Coupled substitution of gallium by magnesium and zirconium in single crystals of gadolinium gallium garnet

Single crystals of gadolinium gallium garnet in which the gallium ions on the octahedral sites were partially substituted by coupled substitution of magnesium and zirconium have been grown using the Czochralski technique. Single crystals of 36 mm in diameter and 100 mm in length corresponding to the formula Gd₃Ga_5-x-yMg_xZr_yO₁₂ have been obtained from melt compositions in which 0.1 ? x = y ? 0.7. The dislocation and inclusion densities of the single crystals are below 5 cm^-2. The lattice parameters increase linearly from 12.382 Å for gadolinium gallium garnet to 12.489 Å for x = y ≈ 0.54. The distribution coefficient increases in this concentration range from K_eff = 0.58 to K_eff = 0.89. Boules grown from melt compositions in which x = y ? 0.7 appear cloudy through precipitation of Gd₂Zr₂O₇ as a second phase.     

Composition,morphology, and properties of sodium-bismuth tungstate crystals

A correlation has been revealed between the formation conditions, composition, morphology, and physicochemical properties of NaBi_{1 − x} (W_{1 + y} O₄)₂ crystals (0 ≤ x ≤ 0.16, 0 ≤ y ≤ 0.11). The effect of melt deviation from stoichiometry on the decomposition rate of grown crystals under electron beam irradiation is shown by transmission electron microscopy. A nonuniform dopant distribution over the crystal boule cross-section is found by microprobe analysis. The Raman spectra of the samples depend on their crystallographic orientation.

     

Coexistent Phases and their Electrical and Structural Behaviour in the Ternary Re/Mo/O System

In order to complete and improve phase diagrams of transition metal oxides the existence and properties of compounds in the Re/Mo/O system have been investigated. Single crystalline solid solutions Re_1-xMo_xO₂ (0 < x < 0.37) and Mo_1-yRe_yO₂ (0 < y < 0.42) were prepared by Solid State Reactions and Chemical Transport Reactions (CTR) and characterized by means of X-ray-diffraction, ICP-AES, and EPMA. In addition, it was shown that the trioxides Re_1-xMo_xO₃ or Mo_1-yRe_yO₃ respectively, do not prove a distinct solubility. First results on Re-doped Magneli phases of Mo are also discussed. There were found two series of solid solutions Mo_4-zRe_zO₁₁ (0 < z < 0.40) which derive from γ-Mo₄O₁₁ and η-Mo₄O₁₁. The other Magneli phases did not show a significant Re content. Using X-ray diffraction, AFM and optical microscopy the structure and morphology of single crystals has been studied. It was steated that the dioxide solid solutions were very homogeneous and structural phase transitions depending on x or y did not occur. That is in good agreement with measurements of electrical conductivity σ in the temperature range from 20 K to 300 K in which the samples showed the behaviour of metals with lattice defects. The Magneli phases Mo₈O₂₃ and Mo₉O₂₆ turned out to be “narrow gap semiconductors” in the low temperature range with activation energies of less than 0.1 eV. The γ-Mo₄ O_11- and γ-Mo₄O₁₁ crystals, the pure and Re-doped ones, were found as metallic conductors at higher temperatures and below a transition temperature they show a semiconductive behaviour.     

Ionic conductivity of congruently melting Ca0.6Sr0.4F2 and Ca1 ? x ? ySryRxF2 + x (R = La, Ce, Pr, Nd) single crystals with fluorite structure

