Solubility of YBa2Cu3O7−δ and Nd1+xBa2−xCu3O7±δ in the BaO/CuO flux

The knowledge of the phase relations and solubilities in the Y–Ba–Cu–O and Nd–Ba–Cu–O systems are of fundamental importance for crystal growth and liquid-phase epitaxy of YBa₂Cu₃O_7−δ (YBCO) and Nd_1+xBa_2−xCu₃O_7±δ (NdBCO). The determination of the solubility curve of YBCO and NdBCO in a BaO/CuO flux containing 31 mol% BaO was done by observation of the formation and dissolution of crystals on the surface of the high-temperature solution. The heat of the solution of YBCO at 1000°C was found to be 34.7 kcal/mol, and for NdBCO at 1060°C, it was found to be 28.1 kcal/mol. The determination of the solubility curves requires special care, and the problems of the time-dependent shift of the solution composition due to the corrosion of the crucible is discussed. The scatter of the solubility data published by different authors could be due to the use of solutions with different Ba : Cu ratios, different determination methods, i.e. different crystallization mechanisms, different crucibles and starting chemicals.     

Growth and spectral properties of Nd:LaVO4 crystal

This paper reports the growth and spectral properties of 3.5 at% Nd³⁺:LaVO₄ crystal with diameter of 20×15 mm² which has been grown by the Czochralski method. The spectral parameters were calculated based on Judd–Ofelt theory. The intensity parameters Ω_λ are: Ω₂=2.102×10⁻²⁰ cm², Ω₄=3.871×10⁻²⁰ cm², Ω₆=3.235×10⁻²⁰ cm². The radiative lifetime τ_r is 209 μs and calculated fluorescence branch ratios are: β₁(0.88μm)=45.2, β₂(1.06μm)=46.7, β₃(1.34μm)=8.1. The measured fluorescence lifetime τ_f is 137 μm and the quantum efficiency η is 65.6%. The absorption band at 808 nm wavelength has an FWHM of 20 nm. The absorption and emission cross sections are 3×10⁻²⁰ and 6.13×10⁻²⁰ cm², respectively.     

Facets formation of pyramidal Si nanocrystals selectively grown on Si(0 0 1) windows in ultrathin SiO2 films

We have used in situ scanning tunneling microscopy (STM) to study the facet formation in the selective growth of pyramidal Si nanocrystals on Si(0 0 1) windows in ultrathin 0.3-nm-thick SiO₂ films. Broad (0 0 1) surfaces developed as the top of the crystals, and {1, 1, (2n+1)} (n=1–6) facets formed the sidewalls. As growth continued, the slope angle of sidewall facets increased, and {1, 1, 9} and {1, 1, (2m+1)} (0 <m < 4) facets often came to coexist on the sidewalls. On well-oriented Si(0 0 1) surfaces, layer-by-layer growth in the [0 0 1] direction was dominant. On vicinal Si(0 0 1) surfaces, lateral step growth took place in the initial stage, and the layer-by-layer growth was suppressed until after a large (0 0 1) surface had formed as the top of the crystal.     

Porous crystal structures obtained from directionally solidified eutectic precursors

Interconnecting cage-like porous structures of several halide compounds were prepared by the selective leaching of one eutectic phase method. The binary eutectic precursors were prepared by directional solidification using the Bridgman crystal growth technique. Porous NaMgF₃ (40% pore volume), CaF₂ (57% pore volume) and BaF₂ (43% pore volume) crystals were obtained after water leaching the NaF component of the directionally solidified NaF/NaMgF₃, NaF/CaF₂ and NaF/BaF₂ eutectics with the appropriate entangled microstructure. The growth conditions for eutectic-coupled growth and the morphology of the eutectics have been determined. In the coupled growth regime, the size of the eutectic phases “λ” is fairly uniform and varies with the eutectic growth rate “v” as λ²v=constant, which allows us to control the pore size within the 0.5–10 μm range. The simplicity and versatility of the eutectic growth also allows us to fabricate highly aligned porous structures at relatively high production rates.     

