Growth of big single crystals of Sr2YRu1‐xCuxO6 from high temperature solutions

Single crystals of Sr₂YRu_1‐xCu_xO₆ (x = 0 ‐ 0.4) have been grown from PbO‐PbF₂ based solutions in the temperature range 1150 – 1350°C. A silicon carbide heating element furnace (with a recrystallized alumina tube lining) in a vertical configuration was used to grow the crystals in platinum crucibles. Conditions for the stable growth of big crystals have been investigated. The morphology of the crystals containing Cu was found to change from octahedral to cube octahedral as the growth temperature is increased from 1150 to 1350°C. Crystals measuring up to 4.5 mm across and 2.5 mm thick have been grown from 1250°C. The incorporation of Cu into the crystals was ascertained by EDS and x‐ray diffraction analysis. A diamagnetic transition which increased in magnitude and temperature with x was observed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of Pb on the properties of Sr2YRu1‐xCuxO6 crystals grown from PbO‐PbF2 solutions at high temperatures

Single crystals of Sr₂YRu_1‐xCu_xO₆ with x=0 and x=0.1 were grown using PbO‐PbF₂ based solutions at different temperatures in the range 1150–1350°C. The influence of Pb from the solutions and the Cu from the solid solutions of Sr₂YRu_1‐xCu_xO₆ on the resulting crystals was studied using microstructure and magnetic property measurements. The peaks in the powder X‐ray diffraction patterns and Raman spectra do not change in the case of x=0 crystals but shift in the presence of Cu. A diamagnetic transition indicative of superconductivity was observed in the presence of Cu and an antiferromagnetic behavior with x=0. Based on these results it is concluded that Pb may not be incorporated in the crystals and even if it does the influence is not observed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

Properties of AgGa1‐xInxSe2 single crystals grown by Bridgman method

High‐pure and single‐phase AgGa_1‐xIn_xSe₂ (x=0.2) polycrystalline was synthesized by the mechanical and temperature oscillation method. Adopting the modified Bridgman method an integral AgGa_1‐xIn_xSe₂ single crystal with diameter of 14 mm and length of 35 mm has been obtained at the rate of 6 mm/day. It was found that there is a new cleavage face which was (101), and observed the four order X‐ray spectrum of the {101} faces. By the method of DSC analysis the melting and freezing points of the AgGa_1‐xIn_xSe₂ (x=0.2) single crystal were about 828°C and 790°C. The transmission spectra of the AgGa_1‐xIn_xSe₂ (x=0.2) sample of 5×6×2 mm³ were obtained by means of UV and IR spectrophotometer. The limiting frequency was 774.316nm and the band gap was 1.6eV. It can be found in the infrared spectrum that the infrared transmission was above 60% from 4000cm^‐1 to 600cm^‐1. The value of α in 5.3µm and 10.6µm were 0.022cm^‐1 and 0.1cm^‐1 respectively. All results showed that the crystal was of good quality. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth of single crystals of the high-pressure ɛ-FeOOH phase

Single crystals of the high-pressure ?-FeOOH phase are grown from an aqueous solution at p = 7 GPa in the temperature range 580–350°C. Dark brown crystals of prismatic habit are obtained that have characteristic sizes of 0.1 × 0.1 × 0.7 mm. A region of the t-x phase diagram of the H₂O-Fe₂O₃ system at p = 7 GPa is constructed on the basis of the data obtained.     

Single crystal preparation of MnxCr3–xO4 by flux method

Mn_xCr_{3 x}O₄ was prepared by the flux method. Melts of PbO PbF₂, Bi₂O₃ B₂O₃, B₂O₃, Na₂B₄O₇, and Na₂W₂O₇ Na₂WO₄ were used. The best results could be yielded with the PbO PbF₂ flux, from which crystals with 2–4 mm in thickness were grown. The Bi₂O₃ B₂O₃ flux produced crystals with 1–2 mm in thickness. The spinell structure of the chromite was proved by X-ray investigation.     

A new piezoelectric single crystal obtained by Ge doping in the SiO2 structure

The interest of Si_1–xGe_xO₂ single crystals with alpha‐quartz structure is connected to improvement of electromechanical coefficients and rise of α – β phase transition of quartz one. Growth of an α‐Si_xGe_1–xO₂ crystal was realized by a hydrothermal method of temperature gradient in autoclaves, made from Cr–Ni alloys. Nutrient material was prepared from synthetic quartz as crashed rods and placed in the bottom of autoclaves. There was loaded GeO₂ powder additive in proportions to quartz nutrient. Single crystals were investigated by electron microprobe analysis, X‐ray diffraction and atomic force microscopy. The most important result, which was obtained during the investigations, is an experimental proof of growth of α‐Si_xGe_1–xO₂ single crystals under the hydrothermal conditions. The present results thus open the possibility to tune the piezoelectric properties of these materials by varying the chemical composition. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Twin Structure of (La,Nd)GaO3 Solid Solutions

