Synthesis and magnetic properties of copper metaborate single crystals, CuB2O4

Large high-quality single crystals of copper metaborate are grown on the basis of the phase diagram of the ternary Li₂O-CuO-B₂O₃ system. Bright blue crystals with a volume of about 1 cm³ were grown by the method of spontaneous crystallization while slowly cooling the melt. The magnetic susceptibility and electron spin resonance were measured. It is shown that the effective magnetic moment of a Cu²⁺ ion is equal to 1.6 μ_B and the g-factor, to 2.170 and 2.133 for the magnetic field oriented parallel and perpendicular to the fourfold axis, respectively. At 21 and 10 K, sharp anomalies of magnetic susceptibility are observed.     

Growth,structure, and magnetic properties of CuFeTe<Subscript>2</Subscript> single crystals

CuFeTe₂ single crystals were grown and the temperature dependence of their magnetic susceptibility in the temperature range 1.8–400 K was investigated. It is found that the magnetic susceptibility shows anomalies at temperatures T _s = 65 and T _N = 125 K. At T > 125 K, the crystal is in the paramagnetic state controlled by Fe²⁺ and Cu²⁺ ions with an effective magnetic moment of 1.44 μB.     

Floating-zone growth of large high-quality CoAl2O4 single crystals

We report the first successful floating-zone growth of high-quality CoAl₂O₄ single crystals with volume up to 1 cm³ free from inclusions and sub-grains. The neutron rocking curves of the CoAl₂O₄ crystal have the width of about 0.30 degree proving the excellent quality of the grown samples. X-ray synchrotron experiments show that crystals have spinel structure with the lattice constant a₀=8.09853(1) Å. Magnetization measurements give the effective magnetic moment μ_eff=4.63 μ_B per Co⁺² ion in a good agreement with previous measurements on ceramic samples.     

On the spontaneous electro-optic effect in triglycine sulphate crystals with L-threonine admixture

The temperature and spectral dependences of the coefficients R _i2* of the quadratic electro-optic effect (EOE) in triglycine sulphate crystals with 5% L-threonine admixture have been calculated using the temperature and spectral dependences of the refractive indices n _i . It is established that the coefficients R _i2* of the admixture-containing triglycine sulphate crystals exhibit weak spectral and temperature dependences. In the polar direction, R _i2* are substantially different from the coefficients of admixture-free triglycine sulphate crystals. This indicates the occurrence of a bias field, the predominant orientation of the dipole moment of the polar defect, and a decrease in the spontaneous polarization in admixture-containing crystals.     

Diamagnetic and photoabsorption characterisation of gel‐grown cadmium oxalate single crystals

Perfect single crystals of cadmium oxalate trihydrate have been grown using the slow and controlled reaction between Cd⁺² and (C₂O₄)^‐2 ions in agar‐agar gel, resulting in the formation of insoluble product Cd(COO)₂.3H₂O. The optimum growth parameters have been determined. The variation of magnetic moment of the grown crystals under an applied static magnetic field is studied and the material is found to be diamagnetic. The polarizability is found sensitive to optical band gap. An empirical relation between magnetic susceptibility and electronic polarizability has been established. Optical absorption spectra of the sample recorded in the range 200‐2500 nm reveal transitions involving absorption and emission of phonons. The detailed study supports the existence of allowed direct and indirect allowed gaps in the material. The direct allowed transition prevails in the region of relatively higher photon energy. Some feeble disorder in the crystal is conceived to be present. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal electric field in RAgSb2 (R = Ho, Er, Tm) intermetallic compounds

The magnetic scattering spectra of RAgSb₂ (R = Ho, Er, Tm) intermetallic compounds are measured and their crystal electric field parameters are determined using inelastic neutron scattering. It is revealed that the ground state is a nonmagnetic singlet for the HoAgSb₂ compound, a Kramers doublet with a strongly anisotropic g factor for the ErAgSb₂ compound, and a quasi-doublet (random doublet) characterized by an extremely anisotropic g factor for the TmAgSb₂ compound. The exchange interaction is estimated in the molecular field approximation. The magnetic properties of the RAgSb₂ compounds are analyzed in terms of the energy level schemes and eigenfunctions determined in this study. The calculated anisotropic magnetic susceptibilities for all compounds are in good agreement with the experimental data obtained for single crystals.     

Study of phase transitions and the incommensurate phase in ACBX 4 crystals by the Monte Carlo method

The statistical model of successive phase transitions in the family of crystals described by the general formula ACBX ₄ has been studied. It is assumed that tetrahedral BX ₄ groups in the disordered tetragonal phase can be located in four equally probable equilibrium positions. Five representatives with different sequences of phase transitions in this family of crystals are considered. The effective equilibrium constants of interactions between tetrahedral groups are calculated within the framework of the electrostatic model. The corresponding phase diagrams and the thermodynamic characteristics of the phase transitions are studied by the Monte Carlo method. The experimental data provided the establishment of the sequence of phase transitions in Rb₂ZnCl₄ and K₂SeO₄ crystals with the formation of an intermediate incommensurate phase. The character of the structure modulation in this phase is established. The calculated thermodynamic characteristics of the phase transitions agree quite well with the experimental data for all the crystals under consideration.     