Single crystals of congruently melting compositions of the Ca_0.6Sr_0.4F₂ and Ca_{1 − x − y} Sr _y R _x F_{2 + x} (R = La, Ce, Pr, Nd; x = 0.16–0.21; y = 0.07–0.16) solid solutions with fluorite structure have been grown by the Bridgman-Stockbarger method. Their electrical properties have been investigated in the range from 473 to 823 K, and it is shown that they are ionic conductors. For Ca_0.6Sr_0.4F₂ crystals, the ionic conductivity σ = 2 × 10⁻⁶ S/cm at 673 K, and the ion transport activation energy E _a = 1.1 eV. For Ca_0.77Sr_0.07La_0.16F_2.16, Ca_0.70Sr_0.11Ce_0.19F_2.19, Ca_0.65Sr_0.15Pr_0.20F_2.20, and Ca_0.58Sr_0.21Nd_0.21F_2.21 crystals, the values of σ lie in the range from 9 × 10⁻⁷ to 2 × 10⁻⁶ S/cm at 500 K, and the activation energy E _a is 0.88–0.93 eV. The concentration and mobility of ionic charge carriers in Ca_{1 − x − y} Sr _y R _x F_{2 + x} crystals have been calculated. Original Russian Text ? N.I. Sorokin, D.N. Karimov, E.A. Krivandina, Z.I. Zhmurova, O.N. Komar’kova, 2008, published in Kristallografiya, 2008, Vol. 53, No. 2, pp. 297–303.     

Crystal Structure of 1-(2-Pyridylmethyl)-2,4,6-Triphenyl-Pyridinium Perchlorate

The crystals of 1-(2-pyridymethyl)-2,4,6-triphenylpyridinium perchlorate are monoclinic, space group P 2₁/b. The unit cell parameters are a = 18.941(5), b = 19.502(6), c = 15.135(5),y = 115.99°(2), Z = 8, d₀ = 1.31(3), d_x = 1.319 g/cm³. The structure has been determined by direct methods and refined by block diagonal least squares to R₀ = 0.08 for 2520 reflections. The phenyl rings in both molecules (I) and (II) are planar. These rings are twisted with respect to the central pyridyl rings.     

Investigation of radiation defects in electron irradiated Hg1−xCdxTe crystals using positron annihilation

The electron characteristics of defects in the initial and electron irradiated Hg_1−xCd_xTe (2–3 MeV, 10¹⁸ cm⁻², 300 K) crystals using the positron annihilation method have been investigated. The data of electric measurements are confirmed on connection of p-type conductivity with vacancy defects of metal sublattice initial crystals Hg_1−xCd_xTe. An analysis of correlation curves of irradiated crystals has shown a possibility of formation of associations of initial defects and radiation damages of vacancy type during radiation process. The presence of narrow component on correlation curves in the region of small angles is associated with formation of positronium states localized in the region of radiation defect complex of vacancy type. Identification of positron-sensitive defects with electrically active radiation induced ones has been carried out according to the results of isochronal annealing of irradiated crystals.     

Investigation into the evolution of the structure of K1−x LixTa1−y NbyO3 single crystals under variations in temperature

The evolution of the structure of K_1?x Li_xTa_1?y Nb_yO₃ single crystals with x = 0.001, y = 0.026, and 1900 ppm Cu (KLTN277) and with x = 0.0014 and y = 0.024 (KLTN123), which exhibit an extremely high permittivity (up to 4 × 10⁵ in the quasi-static regime for the KLTN277 crystal), is investigated in the range from room temperature to 20 K. It is demonstrated that, upon cooling to the lowest temperatures, both crystals retain their cubic structure, but the lattice parameters pass through a minimum at the temperature of the observed anomalies of the dielectric response (～50 K). In the neutron diffraction pattern of the KLTN123 sample, satellites appear in the vicinity of the (hhh) reflections at temperatures below ～50 K. These satellites can be associated with the nucleation of the rhombohedral phase.     

Transport Coefficients of (Bi1-xSbx)2Se3 Single Crystals

(Bi_1-xSb_x)₂Se₃(x = 0.0 to 0.2) single crystals were prepared using a modified Bridgman method. Measurements of the Hall coefficient R_H, electrical conductivity σ and Seebeck coefficient α showed that incorporation of the antimony atoms into the Bi₂Se₃ crystal lattice results in an increase in the free electron concentration for a low antimony content, whereas the free electron concentration is suppressed in the range of a high antimony content. This effect is explained qualitatively by changes in the concentrations of point defects in the (Bi_1-xSb_x)₂Se₃ crystals. We asume that the substitution of Bi atoms by Sb atoms results in a decrease in the concentration of Se vacancies V and antisite defects Bí_Se. The course of the dependences of In (R_Hσ) vs In T manifests that in the temperature region of 100–400 K transport properties of the studied crystals are characterized by a mixed transport mechanism of free carriers, mainly on acoustical phonons and ionized impurities.     

