Synthesis, crystal structure, Cu doped EPR, thermal and voltammetric studies of [Ni(isonicotinamide)2(H2O)4]·(sac)2 single crystal

The single crystal of [Ni(ina)₂(H₂O)₄]·(sac)₂, (NINS), (ina is isonicotinamide and sac is saccharinate) complex has been prepared and its structural, spectroscopic and thermal properties have been determined. The title complex crystallizes in monoclinic system with space group P2₁/c, Z=2. The octahedral Ni(II) ion, which rides on a crystallographic centre of symmetry, is coordinated by two monodentate ina ligands through the ring nitrogen and four aqua ligands to form discrete [Ni(ina)₂(H₂O)₄] unit, which captures two saccharinate ions in up and down positions, each through intermolecular hydrogen bands. The magnetic environment of copper(II) doped NINS crystal has also been identified by electron paramagnetic resonance (EPR) technique. The g and A values of Cu²⁺ doped NINS single crystal were calculated from the EPR spectra recorded in three mutually perpendicular planes. These values indicated that the paramagnetic centre has a rhombic symmetry with the Cu²⁺ ion having distorted octahedral environment. The complex exhibits only metal centred electroactivity in the potential range of −2.00, 1.25 V versus Ag/AgCl reference electrode.     

Hydrothermal synthesis of Sb doped and (Sb, Eu) co-doped YBO3 with nearly white light luminescence

Sb³⁺-doped, Eu³⁺-doped and (Sb³⁺, Eu³⁺) co-doped YBO₃ crystals have been synthesized using Y₂O₃, B₂O₃, SbCl₃ and Eu₂O₃ as raw materials through a hydrothermal method. Phase-pure YBO₃ crystal with hexagonal flake shape has been synthesized at 473 K for 3 days. The photoluminescent property of YBO₃ with different activators were investigated using luminescent spectrometer at room temperature. The color of the (Sb³⁺, Eu³⁺) co-doped YBO₃ crystal could be controlled from blue to red by changing the Sb³⁺/Eu³⁺ ratio in the initial reactants. The nearly white emission could be obtained through changing the Sb³⁺/Eu³⁺ ratio in reaction.     

Effect of Sr substitution on photoluminescent properties of BaAl2O4:Eu, Dy

Phosphor material BaAl₂O₄:Eu²⁺, Dy³⁺ with varying compositions of Sr substitution were prepared by the solid-state synthesis method. The phosphor compositions were characterized for their phase and crystallinity by XRD, SEM and TEM. Photoluminescence (PL) properties were investigated measuring PL and decay time for varying Ba/Sr compositions. The PL results show the blue shift in the luminescence properties in Sr substituted BaAl₂O₄:Eu²⁺, Dy³⁺ compared to parent BaAl₂O₄:Eu²⁺, Dy³⁺. It is probably due to the influence of 5d electron states of Eu²⁺ in the crystal field because of atomic size variation causing crystal defects. Dy³⁺ ion doping in the phosphor generates deep traps, which results in long afterglow phosphorescence.     

Power factor enhancement in Pr-substituted alloys prepared by high-pressure sintering

Bi₈₅Sb_15−xPr_x (x=0,1,2,3) alloys with partial substitution of Pr for Sb were synthesized by mechanical alloying followed by high-pressure sintering. The crystal structure was characterized by X-ray diffraction. The electrical conductivity and Seebeck coefficient were measured in the temperature range of 80–300 K. The results show that the electrical conductivity and Seebeck coefficient of Pr-substituted samples are both larger than those of the reference sample, Bi₈₅Sb₁₅, in the whole measurement temperature range. The power factor of Bi₈₅Sb₁₃Pr₂ reaches a maximum value of 3.83×10⁻³ W K⁻² m⁻¹ at 235 K, which is about four times larger than that of the reference sample, Bi₈₅Sb₁₅, at the same temperature.     

Growth of α-Al2O3:C crystal with highly sensitive optically stimulated luminescence

In this work, an α-Al₂O₃:C crystal was directly grown by the temperature gradient technique (TGT) using Al₂O₃ and graphite powders as the raw materials. The optical, optically stimulated luminescence (OSL) properties and dosimetric characteristics of as-grown crystal were investigated. As-grown α-Al₂O₃:C crystal shows strong absorption band at 205, 230 and 256 nm. Three-dimensional thermoluminescence (TL) emission spectrum of the crystal shows a single emission peak at ∼415 nm. The OSL decay curve can be fitted to two exponentials, the faster component and the slower component. The OSL response of the crystal shows a linear-sublinear-saturation characteristic. As-grown α-Al₂O₃:C crystal shows excellent linearity in the dose range from 5×10⁻⁶ to 50 Gy. For doses higher than the saturation dose (100 Gy), the OSL sensitivity decreases as the dose increases.     

