Growth and characterization of a nonlinear optical crystal: l-histidine trifluoroacetate

A novel organic nonlinear optical crystal, l-histidine trifluoroacetate (LHTF), has been prepared, and single crystals had been grown by the controlled evaporation of the aqueous solution. Its solubility curve was determined gravimetrically. The structural, physicochemical properties of the grown crystals were characterized by X-ray powder diffraction, infrared spectroscopy and thermal analysis. Density functional theory at the B3LYP/6-31G (d, p) level had been used to compute the first-order hyperpolarizability of LHTF. The optical transmission spectrum and second-harmonic generation were investigated to study its linear and nonlinear optical properties.     

Nucleation kinetics,micro-crystallization and surface morphology studies of the nonlinear optical single-crystal l-lysinium trifluoroacetate

The organic nonlinear optical crystal of amino-carboxyl acid family, l-lysinium trifluoroacetate (abbreviated as LLTF) was successfully grown from its aqueous solution by the temperature-lowering technique. Its growth morphology was investigated based on the X-ray single-crystal diffraction data and the growth habits were studied using the micro-crystallization method. The metastable zonewidth and induction period were determined for the aqueous solution growth of LLTF. The surface free energy values were calculated from the experimental data. Nucleation kinetics and fundamental growth parameters such as critical radius, critical free energy and volume free energy change were also evaluated. Crystals of LLTF were obtained by the optimized nucleation parameters.     

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.     

Synthesis and characterization of single-crystalline PrCO3OH dodecahedral microrods and its thermal conversion to Pr6O11

Single-crystalline PrCO₃OH dodecahedral microrods with an orthorhombic structure have been successfully synthesized by the hydrothermal method used urea as the precipitator. Pr₆O₁₁ dodecahedral microrods have been obtained by thermal conversion of PrCO₃OH dodecahedral microrods at 600 °C in air for 6 h. The as-synthesized products were characterized by X-ray powder diffraction, field-emission scanning electron microscope, transmission electron microscopy, high-resolution transmission electron microscopy, selected-area electron diffraction, X-ray photoelectron spectra, fourier transform infrared spectroscopy and thermogravimetry–differential thermal analysis. The effect of the reaction parameters on the morphology of the product has been investigated. The dodecahedral microrods with larger size and better crystallinity can be obtained under the higher reaction temperature. The possible formation mechanism of PrCO₃OH microrods was discussed.     

Crystal growth and characterization of two-leg spin ladder compounds: Sr14Cu24O41 and Sr2Ca12Cu24O41

Single crystals of Sr_14−xCa_xCu₂₄O₄₁ (x=0 and 12) are grown by the travelling solvent floating zone technique using an image furnace. The grown crystals are characterized for their single crystallinity by the X-ray and Neutron Laue method. The magnetic susceptibility measurements in Sr₁₄Cu₂₄O₄₁ show considerable anisotropy along the main crystallographic axes. Low-temperature specific heat measurement and DC susceptibility measurement in Ca-doped crystal showed antiferromagnetic ordering at 2.8 K at ambient pressure. High-pressure AC susceptibility measurement on Ca-doped crystal showed a sharp superconducting transition at 2 K under 40 kbars. T_c onset reached a maximum value of 9.9 K at 54 kbars. The bulk superconductivity of the sample is confirmed by the high-pressure AC calorimetry with T_c max=9.4 K and T_N=5 K at 56 kbars.     

Growth of large-sized Ce:Y3Al5O12 (Ce:YAG) scintillation crystal by the temperature gradient technique (TGT)

In this work, Ce:YAG crystal with the size of ?4 in was successfully grown by the TGT method. The optical and scintillation properties of as-grown Ce:YAG crystals were investigated. Three obvious absorption bands at 223, 340 and 460 nm and two weak color-center absorption bands at 296 and 370 nm are observed in as-grown Ce:YAG crystal. Fluorescence with an emission peak at 398 nm is observed due to the color centers, and absorption bands of the color centers can be eliminated by annealing in O₂ or H₂ atmosphere at 1673 K for 24 h. Yellow-green fluorescence centered at 530 nm is found when the crystal was excited at 460 nm and the 530 nm excitation spectrum shows two peaks at 340 and 460 nm. X-ray fluorescence spectrum of as-grown crystal shows three emission peaks at 300, 360 and 530 nm. An average light output of 1360 phe/MeV and a single exponential decay with the decay time constant of 62.97 ns are found in as-grown Ce:YAG crystal.     

