Growth of Cr<Superscript>4+</Superscript>: LiGaSiO<Subscript>4</Subscript> single crystals by floating-zone melting technique

The problems of growth of new promising laser crystals Cr⁴⁺: LiGaSiO₄ by the crucible-free floating-zone method with optical heating are considered. The use of high axial temperature gradients with intense stirring of the melt makes it possible to obtain crystals of satisfactory optical quality from stoichiometric melt, despite the incongruent character of the compound melting.     

Optical,mechanical, and thermal properties of nonlinear LiKB<Subscript>4</Subscript>O<Subscript>7</Subscript> crystals

Nonlinear LiKB₄O₇ single crystals have been grown by the Czochralski method from a stoichiometric melt. The optical, acoustic, piezo-and electro-optical, and thermal properties of these single crystals have been studied.     

The superposition of the lattice radiation and reflectivity spectra of MoO3 and PbMoO4 crystals

The Raman scattering of MoO₃ at 300 and 77 K and the infrared reflectivity spectra of MoO₃ at 300 K have been investigated in different scattering geometries. The Raman spectra of PbMoO₄ crystals at 77 K have been investigated also. The reflectivity spectra of MoO₃ crystals were calculated for E ∥ c and E ∥ a. The phonon parameters and the effective ionic charges of anions and cations for MoO₃ and PbMoO₄ crystals are determined. The diagrams of the splitting of the vibrational levels by the Davydov resonance and by the factor group interactions have been determined. It is shown that the lattice radiation of crystals which have a number of vibrational oscillators (MoO₃, PbMoO₄) begins at low energy vibrational modes and at low values of the damping parameters.     

Experimental investigations of buoyancy-driven convection in vertical (BixSb1−x)2Te3 molten zones

Experimental results for various states of buoyancy driven flow in vertical (Bi_0.23Sb_0.75)₂Te₃ molten zones with covered surface are presented. Critical thermal wall Rayleigh numbers Ra for the onset of time-dependent convection have been determined by means of temperature measurements. The stability diagram obtained for the existing buoyancy driven convection shows the increase of Ra with increasing aspect ratio. This relation is also known from other crystal growth configurations and is due to the damping influence of container walls. At the beginning in the oscillatory region of convection extremely long periods of oscillation (maximum 850 s) were observed, which are caused by another mechanism than periods (25 … 37 s) registered at increasing melt heights. Furthermore, Bi_0.5Sb_1.5Te₃ crystals were grown by using the vertical zone melting technique. The microscopic striations observed in the grown crystals correlate exactly with the temperature signals caused by time dependent convection. However, the fluctuations of the tellurium distribution in axial direction measured by scanning the Seebeck coefficient are presumably generated by unsteady solutal convection during growth.     

Temperature-concentration fields of the crystallization of YbAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> from high-temperature melt solutions based on potassium trimolybdate

The phase relationships in the YbAl₃(BO₃)₄-K₂Mo₃O₁₀-B₂O₃-Yb₂O₃ multicomponent system are investigated in the temperature range 1150–1000°C within the stability region of the YbAl₃(BO₃)₄ compound. The region of single-phase crystallization of the YbAl₃(BO₃)₄ borate is revealed in the section corresponding to the composition containing 15 wt % YbAl₃(BO₃)₄. For the same composition, it is demonstrated that there exists a correlation between the temperatures of saturation of melt solutions with the YbAl₃(BO₃)₄ borate and the composition of the solvent, namely, the contents of B₂O₃, K₂Mo₃O₁₀, and Yb₂O₃ in the solvent. The temperature dependences of the solubility of the YbAl₃(BO₃)₄ compound at different contents are determined for melts of two compositions: melt I containing 55 mol % K₂Mo₃O₁₀ and 45 mol % B₂O₃ and melt II containing 55 mol % K₂Mo₃O₁₀, 40 mol % B₂O₃, and 5 mol % Yb₂O₃. The specific features of the crystallization of the YbAl₃(BO₃)₄ compound are analyzed and compared with those of the yttrium, neodymium, gadolinium, and erbium aluminum borates studied previously.     