Optical absorption spectra and related parameters of ammonium zinc chloride crystal in the antiferroelectric and commensurate phases

Optical absorption along the three crystallographic axes of (NH₄)₂ZnCl₄ single crystals is reported over a temperature range from 276 K to 350 K. Our results clearly confirm the antiferroelectric to commensurate phase transition at 319 K. Analysis reveals that at the absorption edge the type of transition is the indirect allowed one. The indirect band gaps at various temperatures are determined and their temperature dependence is estimated in the antiferroelectric and commensurate phases. Optical parameters related to the temperature dependence of the energy gap are evaluated. The single‐effective oscillator model was used to describe the imaginary part of the dielectric constant, which facilitate calculation of the dipole moment parameters. The steepness parameter is given, its value is used to estimate the temperature dependence of the indirect energy gap and the result is compared with that calculated graphically. In the region of the absorption edge, the absorption coefficient obeys Urbach's rule. Urbach characteristic parameters are determined and their temperature dependence is investigated. Correlation between different parameters is considered. Most of the results confirm the optical isotropic nature of AZC crystals. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Geometrically frustrated Kagome staircase lattice with chemical disorder

The effect of nonmagnetic Mg²⁺ and magnetic Co²⁺ doping in Kagome staircase compounds was investigated using DC magnetic susceptibility. The main effect of doping is to change effective anisotropy of the Ni₃V₂O₈ and Co₃V₂O₈ crystals. It has a considerable effect on magnetic field induced phase transitions in both kinds of crystals. The doping has also an effect on the Dzyaloshinskii–Moriya exchange interactions. In some cases the doping enhances this interaction while in another it suppresses it completely.     

EPR and Optical Absorption Studies of γ-irradiated Pyrene Single Crystals

Pyrene single crystals irradiated with γ rays at room temperature have been investigated by electron paramagnetic resonance and optical absorption experiments. EPR spectra exhibit a triplet characteristic and each line of the triplet shows characteristic features with rotations of the crystals in a magnetic field. From analyses of these spectra the presence of two kinds of hydrogen added pyrene radicals, 3-H₂-pyrene and 2-H₂-pyrene radicals, is concluded. In the optical absorption spectrum nine main absorption bands have been detected. These absorption bands are compared with the theoretically calculated transition energies with SCF-CI molecular orbital calculations for 3-H₂-pyrene and 2-H₂-pyrene radicals. Reasonable correspondences are obtained between theoretical values and the experimental spectrum.     

Single crystal growth from the melt and magnetic properties of hexaferrites–aluminates

Single crystals of aluminum substituted barium hexaferrite were grown by the floating zone method with optical heating. Single crystals were produced from a melt of stoichiometric composition. The process was carried out under a pressure of 50 atm of oxygen. In the system BaO–(x)Al₂O₃–(6?x)Fe₂O₃ the region of single phase crystal growth from the melt is limited by the value x=3. For higher substitutions single-phase crystallization is not observed. The grown single crystals are cylindrical boules with a diameter of 4–5 mm and with lengths up to 50 mm. To avert cracking the crystals have been annealed during the process of growth at 1100 °C. The content of FeO in the composition of single crystals of barium hexaferrite, grown by zone melting under an oxygen pressure of 50 atm, is approximately 0.3 wt%. In the system of hexaferrite–aluminates the macroscopic magnetic moment of the material disappears at x=3.     

Orientation dependence of the NMR signal of deformed NaCl single crystals

The ²³Na signal of different deformed NaCl crystals was measured as function of the angle of rotation of the crystal with respect to the static magnetic field. The second moment of the NMR line is changed periodically determined by the slip mechanism. It is shown that the measured second moment can be obtained by a superposition of the parts originating from two-fold and four fold slip, respectively. The portion of the two slip mechanisms can be calculated quantitatively by fitting the experimental points.     

Electron irradiation‐induced effects on optical spectra of (NH4)2ZnCl4: x Sr2+ single crystals

The effect of electron‐beam irradiation with different doses on optical constants of (NH₄)₂ZnCl₄: x Sr²⁺ crystals with x=0.000, 0.020, 0.039, 0.087 or 0.144 wt% has been studied. The optical transmission in the energy range 3.4‐6.4 eV was measured hence the absorption coefficient was computed as a frequency function. The absorption coefficient was also calculated as a function of electron‐beam dose. Irradiation with e‐beam did not affect the allowed indirect type of transition responsible for interband transitions of (NH₄)₂ZnCl₄: x Sr²⁺ crystals. Values of the optical energy gap E_g and optical moment E_p for electronic interband transition of unexposed and (NH₄)₂ZnCl₄: x Sr²⁺ crystals after e‐beam exposure were deduced. The area under the absorption band at 5.30 eV was used to evaluate the effect of e‐irradiation on optical parameters of samples with x=0.00, 0.020 or 0.039. A shift in the position and a nonmonotonic change in the intensity of this band with increasing e‐beam dose was observed. Changes in the E_g value were used to evaluate the effect of e‐beam exposure dose on (NH₄)₂ZnCl₄: x Sr²⁺ samples with x=0.087 or 0.144. The obtained results were compared with those obtained for the same crystals after irradiation with different γ‐doses.     