Structural phase transitions in Cu2–xFeyS crystals

Crystals with Cu_2−xFe_yS compositions (x = 0.30, 0.25, 0.20, 0.15; y = 0.05) have been synthetized and obtained by the method of slow cooling. X-ray diffractometric studies have shown that at room temperature the above crystals consist of an orthorhombic phase (anilite), a monoclinic phase (djurlite), and their metastable high-temperature facecentered cubic phases (FCC)₁ and (FCC)₂, respectively. A crystallographic relation has been found between the lattices of the orthorhombic, monoclinic and (FCC)₁ phase. It is shown that all these phases transform in the final analysis to a single high-temperature fcc phase. All the transitions are reversible, i.e. in the course of inverse cooling to room temperature, the diffraction patterns are restored completely in reverse order.     

Multimode phonon structure of Be‐containing II ‐ VI mixed crystals determined by IR spectroscopic ellipsometry

Spectroscopic ellipsometry in the infrared spectral range 250‐5000 cm^‐1 is used for analysis of the dielectric response of Zn_1‐x‐yBe_xMg_ySe and Zn_1‐x‐yBe_xMn_ySe crystals grown by a high‐pressure Bridgman method. Ellipsometric spectra display features in the spectral range 390‐500 cm^‐1 associated with BeSe‐type phonon modes. In the optical spectra of Zn_1‐x‐yBe_xMg_ySe crystals both BeSe‐type and MgSe‐type lattice absorption bands are detected. The MgSe‐like modes are located at approximately 300 cm^‐1. The complex dielectric functions can be reproduced using a model with two or three and one or two classical damped oscillators corresponding to the BeSe‐like and the MgSe‐like transverse‐optical phonon modes, respectively. The frequencies of longitudinal‐optical phonons have been derived from the dielectric loss functions. A red‐shift of the BeSe‐like phonons frequencies with a mean rate 0.42 cm^‐1 (0.50 cm^‐1) per mole percent of Mg (Mn) incorporated to the alloy has been found for examined concentration range x, y ≤ 0.25. A noticeable damping the intensities of BeSe‐type modes with increasing fraction of Mg and Mn dopant is observed in comparison to the strengths of BeSe‐type modes in Zn_1‐xBe_xSe crystals. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The Improvement of Superconductivity in PbxBi2-xSr2CaCu2Oy

In this paper we present the results of recent studies on the improvement of superconductivity in Pb_xBi_2-xSr₂CaCu₂O_y single crystals by preventing impurities incorporation, employing ZrO₂ crucible for crystal growth and post annealing the as-grown crystals in vacuum or argon. It is realized that the superconductivity of as-grown crystals is improved.     

Nanostructured crystals of fluorite phases Sr1 ? xRxF2 + x (R are rare-earth elements) and their ordering: IV. Study of the optical transmission spectra in the 2–17-μm wavelength range

Transmission spectra of two-component crystals of Sr_1−x R _x F_2+x (R = Y, La-Lu; 0 ≤ x ≤ 0.5) in the 1–17-μm wavelength range were studied. The spectral characteristics of these crystals and of single-component crystals of MF₂ (M = Ca, Sr, or Ba) and RF₃ (R = La-Nd) were compared. The transmission cutoff of Sr_1−x R _x F_2+x crystals is shifted to shorter wavelengths with increasing x. The same tendency is observed with the increasing atomic number R of rare-earth elements for two isoconcentration series of Sr_1−x R _x F_2+x (x ∼ 0.10 and 0.28). This tendency is pronounced at large x. The transmission cutoff of Sr_1−x R _x F_2+x crystals can be varied in the range of from 10.7 to 12.2 μm by changing their qualitative (R) and quantitative (x) composition. Hence, these crystals can be assigned to multicomponent fluoride optical materials with controlled optical characteristics. The Sr_1−x R _x F_2+x crystals, where R = Ce-Sm, were shown to be promising materials for the design of selective optical filters in the 2–10-μm spectral range.     