Physical chemistry of binary organic eutectic and monotectic alloys; 1,2,4,5-tetrachlorobenzene−β-naphthol and 1,2,4,5-tetramethylbenzene-succinonitrile systems

Phase diagrams of 1,2,4,5-tetrachlorobenzene–β-naphthol and 1,2,4,5-tetramethylbenzene–succinonitrile systems which are organic analogues of a nonmetal–nonmetal and a nonmetal–metal system, respectively, show the formation of a simple eutectic (melting point 103.7°C) with 0.71 mole fraction of β-naphthol in the former case and a monotectic (melting point 76.0°C) with 0.07 mole fraction of succinonitrile and a eutectic (melting point 52.5°C) with 0.97 mole fraction of succinonitrile in the latter case. The growth behaviour of the pure components, the eutectics and the monotectic studied by measuring the rate of movement of the solid–liquid interface in a capillary, suggests that the data obey the Hillig–Turnbull equation, v=u(ΔT)ⁿ, where v is the growth velocity, ΔT is the undercooling and u and n are constants depending on the nature of the materials involved. From the values of enthalpy of fusion determined by the DSC method using Mettler DSC-4000 system, entropy of fusion, interfacial energy, enthalpy of mixing and excess thermodynamic functions were calculated. The optical microphotographs of pure components and polyphase materials show their characteristic features.     

Growth of Tb3Ga5O12 fiber and bulk crystals using micro-pulling-down apparatus

A micro-pulling-down process, using Ir crucibles and RF heating, has been used to grow single-crystal fiber and bulk crystals of Tb₃Ga₅O₁₂ garnet (TGG). Single crystals ranging up to 450 mm in length have been produced. The crystals were 1–4 mm in diameter and were seeded-grown in the direction close to 1 1 1. The maximal crystal diameter achieved was 10 mm. Dependence of behavior of the solid–liquid interface on the growth parameters (temperature and pulling-rate) is discussed in detail.     

High-resolution XRD study of stress-modulated YBCO films with various thicknesses

High-quality epitaxial YBa₂Cu₃O_7−δ (YBCO) superconducting films with thicknesses between 0.2 and 2 μm were fabricated on (0 0 l) LaAlO₃ with direct-current sputtering method. The influence of film thickness on the structure and texture was investigated by X-ray diffraction conventional θ–2θ scan and high-resolution reciprocal space mapping (HR-RSM). The films grew with strictly c-axis epitaxial, and no a-axis-oriented growth was observed up to a thickness of 2 μm. Lattice parameters of the YBCO films with different thicknesses were extracted from symmetry and asymmetry HR-RSMs. The X-ray lattice parameter method was used to determine the residual stress in YBCO films by measuring the a-, b-, c-axis strains, respectively. The results showed that YBCO films within thinner than 1 μm were under compressive stress, which was relieved increasing of film thickness. However, beyond 1 μm in thickness, YBCO films exhibited a tensile stress. Based on the experimental analysis, the variety of residual stresses in the films is mainly attributed to oxygen vacancies with thickness of YBCO film increasing.     

Crystal growth of Ce: PrF3 by micro-pulling-down method

Micro-pulling-down (μ-PD) growth apparatus was modified for fluoride crystals. PrF₃ was grown with various concentrations of Ce³⁺ from 0–100%. The crystals were transparent and colorless (CeF₃) or greenish and 3 mm in diameter and 15–50 mm in length. Neither visible inclusions nor cracks were observed. Radioluminescence spectra and decay kinetics were measured for the sample set at room temperature. In comparison to the Czochralski or Bridgman method, the μ-PD method allows to produce single crystalline material in a faster thus more economic way. Once it is established for the fluoride crystals, it is an efficient tool for exploring the field of new functional fluorides.     