Growth of (CH3)2NH2CuCl3 single crystals using evaporation method with different temperatures and solvents

The bulk single crystals of low-dimensional magnet (CH₃)₂NH₂CuCl₃ (DMACuCl₃ or MCCL) are grown by a slow evaporation method with different kinds of solvents, different degrees of super-saturation of solution and different temperatures of solution, respectively. Among three kinds of solvent, methanol, alcohol and water, alcohol is found to be the best one for growing MCCL crystals because of its structural similarity to the raw materials and suitable evaporation rate. The best growth temperature is in the vicinity of 35 °C. The problem of the crystals deliquescing in air has been solved through recrystallization process. The crystals are characterized by means of X-ray diffraction, specific heat and magnetic susceptibility.     

Distribution coefficient of boron in Si crystal ingots grown in cusp-magnetic Czochralski process

Silicon single crystals are grown by the Czochralski method with various growing conditions. Effective segregation coefficient of boron is found to depend on the magnetic field in cusp-magnetic Cz method. Effects of zero-Gauss plane (ZGP), ZGP shape and magnetic intensity (MI) on the dopant concentration and its distribution in the crystal are experimentally investigated. The shape of ZGP is not only flat but also parabolic due to the magnetic ratio (MR), which is the ratio of the lower to upper electric-current densities in the configurations of the cusp-magnetic field. Equilibrium distribution coefficient of boron calculated by BPS model is 0.698. With the crystal rotation (w) of 16 rpm and the crucible rotation of ?0.5 rpm, the effective distribution coefficient (k_e) is 0.728 in zero magnetic intensity and increases up to 0.8093 in the parabolic ZGP shape. Although the magnetic strength near the crystal–melt interface decreases with increasing MR, it increases in the bulk melt, and hence k_e increases. Flow stability in the bulk melt influences k_e. At the magnetic field and growing conditions, k_e increases with increasing initial charge size of the silicon melt. There is no significant influence of ZGP on the radial distribution of the boron concentration. Simulation results of melt flow in the presence of a parabolic ZGP are outlined, and the segregation results in the experiments are compared with published experimental data.     

Simulation of Simple and Complex Gadolinium Molybdates by the Interatomic Potential Method

Crystals of ferroelectric?ferroelastic gadolinium molybdate Gd₂(MoO₄)₃, calcium molybdate CaMoO₄, and double sodium?gadolinium molybdates of stoichiometric (Na_1/2Gd_1/2MoO₄) and cationdeficient (Na_2/7Gd_4/7MoO₄) compositions, which are used to design solid-state lasers, phosphors, and white LEDs, have been simulated by the interatomic potential method. Their structural, mechanical, and thermodynamic properties are calculated using a unified system of interatomic potentials and effective ion charges, which demonstrated transferability and made it possible not only to describe the existing experimental data but also to predict some important physical and thermodynamic properties of molybdate crystals. The influence of the deviation from stoichiometry and partial ordering of cations on sites in nonstoichiometric crystals on the properties and local structure of sodium?gadolinium molybdates is discussed.     

Spectroscopy studies of pure and chromium-doped calcium gallogermanate crystals, Ca3Ga2Ge4O14

Absorption spectra, the spectra of circular dichroism and magnetic circular dichroism of pure and Cr-doped Ca₃Ga₂Ge₄O₁₄ crystals have been studied. The crystal-field parameters and the transition frequencies of Cr³⁺ ions are calculated. The location of Cr³⁺ and Cr⁴⁺ ions in oxygen octahedra and tetrahedra is confirmed. The spectra of circular dichroism show the maxima due to Cr³⁺ ions and growth-induced defects.     

Electrostatic model of the LiТаO<Subscript>3</Subscript> ferroelectric

Possible combinations of the electronic polarizability tensor components for oxygen and tantalum ions have been established based on the analysis of the refraction coefficients of LiТаO₃ crystal in the far-IR region. The local electric field on structurally nonequivalent ions in the LiТаO₃ unit cell was calculated within the modified point-multipole model. A combination of the electronic polarizability tensor components for oxygen and tantalum ions and their effective charges is established, which provides a good correspondence of the calculation results with the experimental data on LiТаO₃ crystals obtained by ⁷Li nuclear magnetic resonance and ¹⁸¹Та nuclear quadrupole resonance and with the known value of the crystal spontaneous polarization.     

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.