Thermal stability of HoMnO<Subscript>3</Subscript>

The low-oxygen limit of the homogeneity range of HoMnO₃, which dissociates according to the reaction HoMnO₃ = 1/2Ho₂O₃ + MnO + 1/4O₂ in the temperature range 987–1160 K, was established by the static method. The temperature dependences of the equilibrium oxygen pressure, the change in the Gibbs free energy, and the thermodynamic functions of HoMnO₃ formation from elements were derived from the experimental data.     

Neutron scattering investigations of multiferroic YMnO<Subscript>3</Subscript>

Multiferroic materials are the materials that show several cooperative ordering phenomena simultaneously. Here we consider only those materials that show both antiferromagnetism and ferroelectricity and in which the ordering parameters are coupled to each other. I shall review our recent neutron scattering investigations on multiferroic hexagonal manganites YMnO₃. We have determined the spin wave dispersions in YMnO₃ in symmetry directions by inelastic neutron scattering and have fitted the results with a simple nearest-neighbour anisotropic Heisenberg model. We have investigated the spin dynamics of YMnO₃ above T _N ∼ 70 K and have shown the existence of persistent albeit heavily damped spin waves.      

Spin fluctuations in the stacked-triangular antiferromagnet YMnO<Subscript>3</Subscript>

The spectrum of spin fluctuations in the stacked-triangular antiferromagnet YMnO₃ was studied above the Néel temperature using both unpolarized and polarized inelastic neutron scattering. We find an in-plane and an out-of-plane excitation. The in-plane mode has two components just above T _N : a resolution-limited central peak and a Debye-like contribution. The quasi-elastic fluctuations have a line width that increases with q as Dq ^z and the dynamical exponent z = 2.3. The out-of-plane fluctuations have a gap at the magnetic zone center and do not show any appreciable q dependence at small wave vectors.     

Comparative Study of the Magnetoelectric Effect in HoAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and HoGa<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Single Crystals

The comparative study of the magnetoelectric properties and magnetostriction of HoGa₃(BO₃)₄ and HoAl₃(BO₃)₄ single crystals has been carried out. The investigated compounds exhibit qualitatively similar magnetodielectric and inverse magnetoelectric ME _E effects with the close absolute values, which is indicative of the weak effect of a nonmagnetic metal ion. On the contrary, the magnetostriction of the galloborate has been found to be threefold higher than that of the alumoborate. In addition, the difference between the qualitative behaviors of magnetostriction has been established: the magnetic-field dependence of magnetostriction for the alumoborate has the maximum near 70 kOe at T = 4.2 K, while the galloborate magnetostriction has no maximum and does not saturate in a field of 140 kOe.     

Phase transformations in HoMnO<Subscript>3</Subscript> oxide at high temperatures

Hexagonal holmium manganite is investigated by means of high-temperature X-ray radiography and thermal analysis. At 1200°C, the manganite transitions from the structural P6₃cm modification into the P6₃/mmc form. Mechanoactivation in a high-energy ball mill results in the emergence of the orthorhombic phase of HoMnO₃, which undergoes the Jahn–Teller transition in the temperature range of 1000–1160°C.     

Resonant-Phase Conjugation in YAlO<Subscript>3</Subscript>:Nd Single Crystals

A new spectral method for surface investigation based on optical-phase conjugation in an unexcited transparent medium is theoretically developed and experimentally verified. On YAlO₃:Nd (1 at %) single crystals at room temperature, the phase conjugation of light is revealed for a photon energy equal to half the energy of resonant local oscillations of electrons of impurity centers. The dependences of the intensity of the phase-conjugation signal of light on its spectral structure are investigated. An explanation of the effect of the Raman scattering of light electromagnetic waves by neodymium ions is offered.     

Microstructural characterization of nanosized YMnO<Subscript>3</Subscript> powders: the size effect

Nanosized YMnO₃ powders of grain size below 100 nm were prepared and characterized by various techniques to understand the size effect of the microstructures and the stoichiometry of the as-prepared powders. It is revealed that the grain surface oxidization state depends on grain size, with a lower oxidization state for the smaller grains. Raman and infrared spectroscopy studies show a remarkable broadening of the reflection peaks with decreasing grain size, identifying the significant surface structure relaxation effect for small-size powders. The ferromagnetic–antiferromagnetic transition around 65–68 °C is determined by the specific-heat measurement, also indicating the remarkable size dependence. PACS 75.47.Lx; 81.07.Wx; 74.62.Yb     

Stratification of Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript> Single Crystals and Sintering of the Obtained Micro- and Nanoscale Plates

The use of surface active liquids facilitates intense stratification of mechanically strained Bi_0.5Sb_1.5Te₃ crystallites. A Bi_0.5Sb_1.5Te₃ heat element with specified thickness and structure is formed by layer-by-layer deposition of “thermoelectric ink” on its free surface. A heat treatment of the formed thermoelectric element in argon at a temperature of 800 K makes it possible to minimize radically the resistance of the grain boundaries introduced into its bulk.     