Resistance and inductance studies of Bi2−xPbxCa2Sr2Cu3Oy superconducting compounds

Bi_2−xPb_xCa₂Sr₂Cu₃O_y compounds with (x = 0, 0.1, 0.2, 0.25, 0.3 and 0.4) were prepared by solid state reaction. The resistance and inductance results showed that transition temperature increases with increase in lead concentration. The highest value of T_c(0) observed is 109 K for Bi_1.70Pb_0.30Ca₂Sr₂ · Cu₃O_y. The change of inductance per unit volume at liquid nitrogen temperature as a function of composition showed maximum change in x = 0.30 Pb-doped sample. The results showed that the inductance change is maximum in samples which also showed highest T_c.     

Growth,structure, and superconducting properties of Bi2Sr2Ca2Cu3O10 and (Bi,Pb)2Sr2Ca2Cu3O10‐y crystals

Large and high‐quality single crystals of both Pb‐free and Pb‐doped high temperature superconducting compounds (Bi_1‐xPb_x)₂Sr₂Ca₂Cu₃O_10‐y (x = 0 and 0.3) were grown by means of a newly developed “Vapour‐Assisted Travelling Floating Zone” technique (VA‐TSFZ). This modified zone‐melting technique was realised in an image furnace and allowed for the first time to grow Pb‐doped crystals by compensating for the Pb losses occurring at high temperature. Crystals up to 3×2×0.1 mm³ were successfully grown. Post‐annealing under high pressure of O₂ (up to 10 MPa at T = 500°C) was undertaken to enhance T_c and improve the homogeneity of the crystals. Structural characterisation was performed by single‐crystal X‐ray diffraction (XRD) and the structure of the 3‐layer Bi‐based superconducting compound was refined for the first time. Structure refinement showed an incommensurate superlattice in the Pb‐free crystals. The space group is orthorhombic, A2aa, with cell parameters a = 27.105(4) Å, b = 5.4133(6) Å and c = 37.009(7) Å. Superconducting studies were carried out by A.C. and D.C. magnetic measurements. Very sharp superconducting transitions were obtained in both kinds of crystals (ΔT_c ≤ 1 K). In optimally doped Pb‐free crystals, critical temperatures up to 111 K were measured. Magnetic critical current densities of 2�10⁵ A/cm² were measured at T = 30 K and μ₀H = 0 T. A weak second peak in the magnetisation loops was observed in the temperature range 40‐50 K above which the vortex lattice becomes entangled. We have measured a portion of the irreversibility line (0.1‐5 Tesla) and fitted the expression for the melting of a vortex glass in a 2D fluctuation regime to the experimental data. Measurements of the lower critical field allowed to obtain the dependence of the penetration depth on temperature: the linear dependence of λ(T) for T < 30 K is consistent with d‐wave superconductivity in Bi‐2223. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nanostructured crystals of Sr1?xRxF2+x fluorite phases and their ordering: 6. Microindentation analysis of crystals

Hardness, crack resistance, brittleness, and effective fracture energy have been studied for crystals of 24 fluorite phases Sr_{1 − x} R _x F_{2 + x} (R are 14 rare earth elements (REEs); 0 < x ≤ 0.5) and SrF2 grown by the Bridgman method from a melt. These characteristics change nonlinearly with an increase in the REE content for Sr_{1 − x} R _x F_{2 + x} (0 < x ≤ 0.5) with R = La, Nd, Sm, Gd, and Lu; it is maximum in the range x < 0.1 for all REEs. The changes in a number of REEs have been traced for an isoconcentration series of Sr_0.90 R _0.10F_2.10 crystals (R = La, Nd, Sm, Gd, Ho, Er-Lu, or Y) and crystals (similar in composition) with R = Tb and Dy. The hardness of Sr_{1 − x} R _x F_{2 + x} crystals is higher by a factor of ∼2–3 than that of SrF2. The effect of decrease in microstresses in SrF₂ crystals is confirmed by the isomorphic introduction of R ³⁺ ions into this crystalline matrix.     