In vitro degradation studies of calcium phosphate glass ceramics prepared by controlled crystallization

Calcium phosphate glass ceramics with incorporation of small additions of two nucleating agents, MgO and K₂O were prepared in the metaphosphate and pyrophosphate region, using an appropriate two-step heat treatment of controlled crystallization defined by differential thermal analysis results. Identification and quantification of crystalline phases precipitated from the calcium phosphate glass were performed using X-ray diffraction and Rietveld analysis. The β-Ca₂P₂O₇ (β-DCP), KCa(PO₃)₃, β-Ca(PO₃)₂ and Ca₄P₆O₁₉ phases were detected in the glass ceramics. In order to evaluate the degradation of the glass ceramics prepared, degradation studies were carried out during 42 days in Tris-HCl solution at 37 °C, pH 7.4, using granules in the range of 355–415 μm. The materials presented a weight loss ranging up to 12%. The ions leached during the immersion mainly originated from the KCa(PO₃)₃ phase, probably due to the presence of K⁺ ion in the calcium metaphosphate, and the residual glassy phase. The structural changes at the surface of materials during degradation have been analyzed by Fourier transform infrared spectroscopy and X-ray diffraction. Results showed that significant surface changes occurred with immersion time, with the decrease of KCa(PO₃)₃, β-Ca₂P₂O₇ and β-Ca(PO₃)₂ phases occurring at different periods of immersion. This study has demonstrated an easy way to prepared calcium phosphate materials with specific calcium phosphate phases and crystallization, and therefore specific degradation rates.     

Growth and morphology of ruby crystals with unusual chromium concentration

Single crystals of ruby have been obtained from fluxed melts based on the systems Li₂O–MoO₃, Li₂O–WO₃, Na₂O–WO₃, 2PbO–3V₂O₅, PbO–V₂O₅–WO₃, PbF₂–Bi₂O₃ and Na₃AlF₆ by both the TSSG method and spontaneous crystallization at the temperatures 1330–900 °C. Al₂O₃ solubility has been measured for the flux composition of 2Bi₂O₃–5PbF₂ in the temperature range 1200–1000 °C and dissolution enthalpy has been defined as 29.4 KJ/Mol. The composition of grown crystals was studied by electron microprobe analysis. The synthetic ruby contains from 0.51 to 6.38 at% of chromium admixture depending on the crystal growth conditions. Experimental results on growth conditions, composition and morphology of grown crystals are presented for each flux and temperature interval.     

Al–O–Al and Si–O–Si sites in framework aluminosilicate glasses with Si/Al=1: quantification of framework disorder

We present for the first time, direct and clear experimental evidence of Al–O–Al and Si–O–Si linkages in charge-balanced aluminosilicate glasses with Si/Al=1, such as NaAlSiO₄ (nepheline) and LiAlSiO₄ (β-eucryptite) compositions using ¹⁷O triple quantum MAS (3QMAS) NMR and quantify the extent of disorder in framework cations (Si/Al). The degree of Al avoidance in NaAlSiO₄ glass is 0.942 at 1050 K, and in LiAlSiO₄ glass is 0.928 at 930 K (0.902 at 1050 K), which demonstrates the effect of cation field strength on the extent of disorder. In addition, we find a remarkable similarity between the ordering state of the liquid and that of the first, disequilibrium phase to crystallize.     

Formation of single-crystal γ-MnO2 nanowires at room temperature

In this study, single-crystal γ-MnO₂ nanowires have been successfully synthesized at room temperature in the absence of catalysts or templates, the diameter was found to be ca. 10–20 nm and the characteristic lengths up to several micrometers. The crystal phase of nanowires was confirmed by XRD and TEM measurements. Further, a dissolution– condensation–recrystallization process was proposed for the formation of nanowires under the room temperature condition.     

InP/InGaAlAs distributed Bragg reflectors grown by low-pressure metal organic chemical vapor deposition