Radiation Resistance of Yb:LaSc<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and Yb:LuYSiO<Subscript>5</Subscript> Laser Crystals

The optical transmission (OT) spectra of Yb:LaSc₃(BO₃)₄ and Yb:LuYSiO₅ laser crystals have been analyzed before and after irradiation from a ⁶⁰Co source with doses up to 45 Mrad. The OT spectra of the Yb:LuYSiO₅ crystal are found to be the same (within the measurement error) before and after irradiation. The irradiation of the 10 at.%Yb:LaSc₃(BO₃)₄ crystal significantly changes its OT spectra in a wide spectral range (330 to 700 nm). A 975-nm laser based on a previously irradiated 4 at.%Yb:LuYSiO₅ crystal has exhibited a differential efficiency of 23% under diode pumping. The up-conversion luminescence spectra in the visible range of the crystals under study have been explained.     

Magnetoreflection and Magnetostriction in Ferrimagnetic Spinels CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>

It is shown that magnetoreflectance of natural light up to +4% exists in magnetostrictive ferrimagnetic spinel CoFe₂O₄ single crystal; this effect is associated with a change of the fundamental absorption edge, the impurity absorption band, and the phonon spectrum under the action of a magnetic field. The correlation between the field dependences of magnetoreflectance and magnetostriction has been established. The physical mechanisms responsible for the spectral and field peculiarities of magnetoreflection have been explained. It is shown that the magnetorefractive effect in CoFe₂O₄, which is associated with magnetoelastic properties of the spinel, amounts to +1.5 × 10^–3 in magnetic fields exceeding the saturation field. Analysis of magnetooptical and magnetoelastic data has made it possible to estimate deformation potential as Ξ _u = 20 eV for the valence band of the spinel.     

High-pressure effect on the crystal and magnetic structures of the frustrated antiferromagnet YMnO<Subscript>3</Subscript>

The high-pressure (to 5 GPa) effect on the crystal and magnetic structures of the hexagonal manganite YMnO₃ is studied by neutron diffraction in the temperature range 10–295 K. A spin-liquid state due to magnetic frustration on the triangular lattice formed by Mn ions is observed in this compound at normal pressure and T > T_N = 70 K, and an ordered triangular antiferromagnetic state with the symmetry of the irreducible representation Γ₁ arises at T < T_N. The high-pressure effect leads to a spin reorientation of Mn magnetic moments and a change in the symmetry of the antiferromagnetic structure, which can be described by a combination of the irreducible representations Γ₁ and Γ₂. In addition, it is observed that the ordered magnetic moment of Mn ions decreases from 3.27 μ_B (5 GPa) to 1.52 μ_B (5 GPa) at T = 10 K and diffuse scattering is enhanced at temperatures close to T_N. These effects can be explained within the model of the coexistence of the ordered antiferromagnetic phase and the spin-liquid state, whose volume fraction increases with pressure due to the enhancement of frustration effects.     

Superhyperfine Structure of EPR Spectra in LiLuF<Subscript>4</Subscript>:U<Superscript>3+</Superscript> and LiYF<Subscript>4</Subscript>:Yb<Superscript>3+</Superscript> Single Crystals

Electron paramagnetic resonance (EPR) spectra of doped paramagnetic crystals LiLuF₄:U³⁺ and LiYF₄:Yb³⁺ have been investigated at a frequency of about 9.42 GHz in the temperature range of 10–20 K. The U³⁺ ion spectrum is characterized by g-factors g _∥ = 1.228 and g _⊥ = 2.516, and contains the hyperfine structure due to the ²³⁵U isotope with nuclear spin I = 7/2 and natural abundance of 0.71%. The observed hyperfine interaction constants are A _∥ = 81 G and A _⊥ = 83.8 G. Moreover, the spectrum reveals the well-resolved superhyperfine structure (SHFS) due to two groups of four fluorine ions forming the nearest surrounding of the U³⁺ ion. This SHFS contains up to nine components with the spacing between components being about 12.7 G. The SHFS is observed also in the EPR spectrum of the LiYF₄:Yb³⁺ crystal; up to 17 components with spacing of about 3.7 G may be traced. Some parameters of the effective Hamiltonian of the SHF interaction are estimated, the contribution of covalent bonding of f-electrons with ligands into these parameters is discussed. Authors' address: Igor N. Kurkin, Kazan State University, Kremlevskaya ulitsa 18, Kazan 420008, Russian Federation     

Effect of a Rare-Earth Ion on the Structural Instability in RFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Crystals

The dynamics of the crystal lattice of RFe₃(BO₃)₄ (R = Pr, Nd, Sm, Gd, Tb, Dy, and Ho) compounds in the high-symmetry R32 phase has been calculated. Significant changes in spectra of compounds with various rare-earth ions have been obtained only near the edge Λ point of the Brillouin zone (qΛ = 1/3(?2b₁ + b₂ + b₃, where b₁, b₂, and b₃ are the reciprocal lattice vectors) for acoustic oscillation branches. A decrease in the frequency of an acoustic mode at the point Λ has been revealed in all studied compounds. This frequency depends on the type of rare-earth ion and decreases from a compound with Pr to a compound with Ho down to imaginary values. Such a behavior of the frequency of the unstable acoustic mode is in good agreement with experimental data on the dependence of the temperature of the R32 → P3₁21 structural phase transition on the type of rare-earth ion in ferroborates.     