For La_1‐xNd_xGaO₃ crystals the La‐Nd substitution leads to decrease of spontaneous strains and for composition with x≈0.32 the six possible twin states of orthorhombic phase (m3mFmmm) may be degenerated in three twin states inhered in m3mF4/mmm species when a distorted perovskite pseudocell becomes tetragonal. The {110} and {112} reflection twins and axial twins with compositional planes close to (211) and (21‐1) (S‐walls) were identified in La_1‐xNd_xGaO₃ (x=0.07, 0.12, 0.20) solid solutions crystals. All observed twins are typical for crystals with GdFeO₃ type perovskite‐like structure. It has been shown that for x≤0.2 and x≥0.5 orientations of S‐walls weakly depend on La/Nd ratio, whereas in the range of 0.2<x<0.5 they depend strongly on the solid solution composition. The tilt angle between two twin states across twin boundary in La_1‐xNd_xGaO₃ (x<0.6) solid solutions is smaller than that between two twins in pure LaGaO₃ or NdGaO₃.     

Study on K(DxH1‐x)2PO4 Crystals: Growth Habit,Optical Properties and their Improvement by Thermal‐Conditioning

Phosphite, which often exists in growth solutions obtained directly from commercial P₂O₅ , was found to have significant inhibiting effects on the growth of pyramidal face of KDP crystals. K(D_xH_1‐x)₂PO₄ (referred to as DKDP) crystals with different deuterium fraction x were grown and the optical performances were investigated. The absorption coefficients at 1.05 μm decreases monotonically with the increase of x. The transmission threshold shift from 1.65μm at x=0 to 2.10 μm at x=0.96. The high temperature phase transition temperature and latent heat were measured using the method of differential scanning calorimetry (DSC). Thermal conditioning experiments were carried out at 180°C and 140°C for KDP and DKDP, respectively. After conditioning, a different degree of improvement was observed in the optical homogeneity of the samples, while the laser damage threshold and light absorption coefficient showed no significant change.     

Synthesis and improved electrochemical performance of LiCo1‐xSnxO2 (x= 0 to 0.1) powders

Layered intercalation compounds LiCo_1‐xSn_xO₂ (x= 0 to 0.1) have been prepared using a simple combustion route method. X‐ray diffraction patterns and Laser Raman spectrum suggest that the synthesized materials had the R‐3m structure. Scanning electron images show that particles are well‐crystallized with a size distribution in the range of 50‐100 nm. The room temperature electrical conductivity of the sample increased with Sn content. For LiCo_1‐xSn_xO₂(x = 0, 0.01, 0.03, 0.05 and 0.1), the first discharge capacity increased with increase in Sn content. Among these samples, LiCo_0.95Sn_0.05O₂had produced the best performance of all others with a stable reversible capacity of 186 mAhg^‐1 after 30 cycles. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth of barium aluminum (gallium) borates

Crystals listed in the JCPDS card in the BaO‐B₂O₃‐Al₂O₃ and BaO‐B₂O₃‐Ga₂O₃ systems are of interest from a viewpoint of the Second Harmonic Generation (SHG). Ba₅Al₄B₁₂O₂₉ and Ba₅Ga₄B₁₂O₂₉ are promising new crystals with SHG activity and with congruent melting mode. These crystals can be grown by the Czochralski method with a size of 3 × 3 × 0.1‐1mm. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Soft‐Mode Spectroscopy in Fe:KTa1‐xNbxO3 Crystals

Fe‐doped potassium tantalite niobate, Fe:KTa_1‐xNb_xO₃ (Fe:KTN), crystallizes with x = 0.48 and a perovskite‐type structure in tetragonal system with point group 4mm, conforming space group P4mm. The paraelectric‐ferroelectric structural transition of the Fe:KTN is studied by Raman scattering investigations. A condensed soft lattice vibrational mode at the phase transition has been analyzed. It originates from the symmetric O2/O3‐Nb/Ta‐O3/O2 in‐plane bending of the Nb/TaO₆ group. The soft optical phonon mode concerns the extraordinary transverse optical phonons propagating along the [110] direction. The Raman spectra measured reflect the crystal disorder. Curie temperature measured by two methods is within 353 and 356.5 K.     

Thermodynamical miscibility in 0.8[xB2O3-(1 − x)P2O5]-0.2K2O glasses

The thermodynamical miscibility in 0.8[xB₂O₃-(1 − x)P₂O₅]-0.2K₂O glasses has been studied by measuring the glass transition temperature and the mixing enthalpy. Measurements have been performed by differential scanning calorimeter and hydrofluoric acid solution calorimetry at 298 K. The enthalpies of mixing are significantly negative over the whole range of composition. The results are discussed in terms of intermolecular associations.     