Long-wavelength vertical cavity surface emitting lasers (VCSELs) are considered the best candidate for the future low-cost reliable light sources in fiber communications. However, the absence of high refractive index contrast in InP-lattice-matched materials impeded the development of 1.3–1.5 μm VCSELs. Although wafer fusions provided the alternative approaches to integrate the InP-based gain materials with the GaAs/AlAs materials for their inherent high refractive index contrast, the monolithic InP-based lattice-matched distributed Bragg reflectors (DBRs) are still highly attractive and desirable. In this report, we demonstrate InP/InGaAlAs DBRs with larger refractive index contrast than InP/InGaAsP and InAlAs/InGaAlAs DBRs. The switching between InP and InGaAlAs layers and growth rate control have been done by careful growth interruption technique and accurate in situ optical monitoring in low-pressure metal organic chemical vapor deposition. A 35 pairs 1.55 μm centered InP/InGaAlAs DBRs has the stopband of more than 100 nm and the highest reflectivity of more than 99%. A VCSEL structure incorporating 35 pairs InP/InGaAlAs DBR as the bottom mirror combined with a 2λ thick periodic gain cavity and 10 pairs SiO₂/TiO₂ top dielectric mirrors was fabricated. The VCSELs lased at 1.56 μm by optical pumping at room temperature with the threshold pumping power of 30 mW.     

Sol–gel synthesis and optical properties of size controlled Indium Arsenide nanocrystals embedded in silica glasses

III–V semiconductor Indium Arsenide (InAs) nanocrystals embedded in silica glasses was synthesized by combining the sol–gel process and heat treatment in H₂ gas. The size of InAs nanocrystals can be easily controlled via changing the In and As content in the starting materials and the heating temperature in a H₂ gas atmosphere. Absorption measurements indicate a blue shift in energy with a reduction on the In and As content in the SiO₂ gel glasses as a result of quantum confinement effects. A near-infrared photoluminescence with peak at 3.40 μm was observed at 6 K under 514.5 nm Ar⁺ laser excitation from InAs nanocrystals embedded in the silica gel glasses.     

Drastic effect of Mo on diamond nucleation in the system of MgCO3–CaCO3–graphite at 7.7 GPa

Drastic effect of additional Mo on diamond nucleation was observed in the system of Mc60Cc40 (mixture of 60 mol% MgCO₃ and 40 mol% CaCO₃)–graphite at 7.7 GPa, 1700 and 1800°C for 1 h. The decrease of temperature required for nucleation of diamond by addition of Mo is 200°C, compared with the temperature in the system of Mc60Cc40–graphite (Sato et al., Diamond Related Mater. 8 (1999) 1900). These results indicate that a lower energy barrier is expected for the nucleation in the Mc60Cc40–Mo–graphite system. Therefore, this nucleation process in the system of Mc60Cc40–graphite–Mo can be considered to be different from the spontaneous nucleation in the system of Mc60Cc40–graphite. Two probable models for nucleation can be suggested: (1) heterogeneous nucleation in which nucleation is affected by MoC that is formed by the reaction between the carbonate and Mo and (2) achievement of enough concentration of carbon for formation of nuclei by the reaction between the carbonate and Mo.     

A simple method to synthesize single-crystalline β-wollastonite nanowires

The single-crystalline β-wollastonite (β-CaSiO₃) nanowires were prepared via a simple hydrothermal method, in the absence of any template or surfactant using cheap and simple inorganic salts as raw materials. Xonotlite [Ca₆(Si₆O₁₇)(OH)₂] nanowires were first obtained after hydrothermal treatment at a lower temperature of 200 °C for 24 h, and after being calcinated at 800 °C for 2 h, xonotlite nanowires completely transformed into β-wollastonite nanowires and the wire-like structure was preserved. The synthesized β-wollastonite nanowires had a diameter of 10–30 nm, and a length up to tens of micrometers, and the single-crystalline monoclinic parawollastonite structured β-wollastonite was identified by XRD with the space group of P2₁/a and cell constants of a=15.42 Å, b=7.325 Å, c=7.069 Å and β=95.38°. A possible growth mechanism of β-wollastonite nanowires was also proposed. The advantages of this method for the nanowire synthesis lie in the high yield, low temperature and mild reaction conditions, which will allow large-scale production at low cost.     