Growth and characterization of Nd:CLNGG crystal

The disordered laser crystal neodymium-doped calcium lithium niobium gallium garnet (Nd:CLNGG) was successfully grown by the Czochralski method. Its thermal properties, including the average linear thermal expansion coefficient, thermal diffusion coefficient, specific heat, and thermal conductivity were measured, and continuous-wave (CW) laser performance at 1.06 μm was demonstrated. The maximum power of 1.48 W was achieved with corresponding optical conversion efficiency of 12.4% and slope efficiency of 16.2%.     

Effects of Li replacement on the nucleation, crystallization and microstructure of Li2O-Al2O3-SiO2 glass

The Li replacement including the Li₂O replaced by other oxides and the expensive Li₂CO₃ replaced by low-cost spodumene mineral was studied to lower the product cost of (Li₂O-Al₂O₃-SiO₂, LAS) glass ceramic, and the effects of Li replacement on the nucleation, crystallization and microstructure of LAS glass were investigated by the differential thermal analysis (DTA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that Li₂O replacement increases the crystallization activation energy, lowers the crystal growth, and increases the nucleation and crystallization temperature by restraining the formation of crystalline phases. The Li₂CO₃ replacement decreases the crystallization activation energy, promotes the crystal growth, without affecting the nucleation, and lowers the crystallization temperature by adding some beneficial compositions with mixed alkali effect.     

Crystallization behavior of (GeS2)0.1(Sb2S3)0.9 glass

The crystal growth kinetics of antimony trisulfide in (GeS₂)_0.1(Sb₂S₃)_0.9 glass has been studied by microscopy and DSC. The linear crystal growth kinetics has been confirmed in the temperature range 492 ? T ? 515 K (E_G = 405 ± 7 kJ mol⁻¹). The applicability of standard growth models has been assessed. From the crystal growth rate corrected for viscosity plotted as a function of undercooling it has been found that the most probable mechanism is interface controlled 2D nucleated growth. The non-isothermal DSC data, corresponding to the bulk sample, can be described by the Johnson-Mehl-Avrami equation.     

A study of nonlinear optical properties in Bi2O3-WO3-TeO2 glasses

A series of bismuth tungsten tellurite glasses were prepared and their densities, linear refractive indices and transmission spectra were measured. The optical bandgaps E_opt and Urbach energies E_e of glasses were obtained from ultraviolet absorption edges. Both the optical gap (E_opt) and the band tail (E_e) are behaving oppositely. As the value of E_opt decreases with increasing WO₃ content, the degree of disorder increases which causes more defects or localized states resulting in deep localized in the bandgap with the tailing increased. Z-scan technique was carried out to investigate the third-order nonlinear optical properties of Bi₂O₃-WO₃-TeO₂ glasses. The third-order optical nonlinearity increases with decreasing the optical bandgap E_opt, since a increase of WO₃ content can provide the non-bridging oxygen ion content.     

Crystal growth and characterization of K2B4O11H8

Single crystals of K₂B₄O₁₁H₈, a non-centrosymmetric borate material, have been prepared by slow evaporation of water solution at room temperature. The crystals were colorless and transparent with smooth faces. The single-crystal X-ray diffraction analysis showed that K₂B₄O₁₁H₈ crystallized in the orthorhombic space group P2₁2₁2₁ with a=6.8556(6) Å, b=11.7787(12) Å, c=12.8949(14) Å, Z=4, R₁=0.0188, and wR₂=0.0464. The powder X-ray diffractometry (PXRD), infrared spectrum, transmittance spectrum, TG–DTA curves and second harmonic generation properties of title compound have been determined.     

