Microstructure and superconducting properties of the DyBaCuO ceramic doped with Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>, NaCl,and KClO<Subscript>3</Subscript>

This paper reports on a study of the effect of doping with Na₂CO₃, NaCl, and KClO₃ salts on the microstructure and superconducting characteristics of ceramics with nominal compositions Dy_{1 ? x} M _x Ba₂Cu_{3 ? y} O_{7 ? δ} and DyBa₂Cu_{3 ? y} O_{7 ? δ} : M _x for M = Na, K; x = 0.2, 0.3, and y = 0, 0.2. The microstructure was characterized by transmission electron microscopy with local energy-dispersive x-ray in situ analysis (probe size ～1 nm). An analysis shows that none of the doping elements (Na, K, or Cl) enters into 123 grains in sizable amounts and that, as a result, the critical temperature of the superconducting transition remains practically constant in the range 90.0–93.5 K. Potassium and chlorine segregate at grain boundaries. It is shown that grain-boundary segregation of chlorine leads to a substantial increase in the superconducting critical current (by a factor 3–5 at 70 K) as compared to the undoped sample. The possible mechanisms accounting for the effect of Cl on intergrain critical current are discussed.     

Nonstoichiometric high-pressure phase of Tm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

Tm _x Cu₃V₄O₁₂, a perovskite-like oxide (space group, Im-3; Z = 2; a = 7.279–7.293 Å) containing vacancies in its cationic sublattice, was obtained barothermally (P = 7.0–9.0 GPa, t = 1000–1100°C) for the first time. The temperature dependences on the electrical resistivity (10–300 K) and the magnetic susceptibility (0–300 K) were investigated. It was shown that the oxide Tm _x Cu₃V₄O₁₂ is characterized by metal-type conductivity and paramagnetic properties.     

Structural transformations of K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals with variations in temperature

Single crystals of the K₃H(SO₄)₂ compound are investigated using X-ray diffraction on Xcalibur S and Bruker diffractometers. The structure of the low-temperature monoclinic phase is refined (space group C2/c, z = 4, a = 14.698(1) Å, b = 5.683(1) Å, c = 9.783(1) Å, β = 103.01(1)°, T = 293 K, Bruker diffractometer), the structural phase transition is revealed, and the structure of the high-temperature trigonal phase is determined (space group R \(\bar 3\) m, z = 3, a = 5.73(1) Å,c = 21.51(1) Å,T = 458 K, Xcalibur diffractometer).     

Low-temperature thermal-expansion anomaly in Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>CuO<Subscript>6</Subscript>

Single-crystal samples of the Bi_{2 + x}Sr_{2 ? x ? y}Cu_{1 + y}O_{6 + δ} system revealed anomalous (negative) thermal expansion in the temperature range 10–20 K. Magnetic fields of 1–3 T were found to strongly affect the position and width of the anomaly region. A thermal-expansion singularity was detected at temperatures T≈30–50 K, which may be related to the formation of a pseudogap.     

Spin-spin interaction and the EPR spectrum of KDy(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The EPR spectrum of a KDy(WO₄)₂ monoclinic crystal is investigated. It is found that the EPR spectrum of magnetically concentrated materials at a low frequency (9.2 GHz) undergoes a substantial transformation in addition to the well-known broadening of the EPR lines. At low Dy³⁺ concentrations (x<10^?2), the EPR spectrum of an isomorphic crystal, namely, KY_(1?x)Dy_x(WO₄)₂, is characterized by the parameters g_x=0, g_y=1.54, and g_z=14.6. For a magnetically concentrated crystal KDy(WO₄)₂, the g values are as follows: g_x=0, g_y=0.82, and g_z=2.52. It is demonstrated that the difference in the parameters is associated with the specific spin-spin interaction between Dy³⁺ ions, including the Dzyaloshinski interaction, which is not observed at high frequencies.     

Optical and x-ray diffraction studies of the symmetry of distorted phases of the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>ZrF<Subscript>7</Subscript> crystal

(NH₄)₃ZrF₇ single crystals were grown, and polarization-optical and x-ray diffraction studies were performed on powders and crystalline plates of various cuts over a wide temperature range. Phase transitions are revealed at temperatures T _1↑ = 280 K, T _2↑ = 279.6 K, T _3↑ = 260–265 K, and T _4↑ = 238 K on heating and at T _1↓ = 280 K, T _2↓ = 269–270 K, T _3↓ = 246 K, and T _4↓ = 235 K on cooling. The sequence of changes in symmetry is established to be as follows: O _h ⁵ (Z = 4) ? D _2h ²⁵ (Z = 2) ? C _2h ³ (Z = 2) ? C _i ¹ (Z = 108) ? monoclinic²(Z = 216).     