Deposition of duplex Al2O3/aluminum coatings on steel using a combined technique of arc spraying and plasma electrolytic oxidation

Plasma electrolytic oxidation (PEO) is a cost-effective technique that can be used to prepare ceramic coatings on metals such as Ti, Al, Mg, Nb, etc., and their alloys, but this promising technique cannot be used to modify the surface properties of steels, which are the most widely used materials in engineering. In order to prepare metallurgically bonded ceramic coatings on steels, a combined technique of arc spraying and plasma electrolytic oxidation (PEO) was adopted. In this work, metallurgically bonded ceramic coatings on steels were obtained using this method. We firstly prepared aluminum coatings on steels by arc spraying, and then obtained the metallurgically bonded ceramic coatings on aluminum coatings by PEO. The characteristics of duplex coatings were analyzed by X-ray diffractometer (XRD) and scanning electron microscopy (SEM). The corrosion and wear resistance of the ceramic coatings were also studied. The results show that, duplex Al₂O₃/aluminum coatings have been deposited on steel substrate after the combined treatment. The ceramic coatings are mainly composed of α-Al₂O₃, γ-Al₂O₃, θ-Al₂O₃ and some amorphous phase. The duplex coatings show favorable corrosion and wear resistance properties. The investigations indicate that the combination of arc spraying and plasma electrolytic oxidation proves a promising technique for surface modification of steels for protective purposes.     

Spectroscopic features of erbium-doped CaM2O6 (M=Nb, Ta) single crystal fibers grown by the laser-heated pedestal growth technique

Erbium-doped single crystal fibers, with low phonon energy and fairly high absorption and emission cross sections are interesting laser active media, for compact, near-infrared and/or upconversion lasers. In this work, high optical quality Er³⁺-doped CaNb₂O₆ and CaTa₂O₆ single crystal fibers were successfully grown by the versatile laser-heated pedestal growth technique, and characterized from the structural and spectroscopic points of view. The results indicate that these crystal fiber compositions, which had not been explored so far, offer potential applications, not only as laser active media, but also in other optical devices.     

Laser frequency stabilization at 1.5 microns using ultranarrow inhomogeneous absorption profiles in Er:LiYF4

Single-frequency diode lasers have been frequency stabilized to 1.5 kHz Allan deviation over 0.05-50 s integration times, with laser frequency drift reduced to less than 1.4 kHz/min, using the frequency reference provided by an ultranarrow inhomogeneously broadened Er³⁺:⁴I_15/2→⁴I_13/2 optical absorption transition at a vacuum wavelength of 1530.40 nm in a low-strain LiYF₄ crystal. The 130 MHz full-width at half-maximum (FWHM) inhomogeneous line width of this reference transition is the narrowest reported for a solid at 1.5 μm. Strain-induced inhomogeneous broadening was reduced by using the single isotope ⁷Li and by the very similar radii of Er³⁺ and the Y³⁺ ions for which it substitutes. To show the practicability of cryogen-free cooling, this laser stability was obtained with the reference crystal at 5 K; moreover, this performance did not require vibrational isolation of either the laser or crystal frequency reference. Stabilization is feasible up to T=25 K where the Er³⁺ absorption thermally broadens to ∼500 MHz. This stabilized laser system provides a tool for interferometry, high-resolution spectroscopy, real-time optical signal processing based on spatial spectral holography and accumulated photon echoes, secondary frequency standards, and other applications such as quantum information science requiring narrow-band light sources or coherent detection.     

A comparative study on Zn0.8Cd0.2O films deposited on different substrates

Highly (0 0 2)-oriented Zn_0.8Cd_0.2O crystal films were prepared on different substrates, namely, glass, Si(1 1 1) and α-Al₂O₃(0 0 1) wafers by the dc reactive magnetron sputtering technique. The Zn_0.8Cd_0.2O/α-Al₂O₃ film has the best crystal quality with a FWHM of (0 0 2) peak of 0.3700°, an average grain size of about 200 nm and a root-mean-square surface roughness of about 70 nm; yet the Zn_0.8Cd_0.2O/glass holds the worst crystal quality with a much larger FWHM of 0.6281°. SIMS depth profile shows that the Zn and O compositions change little along the film depth direction; the Cd incorporation also almost holds the line towards the top surface other than an accumulation at the interface between the film and the substrate. The Cd content in the film is nearly consistent with that in target.     