Resonance Frequency and NMR Relaxation Times in Two Inequivalent <Superscript>133</Superscript>Cs in Cs<Subscript>2</Subscript>CuBr<Subscript>4</Subscript> and Cs<Subscript>2</Subscript>ZnBr<Subscript>4</Subscript> Single Crystals

The resonance frequencies and relaxation mechanisms of Cs₂CuBr₄ and Cs₂ZnBr₄ were examined by static nuclear magnetic resonance (NMR) method. Here, the two inequivalent Cs(1) and Cs(2) sites surrounded by Br ions were distinguished. The saturation recovery traces for ¹³³Cs nuclei in Cs₂CuBr₄ with the paramagnetic ions, and those in Cs₂ZnBr₄ without the paramagnetic ions were each fitted by four exponential functions. From these results, the spin–lattice relaxation times T₁ in the laboratory frame of ¹³³Cs nuclei in the two crystals were obtained, and Cs(1) surrounded by 11 bromide ions has a longer relaxation time than Cs(2) surrounded by 9 bromide ions.     

Thermodynamic properties and structure of oxyfluorides Rb<Subscript>2</Subscript>KMoO<Subscript>3</Subscript>F<Subscript>3</Subscript> and K<Subscript>2</Subscript>NaMoO<Subscript>3</Subscript>F<Subscript>3</Subscript>

According to the results of calorimetric and structural studies, the Fm{ie1202-1}m phase in K₂NaMoO₃F₃ remains stable at least to 100 K. No ferroelectric transformation assumed earlier has been revealed in a series of Rb₂KMoO₃F₃ samples prepared using various technologies. Only a phase transition of nonferroelectric origin has been observed near 195 K, and its thermodynamic characteristics have been determined. An analysis of the stability of the cubic structure of molybdenum fluorine-oxygen elpasolites-cryolites has been performed in the framework of the hypothesis on strengths of interatomic bonds. The barocaloric effect in Rb₂KMoO₃F₃ has been estimated.     

Luminescence of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> Crystals Excited with a Runaway Electron Beam

The spectra and amplitude–time characteristics of the radiation of studied Sn and Fe-doped Ga₂O₃ crystals excited with a runaway electron beam and an excilamp with a wavelength of 222 nm were investigated. The main contribution to the luminescence of samples in the region of 280–900 nm under excitation with a beam was shown to be made by cathodoluminescence. In the Fe-doped crystal, a new cathodeand photoluminescence band was detected within a wavelength range of 650–850 nm. In the Sn-doped crystal, Vavilov–Cherenkov radiation was detected in the region of 280–300 nm using a monochromator and a photomultiplier.     

Study of Oxygen Diffusion in Reduced LiNbO<Subscript>3</Subscript> Crystals

Using the method of impedance spectroscopy and optical density measurements, the diffusion of oxygen in single crystals of lithium niobate of the congruent composition after the reductive thermochemical processing is studied. The parameters describing the diffusion of oxygen in the temperature range 493–693 K are established.     

Manifestations of Phase Transitions and the Thermooptical-Memory Effect in the Absorption Spectra of (N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>)<Subscript>2</Subscript>CuCl<Subscript>4</Subscript> Crystals

The manifestations of phase transitions and the spatial modulation of the structure of the (N(CH₃)₄)₂CuCl₄ crystal in its absorption spectra have been investigated. It has been established that the thermooptical-memory effect manifesting itself in the absorption spectra of this crystal entirely corresponds to the model of ordering of defects and impurities in a sample with a modulated structure. It is shown that, as a result of stabilization of the crystal studied in the incommensurate phase, its symmetry and the symmetry of the metal-halogen complex in it lower depending on the defect wave. This manifests itself as a marked shift of the intraionic-absorption bands and an increase in their intensity. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 386–390, May–June, 2005.     

Vibrational spectra of disordered oxyfluoride (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>WO<Subscript>3</Subscript>F<Subscript>3</Subscript>

Comparative analysis of the IR absorption and Raman scattering spectra of a polycrystalline sample of perovskite-type oxyfluoride (NH₄)₃WO₃F₃ has been performed in the frequency range 370–4000 cm^?1 at temperatures from 92 to 303 K, including the transition between the orientationally disordered cubic and low-symmetry phases. The conformation of WO₃F₃ octahedral groups is established and transitional anomalies of the internal modes of these groups and ammonium ions are revealed. Comparative analysis of the IR and Raman spectra suggests that the phase transition under study is mainly related to the ordering of octahedral groups and formation of W-O…H-N hydrogen bonds.