Magnetic properties of the Gd<Subscript>2</Subscript>V<Subscript>0.67</Subscript>Mo<Subscript>1.33</Subscript>O<Subscript>7</Subscript> and Y<Subscript>2</Subscript>VMoO<Subscript>7</Subscript> pyrochlore compounds

It is demonstrated that 50% substitution of vanadium for molybdenum in the pyrochlore lattice of the complex oxide Y₂(V _x Mo_{1 ? x} )₂O₇ results in a transition from the spin-glass ground state (at x = 0) to the ferromagnetic state in Y₂VMoO₇ (a = 10.1645(2) Å, T _C = 55 K). The Gd₂V_0.67Mo_1.33O₇ compound (a = 10.2862(3) Å) is a ferromagnet with T _C (84 K) exceeding that of undoped Gd₂MnO₂O₇.     

Tellurium Solubility in TlGaTe<Subscript>2</Subscript> and TlInTe<Subscript>2</Subscript> and the Electrophysical Properties of Solid Solutions

The complex methods of the physicochemical analysis are used to study TlGaTe₂–Te and TlInTe₂–Te alloys in which the tellurium solubility region up to 5.0 at % is observed. The temperature dependences of the lattice parameters and the electrical conductivity of TlGaTe_{2 + x} and TlInTe_{2 + x} have been studied in different crystallographic directions. The TlGaTe_{2 + x} and TlInTe_{2 + x} solid solutions undergo a phase transition at a temperature of 498 K. The transition nature is interpreted.     

Crystal-structure and magnetic phase transformations in solid solutions of BiFeO<Subscript>3</Subscript>-AFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (A = Ca,Sr, Ba,Pb)

Solid solutions of Bi_{1 ? x} A _x (Fe_{1 ? x/2}Nb _x/2)O₃, where A = Ca, Ba, and Pb, are obtained and their crystal structure and magnetic properties are investigated. It is shown that for A = Ca and x ≈ 0.15, the symmetry of the unit cell changes from rhombohedral (space group R3c) to orthorhombic (Pbnm). The transformation leads to the emergence of spontaneous magnetization due to the Dzyaloshinskii-Moriya interaction. Solid solutions with A = Pb remain rhombohedral up to a concentration of x = 0.3. Spontaneous magnetization sharply increases in the compound with x ≈ 1 at low temperatures and is due to the formation of the spin-glass component.     

The Nernst-Ettingshausen coefficient in the normal phase of doped HTSCs of the YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>y</Subscript> system

The temperature dependence of the Nernst-Ettingshausen coefficient Q(T) in the normal phase of doped HTSCs of the yttrium system was studied. The main features characterizing the behavior of this coefficient were revealed, and the character and mechanism of the effect that various nonisovalent substituents exert on the Q(T) dependence were analyzed. It is shown that the narrow-band model permits one not only to describe all the specific features observed in the Q(T) curves but also to perform a simultaneous quantitative analysis of the temperature dependences of four kinetic coefficients (the electrical resistivity and the Seebeck, Hall, and Nernst-Ettingshausen coefficients) with the use of a common set of model parameters characterizing the band structure and carrier system in the normal phase of an HTSC. This approach was employed to determine the carrier mobilities and the asymmetry of the dispersion curve in the systems studied (YBa₂Cu₃O_y, y = 6.37–6.91; YBa₂Cu_3?xCo_xO_y, x = 0–0.3; Y_1?xCa_xBa₂Cu₃O_y, x = 0–0.25; Y_1?xCa_xBa_2?xLa_xCu₃O_y, x = 0–0.5) and to analyze the effect of the substitutions involved on the variation of these parameters.     

Oxygen isotope effect in chromium-doped Pr<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganites

The effect of oxygen isotope substitution on the properties of Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x O₃ manganites (x = 0, 0.02, 0.05) have been studied. The introduction of chromium favors (i) the decomposition of a charge-ordered state and (ii) the appearance of a ferromagnetic metallic phase in Pr_0.5Ca_0.5Mn_{1 ? x} Cr _x ^16–18O₃. The isotope substitution ¹⁶O → ¹⁸O leads to a decrease in the content of the ferromagnetic phase, an increase in the charge-ordering transition temperature (T _CO), and a decrease in the ferromagnetic transition temperature (T _FM). The isotope mass exponent is evaluated.     

