Orthorhombic structure: a necessity in superconducting 1-2-3 compounds

X-ray and resistivity measurements on YBa₂Cu₃O_7−δ (1-2-3) samples show that for the same but low oxygen concentration,δ⋍0·55, no superconducting transition down to 4·2 K is observed for the tetragonal phase samples while the orthorhombic phase shows aT _c ∼ 31 K. The effect of oxygen concentration onT _c is isolated.T _c=91±1 K has, however, been observed continuously for the normal oxygen annealed samples,δ⋍0·07. The experimental results suggest strongly the necessity of the 1-2-3 compound to be in the orthorhombic phase for the superconducting mechanism to be operative.     

Potentiometric CO2 - sensors with ion - conducting glasses as solid electrolytes

Alkali-ion conducting glasses/glass ceramics of the system Me₂O-A1₂O₃-SiO₂ (Me=Li, Na) were applied as solid electrolytes in potentiometric gas sensors to detect CO₂ in the presence of O₂ at increased temperatures. The corresponding Me-Carbonates were utilized as auxiliary electrodes. Sensors using the direct Au-glass contact as a kind of reference electrode (type I), as well as symmetrical sensors with carbonate phase at the reference and measuring electrode (type II - for comparative measurements) were manufactured. By applying Au as electrode metal, the theoretically expected EMF difference and the observed EMF difference of both sensor types agree quite well with the expected values according to the Nernst equation between 500 and 600 °C (over four orders of magnitude of CO₂ partial pressure (10⁻⁵ – 10⁻¹ bar) at constant O₂ partial pressure (2.1×10⁻¹ bar)). A long time stability of 120 days for sensors of type I with Li glasses has been observed, although evaporation of carbonate phase (Li₂CO₃) was detected under the conditions of sensor application. Sensors of type I (with Li₂CO₃) show thermodynamically unexpected cross-sensitivities to H₂O. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Identification ofμ +-sites in the 1-2-3 compoundin the 1-2-3 compound

Possibleμ ⁺ sites have been identified by a comparison of measured spontaneous internal fields in YBa₂Cu₃O_6+δ and REBa₂Cu₃O_7−δ and of measured second moments and width of transverse field powder spectra with the corresponding calculated quantities. In the YBa₂Cu₃O₇ system only one possibleμ ⁺ site emerges at a distance of ∼1.05 A from a chain oxygen O(4) at the position (0.15(1), 0.44(1), 0.071(1)). In the system YBa₂Cu₃O₆ the only possibleμ ⁺ sites are near to an oxygen O(1) with z/c=0.133 and the same distance as above. The analysis leads also to improved valuesμ _Ho = 2.2(1)μ _B andμ _Cu = 0.67(4)μ _B and to a determination of the latters direction:μ _Cu ‖〈110〉.     

Atomic structures of gallium-rich GaAs(001)-4×2 and GaAs(001)-4×6 surfaces

Scanning tunneling microscopy is applied for the first time to an atomic-resolution investigation of the 4×2 and 4×6 phases on a gallium-rich GaAs(001) surface obtained by molecular-beam epitaxy and migration-enhanced epitaxy. A unified structural model is proposed with consideration of the results of experiments and first-principles calculations of the total energy. In this model the 4×2 phase consists of two Ga dimers in the top layer and a Ga dimer in the third layer, and the 4×6 phase is matched to periodically arranged Ga clusters at the corners of a 4×6 unit cell on top of the 4×2 phase. Zh. éksp. Teor. Fiz. 111, 1858–1868 (May 1997)     

Magnetization scaling in the ruthenate-cuprate RuSr2Eu1.4Ce 0.6Cu2O10-δ (Ru-1222)

The magnetic properties of the superconducting ruthenate-cuprate RuSr₂Eu _1.4Ce_0.6Cu₂O_10-δ (Ru-1222) have been studied by a scaling analysis of the dc magnetization and ac susceptibility measurements. Non-linear M(H) curves reveal the presence of nano-size clusters with a net magnetic moment of ∼10² μ_B at 180 K, near the deviation from a Curie-Weiss behavior. On cooling, no scaling was observed down to 90 K, discarding the possibility of magnetic phase separation of collinear ferromagnetic particles. We explain this result in terms of a variable number of contributing particles, with a temperature dependent net magnetic moment. For 70 K ≤T≤ 90 K the scaling plots evidence the emergence of a system of non-interacting particles, which couple on further cooling. The observed cluster-glass features are preserved down to the lowest measured temperature (10 K); no signature of long-range order was detected. The frequency shift of the peak in the real part of the ac susceptibility does not follow the Vogel-Fulcher type dependence, as previously reported. The puzzling temperature dependence of the coercive field, H_C(T), is correlated with the changes in the scaling factors.     