Growth and spectroscopic properties of Er single doped and Er–Yb co-doped YAl3(BO3)4 crystals

Er³⁺-doped and Er³⁺–Yb³⁺ co-doped yttrium aluminum borate (YAB) single crystals have been grown by the top-seeded solution growth method using a new flux system, namely NaF–MoO₃–B₂O₃. The Er³⁺ concentrations were 1.3 mol% for both single doped and co-doped crystals and the Yb³⁺ concentration in the Er³⁺–Yb³⁺ co-doped crystal was 20.0 mol% in the raw materials. The distribution coefficients of Er³⁺ single doped and Er³⁺–Yb³⁺ co-doped crystals were measured. The polarized absorption and fluorescence spectra of Er³⁺–Yb³⁺ co-doped crystal were recorded and compared with those of Er³⁺ single doped crystal. The results demonstrate that Er³⁺–Yb³⁺ co-doped YAB crystal is a potential candidate for 1.55 μm laser materials.     

Charge transfer in CdTe at 200 and 300 K

Using a perfect single crystal sample of CdTe grown using PVT method, the electronic charge transfer in the II–VI compound semiconductor CdTe at 200 and 300 K has been evaluated using two different approaches: (1) by solving a quadratic equation involving the observed structure factors of h+k+l=4n+2 type reflections; and (2) by a graphical approach in which the observed and calculated atomic form factors are extrapolated to sinθ/λ=0, to determine the transferred charge. Precise X-ray structure factors collected using MoK radiation have been used for the analysis. The results obtained are reasonable and clearly indicate the ionicity by which charge is transferred from Cd to Te in CdTe.     

Erbium-activated silica xerogels: spectroscopic and optical properties

Silica-based sol–gel glasses activated by Er³⁺ ions are attractive materials for integrated optics (IO) devices such as frequency upconverters and optical amplifiers. Monolithic erbium-activated silica xerogels with erbium content ranging from 0 up to 40 000 ppm were prepared by the sol–gel technique. Samples were densified by thermal treatment in air at 950°C for 120 h. The densification degree and the relative content of hydroxyl groups were studied by Raman spectroscopy. Refractive indices were measured at 632.8 and 543.5 nm by a prism coupling technique. Green to blue and violet upconversion luminescence upon continuous-wave excitation at 514.5 nm was observed for all samples. Emission at 1.5 μm, characteristic of the ⁴I_13/2→⁴I_15/2 transition of Er³⁺ ions, was observed at room temperature for all samples upon continuous-wave excitation at 980 nm. For the 5000 Er/Si ppm-doped xerogel, a photoluminescence was observed and a lifetime of 8 ms for the metastable ⁴I_13/2 level was measured.     

The effect of MgO on the thermodynamics of the Fe/Fe-redox equilibrium and the incorporation of iron in soda-magnesia-aluminosilicate melts

Melts with the basic compositions 10Na₂O · 10MgO · xAl₂O₃ · (80−x)SiO₂ (x=0, 5, 10, 15 and 20), 10Na₂O · xMgO · 10Al₂O₃ · (80−x)SiO₂ (x=5, 10, 15 and 20) and xNa₂O · 10MgO · 10Al₂O₃ · (80−x)SiO₂ (x=5, 10 and 15) all doped with 0.25 mol% Fe₂O₃ were studied using square-wave voltammetry. The temperatures applied were in the range of 1000–1600 °C. The square-wave voltammograms recorded show peaks caused by the reduction of Fe³⁺ to Fe²⁺. The attributed peak potentials measured decreased linearly with decreasing temperatures. Increasing the MgO-concentration led to more negative peak potentials. Introducing alumina in the melt first resulted in less negative peak potentials. If the molar Al₂O₃-concentration is equal to that of Na₂O (=10 mol%) the peak potentials are least negative. Further increase of the Al₂O₃-concentration led to more negative peak potentials. The variation of the Na₂O-concentration led to a maximum in the peak potentials at an Na₂O-concentration of 10 mol%. An empirical formula which allows the calculation of standard potentials from the chemical composition is proposed. Furthermore, a structural explanation for the effect of the chemical composition is given. Especially, the incorporation of Al₂O₃ as AlO₄⁻-tetrahedra at [Al₂O₃] < [Na₂O] and as network modifier at larger concentrations was structurally explained by the similarities of Fe²⁺ and Mg²⁺, with respect to cation radii and metal–oxygen bond lengths.