Growth and characterization of superconductive Nd2‐xCexCuO4‐y single crystals

Nd_2‐xCe_xCuO_4‐y single crystals with different x values have been successfully grown by Traveling Solvent Floating Zone method (TSFZ). Electronic properties of Nd_2‐xCe_xCuO_4‐y single crystals with various x have been studied in detail. The results show that superconductivity can be found in crystals with x > 0.1 (0.13‐0.18) directly grown at oxygen‐reduced atmosphere without post‐annealed, while no superconductivity appears in crystals with x < 0.1 at the same atmosphere. It is also found that, the segregation coefficient of Ce is determined to be 0.946 and transition temperature Tc (onset) reaches maximum value of 23.5 K at nominal composition x = 0.165. With further increase of Ce concentration, transition temperature of single crystals declines due to the precipitation of secondary Phases. In addition, the variation of lattice constants of Nd_2‐xCe_xCuO_4‐y single crystals with different x is also given. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of hexagonal ferrites BaFe12‐2xZnxTixO19 (0 ≤ x ≤ 2) by thermal decomposition of freeze‐dried precursors

Substituted barium hexaferrites, BaFe_12‐2xZn_xTi_xO₁₉ (0 ≤ x ≤ 2), have been synthesized by thermal decomposition of freeze‐dried acetate precursors. Decomposition and phase formation were investigated by means of thermal analysis, XRD and IR spectroscopy. The initially amorphous decomposed precursor reacts to the substituted hexaferrite via a spinel‐like maghemite (γ‐Fe₂O₃) and Zn/Ti containing spinel ferrites. The synthesis method allows a decrease of the reaction temperature and time, necessary for producing a single phase hexaferrite. At relative low reaction temperatures, the substitution rate x shows remarkable differences at different iron sublattices. For x ≤ 0,8 this selective substitution results in an increase of magnetization as x grows. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of InAs1–ySby solid solutions for obtaining decreased lattice mismatch in the InAs-GaSb (AlxGa1–nSb) system

This paper presents the results of investigation of the technological conditions of LPE growth of InAs_1–ySb_y solid solutions on InAs substrates. It is shown that the chosen regions of composition of InAs_1–ySb_y solid solutions and experimentally determined technological conditions allow the obtaining of InAs_1–ySb_y solid solutions with lattice parameter values close to those of the Al_xGa_1–xSb (0 ≦ x ≦ 0.2) solid solutions.     

Homogenitätsuntersuchungen und Bestimmung der molaren Konzentration x an CdxHg1–xTe mit Hilfe der Elektronenstrahlmikrosonde

The semiconductor Cd_xHg_1–xTe serves as a starting material for the production of infrared detectors with a high detectivity and a small time constant. Cd_xHg_1–xTe single crystals are necessary to manufacture detectors efficiently. The single crystals should not contain segregations and have to include a homogeneous molar concentration x. An electron microprobe X-ray analyzer meets all requirements expected from the measuring method for checking the homogeneity of Cd_xHg_1–xTe crystals. — Results of qualitative and quantitative studies in the microscopical and macroscopical range are presented. Typical defects of the crystals were detected by using the qualitative electron microprobe X-ray analysis. The quantitative analysis was carried out with standard samples. The method for determination of the molar concentration x of the standard samples is described.     

On the morphology of BaMoO4 crystals: A theoretical and experimental approach

BaMoO₄ crystals were obtained by a co‐precipitation method, and their structures were characterized by X‐ray diffraction and Rietveld refinement techniques. Field emission scanning electron microscopy was utilized to investigate the morphology of the as‐synthesized aggregates.‐ Through systematic first principle calculations within the density functional theory method at the B3LYP level, we investigated the structure; the surface stability of the (001), (101), (110), (100), (111), and (112) surfaces; and the morphological transformations of BaMoO₄. The relative surfaces energies were further varied to predict a complete map of the available morphologies through a Wulff construction approach. This revealed that the obtained experimental and theoretical morphologies coincided when the surface energy values of the (001) surface decreased while those of the (100) and (101) facets increased simultaneously. Analysis of the surface structures showed that the electronic properties were associated with the presence of undercoordinated [BaO_x] (x = 4, 5, and 6) and [MoO_y] (y = 3) clusters. The presented results provide a comprehensive catalog of the morphologies most likely to be present under realistic conditions, and will serve as a starting point for future studies on the surface chemistry of BaMoO₄ crystals.