The oxygen content and its ordering in the chain planes in fine-grained HTSC YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>

A comparative analysis of the results of the X-ray and Mösbauer studies of the high-temperature superconductor (HTSC) YBa₂Cu₃O _y and YBa₂Cu_{3 ? x} ⁵⁷Fe _x O _y (x = 0.015, T _c ≈ 91.5 K) samples with different average grain sizes <D> in the micron and submicron ranges has been performed. The regularities in the change in the lattice parameter c and in the degree of occupation of different oxygen sites in the CuO_δ chain planes taking place at the decrease in <D> have been studied. The quantitative interrelation between the parameter c and the oxygen content δ in the CuO_δ planes exceeding the amount of the mobile oxygen due to the interplane oxygen redistribution is established.     

Spontaneous ferroelectricity in strained low-temperature monoclinic Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>: A first-principles study

As a single-phase multiferroic material, Fe₃O₄ exhibits spontaneous ferroelectric polarization below 38 K. However, the nature of the ferroelectricity in Fe₃O₄ and effect of external disturbances such as strain on it remains ambiguous. Here, the spontaneous ferroelectric polarization of low-temperature monoclinic Fe₃O₄ was investigated by first-principles calculations. The pseudo-centrosymmetric FeB42–FeB43 pair has a different valence state. The noncentrosymmetric charge distribution results in ferroelectric polarization. The initial ferroelectric polarization direction is in the -x and -z directions. The ferroelectricity along the y axis is limited owing to the symmetry of the Cc space group. Both the ionic displacement and charge separation at the FeB42–FeB43 pair are affected by strain, which further influences the spontaneous ferroelectric polarization of monoclinic Fe₃O₄. The ferroelectric polarization along the z axis exhibits an increase of 45.3% as the strain changes from 6% to -6%.     

Enhancement of pseudogap anomalies induced by nanoscale structural inhomogeneity in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.93</Subscript> high-<Emphasis Type="Italic">T</Emphasis><Subscript>c</Subscript> superconductor

The magnetization M(H) in the superconducting state, dc magnetic susceptibility χ(T) in the normal state, and specific heat C(T) near the superconducting transition temperature T _c have been measured for a series of fine-crystalline YBa₂Cu₃O _y samples having nearly optimum values of y = 6.93 ± 0.3 and T _c = (91.5 ± 0.5) K. The samples differ only in the degree of nanoscale structural inhomogeneity. The characteristic parameters of superconductors (the London penetration depth and the Ginzburg–Landau parameter) and the thermodynamic critical field H _c are determined by the analysis of the magnetization curves M(H). It is found that the increase in the degree of nanoscale structural inhomogeneity leads to an increase in the characteristic parameters of superconductors and a decrease in H _c(T) and the jump of the specific heat ΔC/T _c. It is shown that the changes in the physical characteristics are caused by the suppression of the density of states near the Fermi level. The pseudogap is estimated by analyzing χ(T). It is found that the nanoscale structural inhomogeneity significantly enhances and probably even creates the pseudogap regime in the optimally doped high-T _c superconductors.     

Exponential Increase in the Resistivity upon Cooling and Superconductivity in Indium-Doped Pb<Subscript>0.45</Subscript>Sn<Subscript>0.55</Subscript>Te

We have analyzed the temperature and magnetic-field dependences of resistivity ρ(T, H) of semiconducting compound Pb_0.45Sn_0.55Te doped with 5 at % In under a hydrostatic compression at P < 12 kbar. It is found that the temperature dependence ρ(T) at all pressures at T < 100 K is exponential with the activation energy decreasing upon an increase in pressure; this is accompanied with a superconducting transition on the ρ(T) and ρ(H) dependences at P > 4.8 kbar at T > 1 K (T _c = 1.72 K at a level of 0.5ρ _N at P = 6.8 kbar). We consider the model describing the low-temperature “dielectrization” of the semiconducting solid solution and the formation of the superconducting state upon an increase in the hydrostatic compression P > 4 kbar.     

High-temperature complex impedance and modulus spectroscopic studies of doped Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-BaTiO<Subscript>3</Subscript> ferroelectric ceramics

Lead-free Na_0.5Bi_0.5TiO₃ (NBT) and (1 ? x)Na_0.5Bi_0.5TiO₃ + xBaTiO₃ with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na_0.5Bi_0.5TiO₃ + yBa_0.925Nd_0.05TiO₃ with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba²⁺ ions to the NBT sample whereas it significantly decreased with the addition of Nd³⁺ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.     