Structural state of a radiation-modified Ti<Subscript>50</Subscript>Ni<Subscript>47</Subscript>Fe<Subscript>3</Subscript> single crystal

The structural state of a Ti₅₀Ni₄₇Fe₃ single crystal irradiated by fast neutrons (F = 2.5 × 10²⁰ cm⁻²) at 340 K was studied by thermal neutron diffraction at 78 and 295 K. The melt of this composition was chosen with the purpose of designing a radiation-resistant material exhibiting a shape-memory effect. It was found that the melt remains crystalline after irradiation, whereas the Ti₄₉Ni₅₁ crystal studied earlier becomes amorphous after an analogous irradiation. In spite of the fact that the main structural motif of the crystal remains unchanged after irradiation, martensitic transformations in the crystal do not occur and, consequently, the shape-memory effect is not retained. The radiation resistance of this class of crystals was estimated.     

A new optical medium—Cd<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>F<Subscript>2</Subscript> single crystals

For the first time, single crystals of the Cd_0.75Sr_0.25F₂ solid solution with the fluorite structure are grown from melt by the Bridgman-Stockbarger method. The composition of these single crystals corresponds to the composition congruently melting at the minimum point on the phase diagram. The maximum diameter of the crystal is 50 mm; the maximum height is 30 mm. The vickers microhardness of the semitransparent crystals equals 191 ± 43 kg/mm². The transmission cutoff in the IR range is ～10 μm.     

Effect of doping method on the formation of charge-compensating defects in PbMoO4:Nd3+ crystals

PbMoO₄:Nd³⁺ single crystals have been grown using different doping schemes. Their dielectric properties have been studied in the temperature range of 20?C550°C at frequencies from 25 to 10⁶ Hz. The activation energies of dielectric relaxation are determined for all samples, and the Nd³⁺ luminescence decay kinetics is studied. The most realistic models of activator centers in PbMoO₄:Nd³⁺ crystals are proposed based on the optical and dielectric spectroscopy data.     

Dilatometric and ultrasound study of [NH<Subscript>2</Subscript>(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>]MnCl<Subscript>3</Subscript> · 2H<Subscript>2</Subscript>O crystals

The unit-cell parameters of [NH₂(CH₃)₂]MnCl₃ · 2H₂O crystals are determined by X-ray diffraction analysis and the velocities of longitudinal ultrasonic waves in these crystals are measured by the echo-pulse method in the temperature range 100–315 K. The coefficients of thermal expansion along the principal crystallographic axes are derived from the temperature dependences of the unit-cell parameters. The temperature dependences of the characteristics studied reveal kink anomalies at temperatures of ～125, 179, 203, 260, and 303 K. These anomalies are indicative of structural transformations in the [NH₂(CH₃)₂]MnCl₃ · 2H₂O crystals, which may be related to the dynamics of dimethylammonium cations.     

Crystallization of Ba<Subscript>3</Subscript>Fe<Subscript>2</Subscript>Ge<Subscript>4</Subscript>O<Subscript>14</Subscript> and Ba<Subscript>2</Subscript>Fe<Subscript>2</Subscript>GeO<Subscript>7</Subscript> in oxide-fluoride fluxes

Crystallization of trigonal Ba₃Fe₂Ge₄O₁₄ and tetragonal Ba₂Fe₂GeO₇ barium ferrogermanates is investigated in their own fluxes diluted by B₂O₃-BaF₂ and B₂O₃-PbF₂ mixtures, respectively. The ratios of the components at which the properties of the fluxes satisfy the requirements for controlled crystallization of these incongruently melting compounds are determined. Single crystals of Ba₂Fe₂GeO₇ barium ferrogermanate are grown for the first time.     