In situ investigation of the catalytic reaction H2+< ![IGNORE[O2→H2 O with second-harmonic generation

2 +O₂→H₂ O in the pressure range 0.2 Torr≤p_tot≤10 Torr on Pt(111) surface. At a catalyst temperature of T=700 K the equilibrium oxygen coverage θ_o is determined as a function of hydrogen partial pressure α. The experimentally obtained θ_o is modelled in a two step process considering the mass transport in the gas phase as well as the catalytic reaction on the surface. In this pressure range the mass transport in the gas phase changes from molecular flow conditions to laminar flow, inducing a strong modification of the gas phase present at the catalyst through different diffusivities of the reactants as well as through desorbing reaction products from the catalyst. It is shown that these gas phase alterations have to be taken into account for a proper modelling of the surface mechanism. Simulation calculations allow one to identify the sequential hydrogen addition reaction as the main reaction path for water production in this parameter range. Excellent agreement with previous investigations is obtained for the determined activation energies of the water-producing reaction steps equal to E^f _H2O≥0.7 eV. Received: 20 September 1998 / Revised version: 15 December 1998     

On the nature of the γ-α transition in cerium

In 1964 Davis and Adams established that the large increase of the thermal expansion and compressibility in the critical region of the γ-to α-Ce phase transition occurs predominantly in the α phase. This provides strong evidence that a tricritical point is realized in Ce. This also means that the aforementioned transition is not isomorphic and that α-Ce should have a distorted fcc structure. A careful examination of Jayaraman’s data (1965) shows that a second-order transition line continues beyond the tricritical point to the vicinity of a triple point on the melting curve. The phase boundary with the tricritical point and the minimum of the melting curve are reconstructed within the framework of Landau theory. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 2, 111–117 (25 January 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Electronic structure and superconductivity of κ-(BEDT-TTF)2X salts

We have analyzed the electronic structure and superconducting properties of layered crystals based on BEDT-TTF salts (hereafter denoted as ET), in which intramolecular interaction among electrons is important. For the case of realistic κ-packing of ET-molecules in a plane of ET₂ dimers we have calculated the electron density of states. Using the calculated electronic structure, we have analyzed the symmetry of the anisotropic superconducting pairing. The critical value of the effective attraction between electrons for formation of a bound pair in an empty lattice has been estimated. The relation between the nodes of the d-type order parameter on the anisotropic Fermi surface and superconducting properties of the condensate is discussed in the Bardeen-Cooper-Schrieffer (BCS) model. The results are in agreement with the known band parameters of the normal phase and measurements of the magnetic field penetration depth, heat capacity as a function of temperature in the low-temperature range, and NMR in κ-ET₂X superconducting salts. Zh. éksp. Teor. Fiz. 113, 715–733 (February 1998)     

Fluctuation-Induced Conductivity of Polycrystalline (Ho–Ce)Ba2Cu3O$_{7-\boldsymbol\delta}$ Superconductor

We report on systematic conductivity fluctuation measurements on samples of Ho_1 − x Ce _x Ba₂Cu₃O_7 − δ with x = 0.00, 0.05, and 0.10. The samples were produced by a standard solid-state reaction method, and the microstructure was analyzed by X-ray diffraction. To identify power-law divergences of the conductivity, the results were analyzed in terms of the temperature derivative of the resistivity dρ/dT and with the logarithmic derivative of the conductivity with respect to temperature − dln (Δσ)/dT. It was observed that the critical temperature decreases and that the transition width increases with increasing Ce doping. The data showed the occurrence of a two-stage transition besides the pairing transition splitting, associated with Ce doping and related with the occurrence of a phase separation. Above the critical temperature, the Gaussian and critical regimes were observed. On approaching the zero resistance state, our results showed a power-law behavior that corresponds to a phase transition from a paracoherent to a coherent state of the granular array.     

High oxide ion conductivity in non-stoichiometric pyrochlores and fluorites in the ternary system ZrO2 - Gd2O3 - TiO2

The extents of the cubic fluorite and pyrochlore regions in the ternary oxide system ZrO₂-Gd₂O₃-TiO₂ have been determined experimentally. AC impedance measurements of single phase fluorite and pyrochlore compositions show high oxide ion conduction in compositions containing 20 mol% TiO₂. Resolution of the bulk and grain boundary contributions to the total conductivity show that the bulk ionic conductivity increases with Gd₂O₃ content up to the stoichiometric composition containing 33.33 mol% Gd₂O₃ and then decreases upon further addition of the aliovalent dopant. Trends in conductivity as a function of temperature and dopant density are discussed. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland, Sept. 13–19, 1997.     