Float zone growth of Dy:GdVO4 single crystals for potential use in solid-state yellow lasers

Single crystals of dysprosium-doped gadolinium orthovanadate (Dy:GdVO₄) were successfully grown by the floating zone method and their fluorescence properties were investigated. The as-grown crystals did not contain any macroscopic defects such as cracks and inclusions for any Dy-concentration of up to 4 at%. Every crystal showed optical homogeneity under observation with a polarizing microscope; that is, no low-angle grain boundaries and growth striations were detected. In the visible region, two distinct fluorescence bands were observed around 480 and 575 nm, corresponding to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions, respectively. The excitation spectrum for the emission of 573 nm indicates the possibility to use a commercially available laser diode of 450 nm as a pumping source for solid-state yellow laser.     

Growth and scintillation properties of the Na2W2O7 crystal

The growth and scintillation properties of the Na₂W₂O₇ crystal are reported. The solid reaction between Na₂CO₃ and WO₃ is used to synthesise the Na₂W₂O₇ material. The Na₂W₂O₇ single crystal has been grown by the Bridgman method. And the Na₂W₂O₇ single crystal with sizes 14×7×6 mm³ has been achieved. The transmission spectra, the Ultraviolet fluorescence spectra and the X-ray excited luminescence spectra of the Na₂W₂O₇ crystal are measured. The measurement results show that the Na₂W₂O₇ crystal is a promising intrinsic scintillator.     

Studies on the crystal growth,crystal structure,optical and thermal properties of an organic crystal: Benzophenone hydrazone

Single crystals of benzophenone hydrazone (BH) were successfully grown by slow evaporation method at constant temperature, 30 °C. The crystal structure of BH has been determined, and it belongs to the noncentrosymmetric space group P2₁. The grown crystal has been characterized by FT-IR). The optical transition and the lower cutoff wavelength of the BH have been identified by UV–vis–NIR studies. Thermo gravimetric analysis and differential thermal analysis have been carried out; the BH was found to be thermally stable up to 104 °C. Powder second harmonic generation (SHG) was investigated to explore its nonlinear optical (NLO) properties. The high SHG is due to one dimensional charge transfer between amine and phenyl group. Both the real ε_r and imaginary ε_i components of the dielectric constant have been calculated as functions of photon energy.     

Reduction of grown-in dislocation density in Ge Czochralski-grown from the B2O3-partially-covered melt

Germanium (Ge) single crystals with an extremely low density of grown-in dislocations were grown by the Czochralski (CZ) technique with boron oxide (B₂O₃) liquid. Because attachment of particles floating on the melt surface to a growing Ge crystal leads to generation of dislocations during the growth, partial covering of the Ge melt surface with B₂O₃ liquid was attempted. Such attachment of particles was drastically suppressed or the particles were caught by the introduction of B₂O₃ liquid, and a particle-free Ge melt was realized in the central region of the melt surface. Ge single crystals were successfully grown from such melt, the grown-in dislocation density being 0–1×10³ cm⁻², which was remarkably lower than that in Ge crystals grown by a conventional CZ technique. The contaminations by B and O atoms of the grown crystal detected by SIMS analysis were very low. These Ge crystals have the potential for application to be applied as high-quality, dislocation-free substrates of GaAs solar cells for various usages including in space.     