Crystal growth of zirconium‐doped KTiOPO4 crystals in the K2O‐P2O5‐TiO2‐ZrF4 system

Zirconium‐doped KTiOPO₄ (KTP) crystals were grown using a high temperature flux method in the K₂O‐P₂O₅‐TiO₂‐ZrF₄ system. The dopant content in the single crystals with general composition KTi_1‐xZr_xOPO₄ (where x = 0 – 0.026) strongly depends on zirconium concentration in the homogeneous melts. AES‐ICP method and X‐ray fluorescence analysis were used to determine the composition of the obtained crystals. Phase analyses of the products were performed using the powder XRD. The structures of KTiOPO₄ containing different quantities of Zr were refined on the basis of single crystal XRD data. Applying ZrF₄ precursor for zirconium injection into the flux allowed growing the zirconium‐doped KTP crystals at 930–750°C. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Study on the ferroelectric phase transition in potassium lithium niobate (KLN)

The ferroelectric phase of potassium lithium niobate K₃Li_2–xNb_5+xO_15+2x (KLN) in the range of 0.15 < x < 0.5 is a very promising material for the second harmonic generation (SHG) in the blue visible region (∼410 nm). The ferroelectric phase transition was shown to occur between 400 and 500°C depending on the composition of the KLN phase. In this study several analysis techniques were used to investigate the phase transition on ferroelectric (x = 0.3) KLN samples. The temperature‐dependent measurements of the relative dielectric constant ε₃₃ provided a phase transition temperature of about 470°C. In our DTA experiments, a small but reproducible thermal effect at the phase transition in KLN was indicated. The temperature‐dependent birefringence measurement technique, applied the first time on KLN, shows a second order behaviour at a temperature of 467 °C. However, this phase transition is accompanied by a small thermal effect. The DSC analysis for the other KLN composition (x = 0.5) provided a phase transition temperature of 514 °C. The appearance of a phase transition in the paraelectric KLN phase (Nb content higher than 55 mol%) was also studied. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

Growth of Ba2Re(Y,Pr)Ru1‐xCuxO single crystals in a high temperature solution drop using an infrared imaging system

Infrared imaging furnace was used to grow single crystals of Ba₂YRu_1‐xCu_xO₆ and Ba₂PrRu_1‐xCu_xO₆ using high temperature solutions of PbO‐PbF₂ in the form of a bubble attached to the feed rods. Several small crystals were found deposited on the cooler portions of the sintered rod as well as in the drop like portion at the end of the rod. These crystals were collected and the morphology, microstructure and magnetic properties were studied. The details of these investigations are presented. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectral and conductivity features of novel ternary Tl1–xIn1–xSnxS2 crystals

Complex studies of novel Tl_1–xIn_1–xSn_xS₂ single crystalline alloys (x = 0.1; 0.2; 0.3; 0.4; 0.5) were performed. Here we present the study of the effect of the partial cation substitution of Sn ions by In ions on their optical absorption and photoconductivity characteristics. The dependences of optical and electric properties of the crystals of the crystalline solid solutions on temperature and composition are discussed within a framework of intrinsic defect states forming then fundamental absorption. The calculations of the charged defects responsible for the experimentally determined values of Δ₀ were done. Some increase of the concentration for charged defects with the sample temperature is probably related to the thermal ionization of some of the defects that were neutral at lower temperature. The results obtained will be analyzed within the framework of the intrinsic defect's model.     

Magneto‐transport properties of polycrystalline YBa2(Cu1‐xMx)3O7‐δ (M = B and Mn)

The magnetic and transport properties of polycrystalline YBa₂ (Cu_1‐xM_x)₃ O_7‐δ (M = B and Mn) superconductor was investigated. Samples of YBa₂(Cu_1‐xB_x)₃O_7‐δ doped with several concentrations of boron B(x = 0.05 and 0.1) were investigated using magnetization measurements. A YBa₂(Cu_1‐xMn_x)₃O_7‐δ sample doped with Mn with concentration of x = 0.02 was investigated using current‐voltage (I‐V) measurements. Our results on the YBa₂(Cu_1‐xB_x)₃O_7‐δ samples reveal a considerable increase in the hysterisis width of the magnetization, M versus the applied magnetic field H with increasing boron concentration. The lower critical field was also found to be enhanced by boron doping. The critical current density, J_c was found to be significantly enhanced in the Mn‐doped sample. The enhancement of J_c was found to be more significant at the lower temperatures for all applied magnetic fields used (0 Oe, 300 Oe, and 500 Oe). Thus, chemical doping is suggested to enhance the vortex pinning forces in the YBCO samples. From the resistivity (R‐T) measurements, chemical doping of the samples was found to have no significant effect on the critical temperature, T_c. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Neutron powder diffraction studies in CaMn1‐xCuxO3 (x = 0, 0.2)

Neutron powder diffraction patterns were recorded on CaMn_1‐xCu_xO₃ (x = 0 and 0.20) compounds at different temperatures down to 11K. All the patterns were analyzed by employing Rietveld refinement technique and using the Fullprof program. The observed crystallographic peaks could be refined by using Pbnm space group and no structural transition has been observed down to 11K. An additional peak at 2θ = 16.7° has been observed with decrease in temperature below T_N and its intensity was found to increase with decrease in temperature. It could be indexed to magnetic (101) plane. The magnetic ordering is found to be G‐type antiferromagnetic behaviour. The magnetic moment at 11K for the samples x = 0.0 and 0.20 are found to be 2.69 and 2.42μ_B. The doped Cu ions are found to be in Cu²⁺ state and take part antiferromagnetic interactions with Mn ions. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)