Photodissociation spectroscopy of the chromium trimer ion

The electronic and geometric structures and photodissociation dynamics of the chromium trimer ion, Cr₃ ⁺, were investigated by photodissociation spectroscopy in the photon-energy range from 1.32 to 5.52 eV. The branching fractions of the product ions, Cr⁺ and Cr₂ ⁺, exhibit stepwise changes at the threshold energies for dissociation into Cr⁺+Cr₂, Cr+Cr₂ ⁺, Cr⁺+2Cr, and Cr^*+Cr₂ ⁺. It is noted that Cr₂ ⁺ is produced even above the threshold for atomization; the excess energy is redistributed to produce a fragment atom, Cr^*, in an excited state. The photodissociation action spectrum is well explained by a mixture of simulated spectra for two nearly-degenerate structural isomers identified by density functional calculations: those having a metastable C_2v structure and the most stable structure slightly distorted from the C_2v one. The barrier height between the two isomers which is lower than the zero-point energy suggests that Cr₃ ⁺ has an intrinsically floppy structure.     

Orientation dependence of electrical properties of 0.96Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-0.04BaTiO<Subscript>3</Subscript> lead-free piezoelectric single crystal

In this paper, a single crystal of 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ with dimensions of Φ 30×10 mm was grown by the top-seeded-solution growth method. X-ray powder diffraction results show that the as-grown crystal possesses the rhombohedral perovskite-type structure. The dielectric, piezoelectric and electrical conductivity properties were systematically investigated with 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples. The room-temperature dielectric constants for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples are found to be 650, 740 and 400 at 1 kHz. The (T _m, ε _m) values of the dielectric temperature spectra are almost independent of the crystal orientations; they are (306°C, 3718), (305°C, 3613) and (307°C, 3600) at 1 kHz for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal. The optimum poling conditions were obtained by investigating the piezoelectric constants d ₃₃ as a function of poling temperature and poling electric field. For the 〈001〉 and 〈110〉 crystal samples, the maximum d ₃₃ values of 146 and 117 pC/N are obtained when a poling electric field of 3.5 kV/mm and a poling temperature of 80°C were applied during the poling process. The as-grown 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ crystal possesses a relatively large dc electrical conductivity, especially at higher temperature, having a value of 1.98×10⁻¹¹ Ω⁻¹⋅m⁻¹ and 3.95×10⁻⁹ Ω⁻¹⋅m⁻¹ at 25°C and 150°C for the 〈001〉 oriented crystal sample.     

Temperature dependence of thermal property for lead nitrate crystal

Thermal property was measured in a lead nitrate crystal, Pb(NO₃)₂, at temperatures from 90 to 340 K by use of ac calorimetry technique. The heat capacity derived from the measurements showed temperature dependence with thermal hysteresis, in the temperature region from 240 to 300 K. The anomaly of the heat capacity was found in the vicinity of 275.22 K. The broad temperature variation in the heat capacity was observed in the region from 235 to 260 K.     

Experimental and theoretical studies on bis(glycine) lithium nitrate (BGLiN): A physico-chemical approach

Good quality and bulk size single crystal (size: 20×13×8 mm³) of bis(glycine) lithium nitrate (BGLiN) was grown by a slow evaporation solution technique from the aqueous solutions at constant temperature i.e. 27 °C using synthesized materials. Crystal system and lattice parameters were determined by single crystals as well as powder X-ray diffraction analysis. The lattice parameters of the titled compound are a=10.0223 Å, b=5.0343 Å, c=17.0510 Å, and V=860.312 Å³ and it crystallized in an orthorhombic system with space group Pca2₁ obtained by single crystal XRD. Elemental composition was confirmed by energy dispersive X-ray spectroscopic analysis. Optical absorption spectrum was recorded and various optical parameters such as optical transmission (~60%), and optical band gap (4.998 eV) were calculated. Photoluminescence study shows that the grown crystal is free from major defects. Crystalline perfection of the grown crystal was assessed and found good. Ground state optimized geometry has been obtained by using DFT with 6-31G(d,p) basis set. HOMO and LUMO energy gap was found to be 6.01 eV and dipole moment was 1.65 D.     

Formation and crystal structure of metallic inclusions in a HPHT as-grown diamond single crystal

One of the most important characteristics associated with crystal growth technology is the entrapment of inclusions by the growing crystal. Diamond single crystals prepared under high temperature-high pressure (HPHT) usually contain metallic inclusions. In the present paper, metallic inclusions in a diamond grown from a Fe-Ni-C system using the HPHT method have been, for the first time, systematically examined by transmission electron microscopy (TEM). Energy dispersive X-ray spectrometry (EDS) , combined with selected area electron diffraction (SAD) patterns, has been used to identify the chemical composition and crystal structure of the metallic inclusions. The metallic inclusions were found to be composed mainly of cubic γ-(FeNi), face-centered cubic (FeNi)₂₃C₆, ortho-rhombic Fe₃C and hexagonal Ni₃C, which may have been formed through the entrapment of molten catalyst by the growth front or through reaction of the trapped melt with contaminants in the diamond. Received: 19 June 2000 / Accepted: 21 June 2000 / Published online: 16 August 2000     