Optical properties of mechanically compressed K<Subscript>2</Subscript>SO<Subscript>4</Subscript> crystals

The effect of a uniaxial mechanical compression (σ_m ≤ 100 bar) on the spectral dependences (300–800 nm) of the birefringence Δn _i and refractive indices n _i of K₂SO₄ crystals is studied. The electronic polarizabilities, refractions, and parameters (λ_0i , B _1i ) of ultraviolet oscillators of mechanically compressed crystals are calculated. It is shown that the dispersions of Δn _i(λ) and n _i(λ) are normal and sharply increase near the absorption edge. It is found that the uniaxial compression changes the value of the dispersions dΔn _i/dλ and dn _i/dλ rather than their character. It is ascertained that the simultaneous action of the compressions σ_x and σ_z, as well as of σ_y and σ_z, leads to the appearance of new isotropic states in the K₂SO₄ crystal, which manifests itself in the equality of corresponding birefringences. It is shown that the baric dependences n _i(σ) are determined by the change in the density of oscillators (～30%), by the shift of the absorption edge and effective band maximum and by the change in the oscillator strength (～70%).     

Stabilization of Ferromagnetism in BiFeO<Subscript>3</Subscript>:Ho at Hydrostatic Pressure

The isothermal magnetization of the Bi_{1 – x}Ho _x FeO₃ (x = 0?0.2) multiferroic has been studied at a hydrostatic pressure up to 9 GPa in the range of room temperatures. A new anomaly at P_C ≈ 3.81 GPa related to intermediate phases between the structural transition R3c → Pnma has been found against the background of the pressure-induced antiferromagnetic ordering in BiFeO₃ (BFO) at P ≈ 2.59 GPa. It is established that the ferromagnetic behavior under pressure depends on the Ho impurity concentration: P_C decreases at 0.05 ≤ x ≤ 0.1 because of the decrease in R3c bond lengths in the structure, and the stabilization of ferromagnetism is implemented at 0.1 ≤ x ≤ 0.2 probably because of the coexistence of the R3c and Pnma phases. The results of studies indicate that, in Bi_{1 – x}Ho _x FeO₃ with x = 0.2, the transition pressure P_C = 3.7 GPa exceeds the values for BFO doped with other 4f elements (Eu, Y, Sm) in the region R3c → Pnma of the transition.     

Structure,ionic conduction,and phase transformations in lithium titanate Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>

The spinel structure of lithium titanate Li₄Ti₅O₁₂ is refined by the Rietveld full-profile analysis with the use of x-ray and neutron powder diffraction data. The distribution and coordinates of atoms are determined. The Li₄Ti₅O₁₂ compound is studied at high temperatures by differential scanning calorimetry and Raman spectroscopy. The electrical conductivity is measured in the high-temperature range. It is shown that the Li₄Ti₅O₁₂ compound with a spinel structure undergoes two successive order-disorder phase transitions due to different distributions of lithium atoms and cation vacancies (□, V) in a defect structure of the NaCl type: (Li)_8a[Li_0.33Ti_1.67]_16dO₄ → [Li□]_16c[Li_1.33Ti_1.67]_16dO₄ → [Li_1.33□_0.67]_16c[Ti_1.67□_0.33]_16dO₄. The low-temperature diffusion of lithium predominantly occurs either through the mechanism ... → Li(8a) → V(16c) → V(8a) → ... in the spinel phase or through the mechanism ... → Li(16c) → V(8a) → V(16c) → ... in an intermediate phase. In the high-temperature phase, the lithium cations also migrate over 48f vacancies: ... Li(16c) → V(8a, 48f) → V(16c) → ....     

Visualization of the magnetic flux structure in phosphorus-doped EuFe<Subscript>2</Subscript>As<Subscript>2</Subscript> single crystals

Magnetic flux structure on the surface of EuFe₂(As_1-x P _x )₂ single crystals with nearly optimal phosphorus doping levels x = 0.20 and x = 0.21 is studied by low-temperature magnetic force microscopy and decoration with ferromagnetic nanoparticles. The studies are performed in a broad temperature range. It is shown that the single crystal with x = 0.21 in the temperature range between the critical temperatures T _SC= 22 K and T _C = (18 ± 0.3) K of the superconducting and ferromagnetic phase transitions, respectively, has the vortex structure of a frozen magnetic flux, typical for type-II superconductors. The magnetic domain structure is observed in the superconducting state below T _C. The nature of this structure is discussed.