Crystallographic characteristics and phase transitions in the [N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>CdBr<Subscript>4</Subscript> crystal in the low-temperature range

The results of x-ray structural studies of the [N(C₂H₅)₄]₂CdBr₄ crystal at low temperatures are presented. The unit cell parameters and the thermal expansion coefficients along the main crystallographic directions are measured at temperatures in the range from 90 to 320 K. The integrated intensities of the diffraction reflections are investigated as a function of the temperature. It is shown that the curves a = f(T), c = f(T), I ₅₀₀ = f(T), and I ₀₀₆ = f(T) at temperatures T ₁ ≈ 174 K and T ₂ ≈ 226 K exhibit anomalies in the form of abrupt changes in the lattice parameters and the diffraction reflection intensities. This indicates that the [N(C₂H₅)₄]₂CdBr₄ crystal undergo phase transitions at these temperatures. Moreover, there is an anomaly in the form of a small maximum at the temperature T ₃ = 293 K.     

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).     

Galvanomagnetic properties of atomically disordered Sr<Subscript>2</Subscript>RuO<Subscript>4</Subscript> single crystals

The effect of neutron-bombardment-induced atomic disorder on the galvanomagnetic properties of Sr₂RuO₄ single crystals has been experimentally studied in a broad range of temperatures (1.7–380 K) and magnetic fields (up to 13.6 T). The disorder leads to the appearance of negative temperature coefficients for both the in-plane electric resistivity (ρ_a) and that along the c axis (ρ_c), as well as the negative magnetoresistance Δρ, which is strongly anisotropic to the magnetic field orientation (H ∥ a and H ∥ c), with the easy magnetization direction along the c axis and a weak dependence on the probing current direction in the low-temperature region. The experimental ρ_a(T) and ρ_c(T) curves obtained for the initial and radiation-disordered samples can be described within the framework of a theoretical model with two conductivity channels. The first channel corresponds to the charge carriers with increased effective masses (～10m _e , where m _e is the electron mass) and predominantly electron-electron scattering, which leads to the quadratic temperature dependences of ρ_a and ρ_c. The second channel corresponds to the charge carriers with lower effective masses exhibiting magnetic scattering at low temperatures, which leads to the temperature dependence of the ρ_{a, c}(T) ∝ 1/T type.     

Electrical conductivity and permittivity of the one-dimensional superionic conductor LiCuVO<Subscript>4</Subscript>

The electrical conductivity σ^a and permittivities ?^a, ?^b, and ?^c of a LiCuVO₄ single crystal have been measured along the a, b, and c crystallographic axes, respectively, in the temperature range 300–390 K at a frequency of 10³ Hz. The temperature dependences σ(T) and ?(T) were found to be typical for superionics.     

Anomalous low-temperature behavior of the thermal characteristics of MgB<Subscript>2</Subscript>

We have studied the behavior of the thermal expansion coefficient α(T) (in a zero magnetic field and at H≈4 T), the heat capacity C(T), and the thermal conductivity κ(T) of magnesium boride (MgB₂) in the vicinity of T_c and at lower temperatures. It was established that MgB₂, like oxide-based high-temperature superconductors, exhibits a negative thermal expansion coefficient at low temperatures. The anomaly of α(T) in MgB₂ is significantly affected by the magnetic field. It was established that, in addition to the well-known superconducting transition at T_c≈40 K, MgB₂ exhibits an anomalous behavior of both heat capacity and thermal conductivity in the region of T≈10–12 K. The anomalies of C(T) and κ(T) take place in the same temperature interval where the thermal expansion coefficient of MgB₂ becomes negative. The low-temperature anomalies are related to the presence of a second group of charge carriers in MgB₂ and to an increase in the density of the Bose condensate corresponding to these carriers at T_c2≈10–12 K.     

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) → ....     

Thermophysical study of structural phase transitions in Na<Subscript>0.95</Subscript>Li<Subscript>0.05</Subscript>NbO<Subscript>3</Subscript> solid solution

Temperature dependences of specific heat C_p(T) and coefficient of thermal expansion ;(T) for Na_0.95Li_0.05NbO₃ sodium-lithium niobate ceramic samples are investigated in the temperature range of 100–800 K. The C_p(T) and α(T) anomalies at T₃ = 310 ± 3 K, T₂ = 630 ± 8 K, and T₁ = 710 ± 10 K are observed, which correspond to the sequence of phase transitions N ? Q ? S(R) ? T2(S). The effect of heat treatment of the samples on the sequence of structural distortions was established. It is demonstrated that annealing of the samples at 603 K leads to splitting of the anomaly corresponding to the phase transition Q → R/S in two anomalies. After sample heating to 800 K, the only anomaly is observed in both the C_p(T) and ;(T) dependence. Possible mechanisms of the observed phenomena are discussed.     