AgGaSe2 : A highly photoconductive material

High resistivity single crystals of AgGaSe₂ were grown by the horizontal Bridgman technique. The near band edge photoconductivity of the grown crystal at room temperature was found to be up to 2×10⁴ times higher than the dark conductivity, under the illumination of 10⁻³ W/cm². The photoconductivity spectrum consists primarily of three peaks, which are attributed to the transitions from Γ₇(A), Γ₆(B) and Γ₇(C) states of valence band to the conduction band Γ₆. The crystal field splitting and the spin-orbit splitting were determined from these peak energy positions of the photoconductivity spectrum.     

Pressure induced phase transition of nanocrystalline and bulk maghemite (γ-Fe2O3) to hematite (α-Fe2O3)

Phase transition and bulk moduli of bulk and nanocrystalline γ-Fe₂O₃ were studied using synchrotron X-ray diffraction under high pressure. Contrary to most other nanomaterials, nanocrystalline γ-Fe₂O₃ begins to transform into α-Fe₂O₃ at the same pressure as bulk γ-Fe₂O₃, which is caused by a special structure of γ-Fe₂O₃, in which there exist vacancies of crystal. It is believed that phase transition starts from a certain site of vacancy because of the stress concentration at vacancy sites. Compared to bulk material, nanocrystalline γ-Fe₂O₃ has a larger bulk modulus, which is ascribed to the large ratio of surface to volume.     

First Z-scan n2 measurements on crystal hosts for ultraviolet laser systems

We report the results of the first measurements of the non-linear Kerr refractive index, n₂, for LiBaF₃ and LiLuF₄ crystal hosts, known as prospective UV-emitting tunable laser media when doped with Ce³⁺ ions. These n₂ values (2.7×10^-16 and 1.5×10^-16 cm²/W at 532 nm, respectively), obtained using the well-established Z-scan technique, are important for the characterization of new optical materials particularly in relation to their potential ultrafast applications. Received: 6 June 2000 / Published online: 5 October 2000     

Crystal structure and ferromagnetism of (n-C3H7)4N[CoFe(dto)3] (dto=C2O2S2)

Recently, we have discovered a new type of first order phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto=C₂O₂S₂), where the charge transfer transition between Fe^II and Fe^III occurs reversibly. In order to elucidate the origin of this peculiar first order phase transition. Detailed information about the crystal structure is indispensable. We have synthesized the single crystal of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃] whose crystal structure is isomorphous to that of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃], and determined its detailed crystal structure. Crystal data: space group P6₃, a=b=10.044(2) Å, c=15.960(6) Å, α=β=90°, γ=120°, Z=2 (C₁₈H₂₈NS₆O₆FeCo). In this complex, we found a ferromagnetic transition at T_c=3.5 K. Moreover, on the basis of the crystal data of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃], we determined the crystal structure of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] by simulation of powder X-ray diffraction results.     

The optimum configuration for the third-harmonic generation of 1.064 μm in a YCOB crystal

A method of determining the spatial configuration of a YCa₄O(BO₃)₃ (YCOB) crystal is introduced. The type-I phase-matching points for the sum-frequency of 1.064 μm and 0.532 μm, as well as the conversion efficiency for YCOB samples cut in different directions, have been measured. When the input intensity is 0.76 GW/cm², the third-harmonic generation (THG) conversion efficiency for the (106°, 77.2°)-cut YCOB crystal reaches 26.2%, which is the highest that we know so far. Both the calculations and the experiments show that the optimum THG configuration for a YCOB crystal is near (106°, 77.2°), or other equivalent directions in space. Received: 11 September 2000 / Revised version: 25 January 2001 / Published online: 27 April 2001     

Synthesis and crystal structure of [3,5-(CH3)2C6H3NH3]4P4O12·3H2O

Chemical preparation and crystal structure are given for a new cyclotetraphosphate: [3,5-(CH₃)₂C₆H₃NH₃]₄P₄O₁₂·3H₂O. This compound is triclinic P with the following unit-cell parameters: a=8.298(3), b=8.299(3), c=17.242(7)Å, α=97.13(3), β=102.72(3), γ=64.55(3)°, Z=1 and V=1045.2(8)ų. The crystal structure has been solved and refined to R=0.040 using 6086 independent reflections. The atomic arrangement can be described as layers organization. Layers built by P₄O₁₂ ring anions, ammonium groups and water molecules parallel to the plan (001), between which the organic groups are located. Characterization by X-ray diffraction, IR absorption, and thermal analysis are described.