Anomalous low-frequency phonons in ZrB<Subscript>12</Subscript>

The influence of pressure and temperature on low-frequency lines (100–300 cm^–1) in Raman spectra of ZrB₁₂ and LuB₁₂ single crystals has been investigated. These spectral features have been identified as one-phonon and two-phonon excitations of the acoustic branches of the phonon spectrum. It has been found that the observed spectra of ZrB₁₂ single crystals are more structured and indicate the development of phonon anomalies with a decrease in the temperature. Despite the fact that the low-frequency features in the phonon spectrum of ZrB₁₂ are characterized by a high value of the isothermal Grüneisen parameter, their isobaric Grüneisen parameter has a negative value. This indicates large contributions from the fourth-order anharmonicity, which significantly exceed the volume effects. The appearance of narrow lines in the frequency range from 155 to 175 cm^–1 at temperatures T < 100 K suggests the possibility of a structural transition with an incomplete softening of the lattice.     

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).     

On electron transport in ZrB<Subscript>12</Subscript>, ZrB<Subscript>2</Subscript>, and MgB<Subscript>2</Subscript> in normal state

We report on measurements of the temperature dependence of resistivity, ρ(T), for single-crystal samples of ZrB₁₂, ZrB₂, and polycrystalline samples of MgB₂. It is shown that the cluster compound ZrB₁₂ behaves as a simple metal in the normal state, with a typical Bloch-Grüneisen ρ(T) dependence. However, the resistive Debye temperature, T_R=300 K, is three times smaller than T_D obtained from specific heat data. We observe the T² term in ρ(T) of all these borides, which could be interpreted as an indication of strong electron-electron interaction.     

Raman scattering spectroscopy of inclusions of carbon in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> films and its solid solutions with HfO<Subscript>2</Subscript>

We apply Raman scattering spectroscopy to study the nature of carbon inclusions in Al₂O₃ and (HfO₂) _x (Al₂O₃)_{1 ? x} films deposited using volatile complex compounds. Raman spectra of the films under investigation contain D and G vibrational modes, which indicate that carbon clusters of the sp ² configuration tend to form in the films. We estimate the size of clusters from the integrated intensity ratio I _D /I _G and find it to be in the range of 14–20 Å. The content of hydrogen in carbon clusters is calculated from the height of the photoluminescence pedestal and is found to vary from 14 to 30 at % depending on the regime of the film’s synthesis.     

Thermal quenching of luminescence of BaY<Subscript>2</Subscript>F<Subscript>8</Subscript> crystals activated with Er<Superscript>3+</Superscript> and Tm<Superscript>3+</Superscript> ions

Thermal quenching of interconfigurational 5d-4f luminescence of Er³⁺ and Tm³⁺ ions in BaY₂F₈ crystals is studied in the temperature range of 330–790 K. The quenching temperatures are ~575 and ~550 K for Er³⁺ and Tm³⁺, respectively. It is shown that quenching of 5d-4f luminescence of Tm³⁺ ions is caused by thermally stimulated ionization of 5d electrons to the conduction band.     

Elastic properties of La<Subscript>0.82</Subscript>Ca<Subscript>0.18</Subscript>MnO<Subscript>3</Subscript> single crystal

The temperature dependences of the velocity of longitudinal sound waves and the internal friction in a La_0.82Ca_0.18MnO₃ single crystal with the Curie temperature T _C = 181 K have been studied. As temperature decreases, the single crystal is shown to undergo the transition from the pseudocubic O* to the Jahn–Teller O’ phase at T ~ 254 K and the reverse transition from O’ to O* phase at T ~ 84 K. The velocity of sound and the internal friction in the O’ phase are found to be significantly smaller than those in the O* phase.     

Features of the low-frequency polarization response in the region of the ferroelectric phase transition in multiferroic TbMnO<Subscript>3</Subscript>

The unusual behavior of the low-frequency (10 Hz–1 MHz) permittivity in single crystals of ferroelectric multiferroic TbMnO₃ has been experimentally and theoretically studied in detail in the region of the narrow temperature peak of the permittivity, associated with the ferroelectric phase transition (T_C ~ 27.4 K). It has been found that the ε_c^′(ω, T) maximum sharply decreases with increasing measured field frequency, while the temperature position of the maximum is independent of frequency. It has been shown that the observed features of the polarization response can be satisfactorily described within the Landau–Khalatnikov polarization relaxation theory.     