Low-temperature anomalies in the specific heat and thermal conductivity of MgB<Subscript>2</Subscript>

The temperature dependences of the specific heat C(T) and thermal conductivity K(T) of MgB₂ were measured at low temperatures and in the neighborhood of T _c . In addition to the well-known superconducting transition at T _c ≈40 K, this compound was found to exhibit anomalous behavior of both the specific heat and thermal conductivity at lower temperatures, T≈10–12 K. Note that the anomalous behavior of C(T) and K(T) is observed in the same temperature region where MgB₂ was found to undergo negative thermal expansion. All the observed low-temperature anomalies are assigned to the existence in MgB₂ of a second group of carriers and its transition to the superconducting state at T_c2≈10?12 K.     

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.     

Specific features of anion transfer in HoF<Subscript>3</Subscript> crystals at high temperatures

The anionic conductivity of HoF₃ single crystals with a β-YF₃ structure (orthorhombic crystal system, space group Pnma) is investigated over a wide range of temperatures (323–1073 K). The unit cell parameters of HoF₃ crystals are as follows: a=0.6384±0.0009 nm, b=0.6844±0.0009 nm, and c=0.4356±0.0005 nm. It is revealed that the conductivity anisotropy of the HoF₃ crystals is insignificant over the entire temperature range covered. The crossover from one mechanism of ion transfer to another mechanism is observed near the critical temperature T_c≈620 K. The activation enthalpy of electrical conduction is found to be ΔH₁=0.744 eV at T<T_c and ΔH₂=0.43 eV at T>T_c. The fluorine vacancies are the most probable charge carriers in HoF₃ crystals. The fluorine ionic conductivities at temperatures of 323, 500, and 1073 K are equal to 5×10^?10, 5×10^?6, and 2×10^?3 S cm^?1, respectively.     

High-resolution spectroscopy of HoFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a study of phase transitions

The transmission spectra of HoFe₃(BO₃) multiferroic single crystals are studied by optical Fourier-transform spectroscopy at temperatures of 1.7–423 K in polarized light in the spectral range 500–10 000 cm^–1 with a resolution up to 0.1 cm^–1. A new first-order structural phase transition close to the second-order transition is recorded at T_c = 360 K by the appearance of a new phonon mode at 976 cm^–1. The reasons for considerable differences in T_c for different samples of holmium ferroborate are discussed. By temperature variations in the spectra of the f–f transitions in the Ho³⁺ ion, we studied two magnetic phase transitions, namely, magnetic ordering into an easy-plane structure as a second-order phase transition at T_N = 39 K and spin reorientation from the ab plane to the c axis as a first-order phase transition at T_SR = 4.7 ± 0.2 K. It is shown that erbium impurity in a concentration of 1 at % decreases the spin-reorientation transition temperature to T_SR = 4.0 K.     

Magnetic susceptibility of fine crystalline high-temperature YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.93</Subscript> superconductors. The role of nanoscale structural disordering

Static magnetic susceptibility χ(T) in the normal state (T_c ≤ T ≤ 400 K) and specific heat C(T) near temperature T_c of the transition to the superconducting state are experimentally studied for a series of fine crystalline samples of high-temperature YBa₂Cu₃O_y superconductor, having y and T_c close to optimal but differing in the degree of nanoscale structural disordering. It is shown that under the influence of structural disordering, there is enhancement of anomalous pseudogap behavior of the studied characteristics and a significant increase in the width of the pseudogap.     

Effect of the Lattice and Spin-Phonon Contributions on the Temperature Behavior of the Ground State Splitting of Gd<Superscript>3+</Superscript> in SrMoO<Subscript>4</Subscript>

The temperature behavior of the EPR spectra of the Gd³⁺ impurity center in single crystals of SrMoO₄ in the temperature range T = 99–375 K is studied. The analysis of the temperature dependences of the spin Hamiltonian b ₂ ⁰ (T) = b₂(F) + b₂(L) and P ₂ ⁰ (T) = P₂(F) + P₂(L) (for Gd¹⁵⁷) describing the EPR spectrum and contributing to the Gd³⁺ ground state splitting ΔE is carried out. In terms of the Newman model, the values of b₂(L) and P₂(L) depending on the thermal expansion of the static lattice are estimated; the b₂(F) and P₂(F) spin-phonon contributions determined by the lattice ion oscillations are separated. The analysis of b ₂ ⁰ (T) and P ₂ ⁰ (T) is evidence of the positive contribution of the spin-phonon interaction; the model of the local oscillations of the impurity cluster with close frequencies ω describes well the temperature behavior of b₂(F) and P₂(F).     

Electron transport,penetration depth,and the upper critical magnetic field in ZrB<Subscript>12</Subscript> and MgB<Subscript>2</Subscript>

We report on the synthesis and measurements of the temperature dependences of the resistivity ρ, the penetration depth λ, and the upper critical magnetic field H_c2, for polycrystalline samples of dodecaboride ZrB₁₂ and diboride MgB₂. We conclude that ZrB₁₂ behaves as a simple metal in the normal state with the usual Bloch-Grüneisen temperature dependence of ρ(T) and with a rather low resistive Debye temperature T_R = 280 K (to be compared to T_R = 900 K for MgB₂). The ρ(T) and λ(T) dependences for these samples reveal a superconducting transition in ZrB₁₂ at T_c = 6.0 K. Although a clear exponential λ(T) dependence in MgB₂ thin films and ceramic pellets was observed at low temperatures, this dependence was almost linear for ZrB₁₂ below T_c/2. These features indicate an s-wave pairing state in MgB₂, whereas a d-wave pairing state is possible in ZrB₁₂. In disagreement with conventional theories, we found a linear temperature dependence, of H_c2(T) for ZrB₁₂ (H_c2(0) = 0.15 T).     