Phase diagram of a 2D Ising model within a nonextensive approach

In this work we report Monte Carlo simulations of a 2D Ising model, in which the statistics of the Metropolis algorithm is replaced by the nonextensive one. We compute the magnetization and show that phase transitions are present for q ≠ 1. A q - phase diagram (critical temperature vs. the entropic parameter q) is built and exhibits some interesting features, such as phases which are governed by the value of the entropic index q. It is shown that such phases favors some energy levels of magnetization states. It is also shown that the contribution of the Tsallis cutoff is capital to the existence of phase transitions.     

Solvent and pH Effects on the Fluorescence of 7-(Dimethylamino)-2-Fluorenesulfonate

A novel water-soluble solvatochromic molecule, 7-(dimethylamino)-2-fluorenesulfonate (2,7-DAFS), was prepared by a three-step reaction from 2-nitrofluorene in good overall yield. The pH and solvent effects on the UV-VIS absorption and fluorescence spectra of 2,7-DAFS have been studied. Protonation of the dimethylamino group switches the absorption from intramolecular charge-transfer (ICT) to π → π* transition. The ground state pKa value of 2,7-DAFS was determined as 4.51. The fluorescence spectrum of the excited basic form, *(DAFS), shows a structureless single band with a large Stokes shift, whereas that of the acidic form, *(⁺HDAFS), exhibits a structured band with a small Stokes shift. The emission intensities of the basic and acidic forms versus pH/Ho plots show stretched sigmoidal curves and indicate that (1) the rate of deprotonation of *(⁺HDAFS) is comparable to the fluorescence decay of the species, and (2) the efficient proton-induced quenching of *(DAFS) fluorescence occurs. The pKa* was estimated as −1.7 from the fluorescence titration curve. The fluorescence maximum of *(DAFS) is blue-shifted as the polarity of solvent decreases. However, no clear dependency of the emission intensity and spectral half width, and thus fluorescence quantum yield, on the solvent polarity was revealed. It appears that the fluorescence sensitivity of 2,7-DAFS is 15 ∼ 25 times greater than the sensitivity of a widely utilized fluorescent probe, 5-(dimethylamino)-1-naphthalenesulfonate. This higher sensitivity, together with the ease of derivatization, would provide the fluorene-based fluorescent molecules significant advantages for a variety of applications.     

Superconductivity in TI(Sr2-xPrx)CaCu2O7-δ (0≤x≤1) with an YBa2Cu3O7-δ-like structure

The partial substitution of Sr in TlSr₂CaCu₂O_7-δ with the rare-earth element Pr has the advantage to stablize the tetragonal phase with space group P4/mmm. The T_c value and the superconducting volume fraction increase with increasing Pr concentration up to x=0.5 (T_c=80 K) then decrease. Enhancement of superconductivity by Pr ions in the inherent “over-hole-doping” of the parent TlSr₂CaCu₂O_7-δ compound suggests that the magnetic-pair-breaking effect is very small in this system.     

Dispersion of the Г 6 (1) -Г 6 (2) Nd crystal field excitation in Nd2CuO4

We performed inelastic neutron scattering experiments to determine the dispersion of the Г ₆ ⁽¹⁾ -Г ₆ ⁽²⁾ crystal field excitation in Nd₂CuO₄. Our results can be very well described within the random phase approximation model. This allows a direct determination of the exchange coupling constants between the Nd ions. The superexchange interactions mediated by the oxygen and copper-oxygen layers are determined to be significantly stronger than the in-plane exchange between the Nd ions.     

Phase diagram of a 2D metal system with a variable number of carriers

It is shown that the phase diagram of a 2D metal undergoing a superconducting transition consists of regions of a normal phase where the modulus of the order parameter is absent, an “anomalous normal” phase where the modulus of the order parameter is different from zero but the phase of the order parameter is a random quantity, and a Berezinskii-Kosterlitz-Thouless phase. The characteristic temperatures of transitions between the phases and the behavior of the chemical potential as a function of the fermion density and temperature are found. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 2, 170–175 (25 January 1997)     