Antiferromagnetic Resonance in GdB<Subscript>6</Subscript>

The electron spin resonance has been measured for the first time both in the paramagnetic phase of the metallic GdB₆ antiferromagnet (T_N = 15.5K) and in the antiferromagnetic state (T < T_N). In the paramagnetic phase below T* ~ 70 K, the material is found to exhibit a pronounced increase in the resonance linewidth and a shift in the g-factor, which is proportional to the linewidth Δg(T) ~ ΔH(T). Such behavior is not characteristic of antiferromagnetic metals and seems to be due to the effects related to displacements of Gd³⁺ ions from the centrosymmetric positions in the boron cage. The transition to the antiferromagnetic phase is accompanied by an abrupt change in the position of resonance (from μ₀H₀ ≈ 1.9 T to μ₀H₀ ≈ 3.9 T at ν = 60 GHz), after which a smooth evolution of the spectrum occurs, resulting eventually in the formation of the spectrum consisting of four resonance lines. The magnetic field dependence of the frequency of the resonant modes ω₀(H₀) obtained in the range of 28–69 GHz is well interpreted within the model of ESR in an antiferromagnet with the easy anisotropy axis ω/γ = (H ₀ ² +2H_AH_E)^1/2, where H_E is the exchange field and H_A is the anisotropy field. This provides an estimate for the anisotropy field, H_A ≈ 800 Oe. This value can result from the dipole?dipole interaction related to the mutual displacement of Gd³⁺ ions, which occurs at the antiferromagnetic transition.     

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).     

Optical studies of phase transitions in the (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>Ti(O<Subscript>2</Subscript>)F<Subscript>5</Subscript> crystal

Polarization-optical study of twinning and measurements of the Raman spectra and birefringence in oxyfluoride (NH₄)₃Ti(O₂)F₅ were carried out over the temperature range 90–350 K. Phase transitions were detected at temperatures T ₀₁ = 266 K (second-order transition) and T ₀₂ = 225 K (first order). It is assumed that the crystal symmetry is changed as follows: Fm3m ? I4/mmm ? I4/m. Anomalies of the spectral parameters are established in the frequency range of internal vibrations of ammonium ions and Ti(O₂)F₅ complexes. An analysis of the results shows that the transition at T ₀₁ is likely due to small shifts of the tetrahedral groups from their position on the triad axis and that the transition at T ₀₂ is due to fluorine-oxygen ordering of Ti(O₂)F₅ complexes.     

Synthesis and properties of high-pressure phase [Er<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>](V<Subscript>4</Subscript>)O<Subscript>12</Subscript>

A new perovskite-like compound Er_0.73Cu₃V₄O₁₂ (space group Im \(\bar 3\), Z = 2, a = 7.266 Å) has been synthesized barothermally (P = 8.0 GPa, t = 1000°C). Its electrical and magnetic properties have been studied. It is found that the temperature dependence of the electrical conductivity (in the range 78–300 K) has of semiconductor type. The behavior of the impedance and admittance has been analyzed at 290 K and frequencies of 200 Hz to 200 kHz under atmospheric pressure and at high (15–42 GPa) pressures.     

Internal friction of Li<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> single crystals

This paper reports on the results of measurements of the internal friction Q^?1 and the shear modulus G of Li₂B₄O₇ single crystals along the crystallographic directions [100] and [001] in the temperature range 300–550 K for strain amplitudes of (2–10)×10^?5 at infralow frequencies. The anomalies observed in Q^?1 and G in the temperature range 390–410 K are due to thermal activation of the mobility of lithium cations and their migration from one energetically equivalent position to another. A jump in the internal friction background is revealed in the vicinity of the Q^?1 and G anomalies for the Li₂B₄O₇ crystal. The magnitude of this jump depends on the crystallographic direction.     

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.     

Pressure-induced structural transformations,orbital order and antiferromagnetism in La<Subscript>0.75</Subscript>Ca<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript>

High pressure evolution of structural, vibrational and magnetic properties of La_0.75Ca_0.25MnO₃ was studied by means of X-ray diffraction and Raman spectroscopy up to 39 GPa, and neutron diffraction up to 7.5 GPa. The stability of different magnetic ground states, orbital configurations and structural modifications were investigated by LDA + U electronic structure calculations. A change of octahedral tilts corresponding to the transformation of orthorhombic crystal structure from the Pnma symmetry to the Immaone occurs above P ~ 6 GPa. At the same time, the evolution of the orthorhombic lattice distortion evidences an appearance of the e _g d _{x² ? z²} orbital polarization at high pressures. The magnetic order in La_0.75Ca_0.25MnO₃ undergoes a continuous transition from the ferromagnetic 3D metallic (FM) ground state to the A-type antiferromagnetic (AFM) state of assumedly 2D pseudo-metallic character under pressure, that starts at about 1 GPa and extends possibly to 20–30 GPa.     

The influence of magnetic and structural heterogeneity on thermopower,magnetothermopower, electrical resistivity,and magnetoresistivity of Nd<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> manganite