Structure of Gd<Subscript>0.95</Subscript>Bi<Subscript>0.05</Subscript>Fe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystals at 293 and 90 K

The structure of GdFe₃(BO₃)₄ single crystals has been studied by X-ray diffraction at 293 and 90 K. The crystals are grown from a flux in the Bi₂Mo₃O₁₂–B₂O₃–Li₂MoO₄–Gd₂O₃–Fe₂O₃ system. The results of chemical analysis and structural study show that these crystals contain bismuth as an impurity. It is found that bismuth atoms are located at gadolinium sites in the structure. A decrease in the temperature is accompanied by a lowering of the symmetry from sp. gr. R32 (at 293 K) to sp. gr. P3₁21 (at 90 K). The presence of two types of iron chains with different geometries at 90 K promotes a change in the magnetic properties of these crystals with a decrease in the temperature.     

The Changes of Thermal,Dielectric, and Optical Properties at Insertion of Small Concentrations of Ammonium to K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> Crystals

The structure of (K_1–x(NH₄)_x)₃H(SO₄)₂ crystals with a low ammonium concentration and the behavior of their thermal, optical, and dielectric properties in a temperature range of 275–500 K have been investigated to clarify the influence of doping on the phase transition kinetics. An examination of unit-cell parameters of (K_{1 – x}(NH₄)_x)₃H(SO₄)₂ single crystals has confirmed the existence of a superprotonic phase transition at a temperature of ≈450K. The conducting properties of single-crystal and polycrystalline samples have been studied.     

Comparative analysis of the heat transfer processes during growth of Bi<Subscript>12</Subscript>GeO<Subscript>20</Subscript> and Bi<Subscript>4</Subscript>Ge<Subscript>3</Subscript>O<Subscript>12</Subscript> crystals by the low-thermal-gradient Czochralski technique

The heat transfer processes occurring in the solid and liquid phases during growth of Bi₁₂GeO₂₀ and Bi₄Ge₃O₁₂ crystals by the low-thermal gradient Czochralski method are analyzed and compared. It is experimentally found that, under similar growth conditions, the deflection of the crystallization front for the Bi₁₂GeO₂₀ crystal is considerably smaller than the deflection of the crystallization front for the Bi₄Ge₃O₁₂ crystal and the faceting of the former front is observed at the earlier stage of pulling. The results of the numerical simulation demonstrate that the different behavior of the crystallization fronts is associated with the difference between the coefficients of thermal absorption in the crystals.     

The behavior of thermal conductivity in the chaotic phase of [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystal

A thermal investigation of the modulated structure dynamics at the transition between metastable states in the incommensurate phase of [N(CH₃)₄]₂ZnCl₄ crystal have been performed. It is established that the anomalous behavior of the thermal conductivity in the absence of a defect-density wave is due to the inelastic scattering of thermal phonons from critical phonons of the soft optical branch. In the presence of a defect-density wave, the anomalous increase in thermal conductivity is caused by the existence of a chaotic phase and is related to the contribution that soft optical phonons make to the heat transfer due to the increase in their group velocity.     

Oxygen-conducting crystals of La<Subscript>2</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript>: Growth and main properties

Single crystals of the anionic conductor La₂Mo₂O₉ are grown by crystallization from a nonstoichiometric melt. Their polymorphism and domain structure, as well as the temperature dependences of conductivity and dielectric permittivity, are studied. In the temperature range 750–600°C, the conductivity of these crystals is as high as 10^?1–10^?2 Ω^?1 cm^?1.     

Structural Analysis of the Phase Transitions of (NH<Subscript>4</Subscript>)<Subscript>4</Subscript>HgBr<Subscript>6</Subscript>