Thermo-optic properties of B2O3 doped Li2O-Al2O3-SiO2 glass-ceramics

Reduction in the temperature coefficient of the optical path length, dS/dT of Li₂O-Al₂O₃-SiO₂ glass-ceramics with near-zero thermal expansion coefficient was attempted using control of the temperature coefficient of electronic polarizability, ?, and the thermal expansion coefficient, α. The dS/dT value of 2.6 mol% B₂O₃-doped glass-ceramic was 12.5  × 10⁻⁶/°C, which was 0.9 ×  10⁻⁶/°C smaller than that of B₂O₃-free glass-ceramic. On the other hand, reduction in dS/dT through B₂O₃ doping was not confirmed in precursor glasses. Results showed that reduction in dS/dT of the glass-ceramic through B₂O₃ doping is caused by the reduction in ?. The reduction in ? from B₂O₃ doping was probably attributable to numerical reduction in non-bridging oxide ions with larger ? value by the concentration of boron ions in the residual glass phase. In addition, application of hydrostatic pressure during crystallization was effective to inhibit precipitation of β-spodumene solid solution, which thereby decreases dS/dT. The dS/dT value of B₂O₃-doped glass-ceramic crystallized under 196 MPa was 11.7 ×  10⁻⁶/°C. That value was slightly larger than that of silica glass. The α value of this glass-ceramic was smaller than that of silica glass.     

Floating zone growth and compositional inhomogeneity study of La0.75Y0.05Sr0.2MnO3 single crystals

Single crystals of La_0.75Y_0.05Sr_0.2 MnO₃ have been grown by the floating zone technique. The yttrium distribution in the radial and axial directions in the crystals was studied for different growth rates. The sample grown at high rate showed inhomogeneity in the yttrium content in the growth direction, while the sample grown at relatively low rate was homogeneous in the growth direction, but demonstrated compositional separation between the Y-poor central part and Y-enriched peripheral part in the perpendicular plane. The compositional separation led to magnetic inhomogeneity.     

Preparation of Sb2S3 nanomaterials with different morphologies via a refluxing approach

Single-crystalline antimony trisulfide (Sb₂S₃) nanomaterials with flower-like and rod-like morphologies were successfully synthesized under refluxing conditions by the reaction of antimony trichloride (SbCl₃) and thiourea with PEG400 and OP-10 as the surfactants. X-ray diffraction (XRD) indicates that the obtained sample is orthorhombic-phase Sb₂S₃ with calculated lattice parameters a=1.124 nm, b=1.134 nm and c=0.382 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images show that the flower-like Sb₂S₃ is 9–10 μm in size, which is composed of thin leaves with thickness of 0.05–0.2 μm, width of 0.8–2.2 μm and length of 2.5–3 μm, and the rod-like Sb₂S₃ is 45–360 nm in diameter and 0.7–4 μm in length, respectively. UV–Vis analysis indicates that the band gap of Sb₂S₃ nanorods is 1.52 eV, suitable for photovoltaic conversion. A possible mechanism of formation was proposed. The effects of reaction time and surfactants on the growth of nanomaterials with different morphologies were also investigated.     

Growth and characterization of calcium lithium tantalum gallium garnet single crystal

A new disordered garnet single crystal, calcium lithium tantalum gallium garnet (CLTGG) was grown by the Czochralski method. The lattice parameter of the crystal has been determined to be a=12.508±0.001 Å by X-ray powder diffraction (XRPD). The melting point of CLTGG was measured to be 1548 °C. The crystal possesses a wide transmission range from the ultraviolet to infrared, which is advantageous for applications as a laser host material. The refractive indices were also measured by the V-prism method.     

Characterization of a newly synthesized organic nonlinear optical crystal: Urea ninhydrin monohydrate

Urea ninhydrin monohydrate (UNM) was synthesized and grown for the first time from aqueous solution employing the slow evaporation method. Single crystal structure was determined by X-ray diffraction data and it reveals that the crystal belongs to centrosymmetric with space group of P2₁/c. The grown crystals were characterized by thermogravimetric analysis (TGA), differential thermal analysis (DTA) and UV–vis–NIR spectroscopy. Preliminary Z-scan measurement indicates that nonlinear refractive index of this crystal is −4.1×10⁻⁸ cm²/W. The etching study was performed to assess the growth pattern of the crystal. Dielectric response of the crystal was analyzed for different frequencies and temperatures.