Stability of polymer films as a 2D system

According to classical theory of phase transition, fluctuations in systems with low dimensions are so violent that the phase boundary between unstable and metastable states would be smeared. In this experiment, we measure the growth of surface fluctuations on an unstable polymer film with a thickness, h₀ = 5.1 nm, which is much less than the spinodal thickness, h _sp (= 243 nm) thereby the film is in the very deep unstable region. We find the film to show rupturing behavior markedly different from that of an unstable film. Specifically, nucleation of holes – a characteristic rupturing feature of metastable films – is prominent, which is surprising for a film in the very deep unstable region even provision is given to thin films being two-dimensional and hence are susceptible to broadening of the phase boundary by fluctuations. Monte Carlo simulation shows that the nucleated holes can be caused by stochastic thermal fluctuations. Our result thus confirms the broadening of the phase boundary in thin films by fluctuations to be extremely large. As a consequence, the phase behavior of thin films cannot be predicted by the mean-field calculated phase boundary, which however has been the general practice so far.     

Y-branch - the key component for crosstalk reduced optical switches: modelling analysis

A novel design method for switching devices is demonstrated based on waveguide structures with Y-branches and abrupt waveguide changes as key elements. A combination of BPM calculation and eigenmode analysis is shown to be a promising tool to obtain deep insight into the physical mode behaviour. Based on the analysis, a mode converter to match the eigenmodes in amplitudes and phase can be developed and introduced as a correcting device. This method is demonstrated for the crosstalk compensation of a digital switch (DOS) and a Δβ-reversal switch. A crosstalk of about −20 dB can be reduced to −40 dB by this method. This revised version was published online in November 2006 with corrections to the Cover Date.     

Theoretical calculations of the high-pressure phases of ZnF2 and CdF2

First-principles calculations based on density functional theory were used to study the high-pressure phases of both ZnF₂ and CdF₂. We found that the sequence of the pressure-induced phase transitions is: Rutile (P4₂/mnm) ↦ CaCl₂ (Pnnm) ↦ PdF₂ (Pa-3) and CaF₂ (Fm3m) ↦ PbCl₂ (Pnma) ↦ Ni₂In (P6₃/mmc) for ZnF₂ and CdF₂ respectively. In ZnF₂ the behavior of the ground-state total energy, of the Gibbs free energy and of the lattice constant vs. pressure shown that the phase transition at 4 GPa from the rutile-type phase to the CaCl₂-type phase is a second-order phase transition. The mechanism of the structural change was also revealed by the transition from the PbCl₂-type phase to the Ni₂In-type phase in CdF₂. Moreover, the high-pressure behavior of divalent metal fluorides was compared and discussed.     

d = 3 anisotropic and d = 2 tJ models: phase diagrams, thermodynamic properties, and chemical potential shift

The anisotropic d=3 tJ model is studied by renormalization-group theory, yielding the evolution of the system as interplane coupling is varied from the isotropic three-dimensional to quasi-two-dimensional regimes. Finite-temperature phase diagrams, chemical potential shifts, and in-plane and interplane kinetic energies and antiferromagnetic correlations are calculated for the entire range of electron densities. We find that the novel τ phase, seen in earlier studies of the isotropic d=3 tJ model, persists even for strong anisotropy. While the τ phase appears at low temperatures at 30–35% hole doping away from 〈 n_i〉=1, at smaller hole dopings we see a complex lamellar structure of antiferromagnetic and disordered regions, with a suppressed chemical potential shift, a possible marker of incommensurate ordering in the form of microscopic stripes. An investigation of the renormalization-group flows for the isotropic two-dimensional tJ model also shows a clear pre-signature of the τ phase, which in fact appears with finite transition temperatures upon addition of the smallest interplane coupling.     

Thermodynamic parameters of diffuse phase transitions in Ag2Te

A differential thermal analysis in vacuum and studies of the coefficients of electrical conductivity and thermal conductivity, and of the thermal emf are made in Ag₂Te in the neighborhood of the structural phase transition. It is shown that these data can be used to calculate the switching factor L(T), determine the region in which the phases coexist within the transition, and calculate the thermodynamic parameters. Prior to and after the main phase transition, additional displacement transitions are observed. It is found that the phase transition takes place roughly according to the scheme α _{385 K}→α′_{405 K}→β′_{420 K}→β _{440 K}. The specific heat C _p, changes in entropy ΔS and transition enthalpy ΔH, as well as the minimum phase fluctuation volume V, and the heat Q of the phase transition are determined. It is shown that excesses of Te and Ag have almost no effect on the transition temperatures T ₀, but have a substantial effect on the thermodynamic parameters. Fiz. Tverd. Tela (St. Petersburg) 40, 1693–1697 (September 1998)