Abstract Single crystal diffraction and differential scanning calorimetry DSC techniques have been used to investigate the different phases of (NH₄)₄HgBr₆, tetrammonium mercury hexabromide, from room temperature to 120 K. Two anomalies in thermal behaviour were detected for this compound at 190 and 268 K, by DSC experiment. X-ray diffraction measurements confirm these anomalies. At room temperature the structure is tetragonal P4/mnc (No. 128) with lattice parameters a = b = 9.25560(8) ?; c = 8.8657(11) ?; V = 759.49(9) ?³ and Z = 2. At T = 250 K the structure is orthorhombic Pnnm with lattice parameters a = 8.8436(8) ?; b = 9.2191(8) ?; c = 9.2232(7) ?; V = 751.97(11) ?³ and Z = 2. Below approximately 200 K the structure is monoclinic P2₁/n (No. 14) with: a = 8.8080(9) ?; b = 9.1608(8) ?; c = 9.1498(8) ?; β = 90.230(7)°; V = 738.28(12) ?³ and Z = 2 (T = 120 K). The structure of (NH₄)₄HgBr₆ consists of isolated HgBr₆-octahedra in the whole temperature range which are slightly compressed in c-direction. The ammonium groups are located between the octahedra ensuring the stability of the structure by hydrogen bonding contacts: N–H···Br. The structural phase transformations are described by a rotation of the [HgBr₆]²⁻ octahedra around the c-axis, and this behaviour is attributed to an orientational disorder of ammonium groups. Index abstract Structural analysis of the phase transitions of (NH₄)₄HgBr₆; M. Loukil, A. Kabadou, I. Svoboda, A. Ben Salah and H. Fuess; The phase transformations in (NH₄)₄HgBr₆ are explained by large rotation of [HgBr₆]²⁻ octahedra around the c-axis.      

Vibrational spectra of the YbB<Subscript>12</Subscript> Kondo insulator

The density of phonon states for the YbB₁₂ Kondo insulator is calculated from the inelastic neutron scattering spectra of this compound. It is established that thermal vibrations of rare-earth atoms predominantly occur in the low-energy range. These atoms are most weakly bound in the crystal structure of the YbB₁₂ Kondo insulator. The high-energy part of the vibrational spectrum is determined by thermal vibrations of the boron atoms forming a rigidly connected structure of the compound. It is revealed that the temperature dependence of the intensity of the phonon peak attributed to thermal vibrations of the ytterbium atoms exhibits an anomalous behavior. This circumstance suggests that the magnetoelastic coupling occurring in the structure of the YbB₁₂ Kondo insulator is relatively strong and can contribute to the magnetic excitation spectrum of this compound.     

Growth of ZnGeP<Subscript>2</Subscript> crystals from melt

Some features of the growth of ZnGeP₂ single crystals by the Bridgman method have been considered. The ratio of the thermal-conductivity coefficients of the liquid and solid phases of ZnGeP₂ at the melting temperature was estimated to be 2.3. It is established that, in the case of ZnGeP₂ growth on a seed, the most favorable crystallographic directions are 〈100〉 and 〈001〉. It is shown that annealing and electron irradiation significantly decrease the optical absorption coefficient in the impurity absorption region.     

Low-temperature X-ray diffraction studies of [(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>NH<Subscript>2</Subscript>]<Subscript>5</Subscript>Cd<Subscript>3</Subscript>Cl<Subscript>11</Subscript> crystals

[(CH₃)₂NH₂]₅Cd₃Cl₁₁ crystals are grown by the method of isothermal evaporation from saturated aqueous solutions containing dimethylamine and cadmium chlorides, [(CH₃)2NH₂]Cl and CdCl_2.5H₂O. The crystal grown are studied by the X-ray diffraction method. It is established that the crystals are orthorhombic with the unit-cell parameters at room temperature a = 18.115 ± 0.004 Å, b = 11.432 ± 0.002 Å, and c = 15.821 ± 0.003 Å. The unit-cell parameters a, b, and c of the [(CH₃)₂NH₂]₅Cd₃Cl₁₁ crystals are measured as functions of temperature in the temperature range 100–320 K. The data obtained were used to determine the thermal expansion coefficients along the main crystallographic axes. The temperature curves of the unit-cell parameters and thermal expansion coefficients showed pronounced anomalies in the vicinity of the temperatures T ₁ = 120, T ₂ = 150, and T ₃ = 180 K corresponding to the phase transitions in the [(CH₃)₂NH₂]₅Cd₃Cl₁₁ crystals. The crystals are also characterized by a pronounced anisotropy of thermal expansion.