Magnetic properties of Fe<Subscript>3</Subscript>C ferromagnetic nanoparticles encapsulated in carbon nanotubes

The low-temperature dependences of magnetic characteristics (namely, the coercive force H _c , the remanent magnetization M _r , local magnetic anisotropy fields H _a, and the saturation magnetization M _s ) determined from the irreversible and reversible parts of the magnetization curves for Fe₃C ferromagnetic nanoparticles encapsulated in carbon nanotubes are investigated experimentally. The behavior of the temperature dependences of the coercive force H _c (T) and the remanent magnetization M _r (T) indicates a single-domain structure of the particles under study and makes it possible to estimate their blocking temperature T _B = 420–450 K. It is found that the saturation magnetization M _s and the local magnetic anisotropy field H _a vary with temperature as ～T ^5/2.     

Specific features in thermal expansion of <Emphasis Type="Italic">R</Emphasis>Fe<Subscript>11</Subscript>Ti single crystals

Thermal expansion and its anomalies in the vicinity of spin-reorientation phase transitions in single crystals of RFe₁₁Ti (R=Y, Tb, Dy, Ho, and Er) compounds are investigated by the tensometric technique in the temperature range 77–400 K. The temperature dependences of the thermal expansion coefficient α(T) are obtained. It is found that the YFe₁₁Ti and HoFe₁₁Ti uniaxial magnetic materials exhibit pronounced anomalies in the α coefficient at T=200 and 290 K. For the TbFe₁₁Ti single crystal, the α coefficient is close to zero in the vicinity of the spin-reorientation phase transition (at T=325 K). For the DyFe₁₁Ti single crystal, which is characterized by two spin-reorientation phase transitions (at T=120 and 250 K), no features in the α(T) dependence are revealed in the region of the low-temperature spin-reorientation phase transition. In the ErFe₁₁Ti single crystal, the specific feature of thermal expansion is observed at T ～ 220 K.     

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.     

Synthesis and electrical conductivity of a new Ag<Subscript>6</Subscript>SnS<Subscript>4</Subscript>Br<Subscript>2</Subscript> superionic compound

The conditions of synthesizing a new Ag₆SnS₄Br₂ compound were studied. The crystallographic parameters of the unit cell were determined as follows: space group Pnma, a=6.67050(10) Å, b=7.82095(9) Å, c=23.1404(3) Å, and Z=4. The total electrical conductivity and its ionic component were measured by a dc probe method in the temperature range 210–380 K. Kinks in the conductivity curve and the differential thermogram of heating the alloy were revealed at 235 K. It was concluded that the mass and charge transfers in the compacted Ag₆SnS₄Br₂ alloy powder have an intragrain character.     

Manifestation of pseudogap features in structurally inhomogeneous optimally doped HTSC YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.92</Subscript>

Magnetization M(H,T) in magnetic fields H up to 90 kOe and at temperatures 2 K ≤ T < T _c (where Tc is the superconducting transition temperature), along with magnetic susceptibility χ(T) in the normal state T _c < T < 400 K for optimally oxygen-doped samples of YBa₂Cu₃O_6.92 with varying degrees of defects in the crystal structure, are studied to determine the influence of structural inhomogeneity on the electron systems characteristics of cuprate superconductors. It is shown that the existence of structural inhomogeneity of samples leads to the manifestation of peculiarities appropriate to pseudogap regime in their properties.     

Anisotropy of the heat capacity of a mixed-state superconducting Nd<Subscript>1.85</Subscript>Ce<Subscript>0.15</Subscript>CuO<Subscript>4</Subscript> single crystal for various magnetic field orientations with respect to the crystallographic axes

The anisotropy in the superconducting properties of single-crystal Nd_1.85Ce_0.15CuO₄ was studied from measurements of the heat capacity within the temperature interval 2–40 K in zero magnetic field and in a magnetic field of 8 T. We report on the first observation of heat capacity jumps occurring at the superconducting transition for various magnetic field orientations with respect to the crystallographic axes and on a strong anisotropy of the magnetic contribution to heat capacity in magnetic fields oriented in the a-b plane and perpendicular to it. These measurements yielded the anisotropy in the electronic heat capacity coefficient γ_n(H) and in the superconducting transition temperature T_c(H). The angular dependence of the Sommerfeld coefficient γ_n in the a-b plane observed in a magnetic field of 8 T exhibits four-lobe symmetry and zero gap direction of the order parameter. A comparison of the results obtained on the Nd_1.85Ce_0.15CuO₄ single crystal with the data available for La_1.85Sr_0.15CuO₄ permits one to conclude that the mechanisms of superconductivity in the electron-and hole-doped superconductors are similar.