The thermopower, S, magnetothermopower, ΔS/S, resistivity, ρ, and magnetoresistivity, Δρ/ρ, depending on the temperature T and magnetic field H, have been studied in an Nd_0.5Sr_0.5MnO₃ single crystal consisting of three types of clusters: an antiferromagnetic CE-type with charge-orbital ordering (below the Neel temperature T_NCE ~ 145 K) and an A-type with T_NA ~ 220 K; a ferromagnetic at 234 ≤ T ≤ 252 K, and a ferromagnetic metal phase below the Curie temperature T_C = 248 K. The thermopower was found to be negative, indicating the dominance of the electronic type of conductivity. In the S(T) curves, a sharp minimum is observed in the temperature range of 100 K ≤ T ≤ 133 K, close to T_NCE, where the absolute S value attains 53 μV/K. With a further increase in temperature, the absolute S value decreases rapidly; at 200 K it is equal to 7 μV/K. It then slightly increases, reaching its maximum value of 15 μV/K at a temperature of 254 K, which is close to T_C. The absolute thermopower decreased under the influence of the magnetic field; i.e., a negative magnetothermopower occurs. In {ΔS/S}(T) curves, a sharp minimum is observed at T = 130 K close to T_NCE, where the magnetothermopower reaches a huge value of ~45% at H = 13.23 kOe. A broad minimum in the {ΔS/S}(T) curves is observed near the Curie temperature and its value is also high, viz., ~15% in the maximum measuring magnetic field of 13.23 kOe. The extremely high magnetothermopower values mean that the charge-orbital ordered nanoclusters or ferron type make the main contribution to the thermopower of the entire sample. The behavior of the ρ(T) and {Δρ/ρ}(T) curves is similar to that of the S(T) and {ΔS/S}(T) dependencies, which is in agreement with this conclusion.     

Study of the anisotropy of the dielectric response of Na<Subscript>1/2</Subscript>Bi<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> relaxor ferroelectric

The dielectric response, conductivity, and domain structure of (Na_1/2Bi_1/2)TiO₃ single crystals are studied in the temperature range of 290–750 K for the [100], [110], and [111] crystallographic directions. It is shown that the region of optical isotropization is observed in polarized light in the temperature range of 570–620 K. In this case, the birefringence (Δn) decreases and disappears (together with the image of the domain structure) for the [100] directions. The region of optical isotropization in the [111] directions is characterized by the disappearance of the image of the domain structure and by the existence of individual regions with partial quenching. The domain structure in the [110] directions remains distinguished against the background of a significant decrease in Δn in the indicated temperature range. The region of isotropization is also manifested in the temperature dependence of the imaginary part of the dielectric response and is determined by the isotropic character of the conductivity in the range of 570–620 K. The bulk conductivity has a thermally activated character with activation energies E _a = 50?60 meV at T < 500 K and E _a = 700?900 meV for T > 620 K. The low-frequency dispersion of the dielectric response is determined by the Maxwell–Wagner mechanism and is due to an increase in the ionic conductivity at temperatures above 620 K. The anisotropy of the susceptibility holds in the entire studied ranges of frequencies (25 Hz–1 MHz) and temperatures.     

Magnetic and transport properties of colossal magnetoresistance compound EuB<Subscript>6</Subscript>

The galvanomagnetic and magnetic properties of EuB₆ single crystal have been measured over wide temperature (1.8–300 K) and magnetic-field (up to 70 kOe) ranges, and the parameters of charge carriers and the characteristics of the magnetic subsystem are estimated in the paramagnetic and ferromagnetic (T < T _C ≈ 13.9 K) phases of this compound with strong electron correlations. In the temperature range T < T* ≈ 80 K, a magnetoresistance hysteresis Δρ(H)/ρ(0) is detected; it reaches a maximum amplitude of about 5% at T ≈ 12 K. The anomalies of charge transport observed in the temperature range T _C < T < T* are shown to be related to the magnetic scattering of charge carriers (m _eff = (15–30)m ₀, where m ₀ is the free-electron mass) that results from a short-range magnetic order appearing upon the formation of ferromagnetic nanoregions (ferrons).     

X-ray study of [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> at low temperatures

The unit cell parameters a, b, and c of [N(CH₃)₄]₂ZnCl₄ have been measured by x-ray diffraction in the temperature range 80–293 K. Temperature dependences of the thermal expansion coefficients α_a, α_b, and α_c along the principal crystallographic axes and of the unit cell thermal expansion coefficient α_V were determined. It is shown that the a=f(T), b=f(T), and c=f(T) curves exhibit anomalies in the form of jumps at phase transition temperatures T₁=161 K and T₂=181 K and that the phase transition occurring at T₃=276 K manifests itself in the a=f(T) and b=f(T) curves as a break. A slight anisotropy in the coefficient of thermal expansion of the crystal was revealed. The phase transitions occurring at T₁=161 K and T₂=181 K in [N(CH₃)₄]₂ZnCl₄ were established to be first-order.     

Pressure-induced antiferromagnetism in La<Subscript>0.75</Subscript>Ca<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript> manganite

The crystal and magnetic structures of La_0.75Ca_0.25MnO₃ manganite are studied under high pressures up to 4.5 GPa in the temperature range 12–300 K by the neutron diffraction method. At normal pressure and temperature T _C = 240 K, a ferromagnetic state is formed in La_0.75Ca_0.25MnO₃. At high pressures P ≥ 1.5 GPa and at temperatures T < T _N ≈ 150 K, a new A-type antiferromagnetic state appears. A further increase in pressure leads to an increase in the volume fraction of the antiferromagnetic phase, which coexists with the initial ferromagnetic phase. The effect of high pressure causes a considerable increase in T _C with the slope dT _C /dP ≈ 12 K/GPa. Calculations performed in the framework of the double exchange model with allowance for the electron-phonon interaction make it possible to explain this pressure dependence of T _C on the basis of experimental data.     

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.