauer spectroscopy was shown to be an excellent method for probing both the type of bonding at tin(II) (ionic or covalent) and the bond strength at the tin sublattice. Tin(II) is covalently bonded in the stoichiometric phases and ionic (Sn²⁺ stannous ion) in the precipitated Ba_1?x Sn _x Cl_1+y F_1?y solid solution. The case of Ba_1?x Sn _x Cl_1+y F_1?y prepared in dry conditions is more complex. At negative y values (Cl: F <1) and more particularly at high x (solid solution rich in tin), a mixture of Sn²⁺ and covalent Sn(II) is observed, with a normal sublattice strength for Sn(II). At positive y values (Cl:F >1) and more particularly at low x (poor in tin), all the tin(II) is in the ionic form. Furthermore, at high x and high y, the tin(II) sublattice strength decreases so drastically that the tin recoil free fraction at ambient temperature is nearly zero. The bonding type and tin sublattice strength can be explained in terms of preference of covalent bonding with F and when tin clustering occurs, whereas an excess Cl around Sn(II) forms ionic bonding and tin rattling due to ionic size mismatch.     

The discovery of a 2H–6H solid state transformation in ZnxCd1−xS single crystals

Single crystals of Zn_xCd_1?xS have been grown from the vapour phase at 1100°C in the presence of H₂S gas. X-ray diffraction studies of the as-grown crystals show that polytypism and stscking faults occur in Zn_xCd_1?xS crystals for x ? 0.94. It is observed that for 0.92 < x < 0.98 the 2H structure of Zn_xCd_1?xS crystals transforms to a disordered 6H structure on annealing in vacuum around 600°C. For 0.95 < x < 0.98 this 6H structure finally transforms to a disordered 3C structure on annealing further at higher temperatures around 800°C. The structural transformations occur through a non-random insertion of stacking faults, as revealed by the diffuse streak joining the X-ray diffraction maxima along the 10.L reciprocal lattice row. Experimental investigation of the diffuse intensity distribution, as recorded on a single crystal diffractometer from partially transformed single crystals, reveals that the mechanism of the transformation is very different from that reported for the same transformation in silicon carbide and cannot be described in terms of a single-parameter model of non-random deformation faulting.     

Forming process of unipolar resistance switching in Ta2O5−x thin films

We investigated the film-thickness and ambient oxygen-pressure dependence of the electric field, E_F, required to initiate unipolar resistance switching (URS) in Ta₂O_5?x thin films. We measured the dependence of E_F by applying a triangular-waveform voltage signal to the film over a wide sweep-rate range (v = 20 mV s^?1 to 5 MV s^?1). Our results showed that the URS-E_F was not influenced by the Ta₂O_5?x film thickness nor ambient oxygen-pressure. This suggested that the URS-forming process in Ta₂O_5?x thin films should be governed by thermally assisted dielectric breakdown in our measurement range.