Effect of Ampoule Rotation on Growth of InGaAs Ternary Bulk Crystals from Solution

In_xGa_1-xAs (x = 0.045) ternary bulk crystals were grown on GaAs seeds from an In–Ga–As solution by the temperature-difference method modified to rotate a growth ampoule. The effect of ampoule rotation on the profiles of the composition and the growth rate were investigated. The In compositional profiles were uniform irrespective of the ampoule rotation. On the other hand, the growth rate at the center of the crystal increased from 40 μm/h at 0 rpm to 55 μm/h at 100 rpm. The profile of growth rate changed from concave to convex toward the seed due to the ampoule rotation. Flow patterns and compositional profiles in the solution were simulated by solving four equations: Navier-Stokes, continuity, energy, and solute diffusion. The ampoule rotation enhanced the transportation of As component from the GaAs feed toward the seed at the central region in the solution. This led to the increase of the growth rate.     

The crystallisation of chromite-magnesiochromite spinels from a calcium magnesium aluminosilicate glass: Nucleation,crystal growth and final crystal sizes

The crystallisation of chromite-magnesiochromite spinels was studied from a calcium magnesium aluminosilicate glass (a simulated slag) containing 3 to 12 percent total iron oxides and 0.3 to 1.5 percent chromium(III) oxide, at temperatures from 1400° to 700 °C. – Spinel crystallisation occurred in glasses with 3–7 percent FeO and 0.7–1.1 percent Cr₂O₃. At temperatures 1100 °C and above, the nucleation was rapid and crystal numbers very high, at FeO contents above 3 percent and Cr₂O₃ contents above 0.7 percent; at 1056° and 1000 °C however, the crystal numbers reached some optimum values but then decreased as clinopyroxene crystals grew onto and enveloped the spinel microcrystals. In these glasses, the crystal lengths varied with growth time according to the relation, l_t = 2 k_g t^α = R_g1 t^α, where α = 0.7–1.0: this time dependence was a compromise between a relation for dendritic growth and one for facetted growth. The growth rates generally increased about five to seven times for 160 °C temperature rise: the energy of activation for the spinel crystal growth was then estimated as 180 ± 60 kJ mole⁻¹. – No spinel crystals were observed in glasses with more than 7 percent FeO content, only clinopyroxene crystals. Probably, these latter had nucleated rapidly and grown onto spinel microcrystals, while the spinel microcrystals were still of < 0.1 μm size.     

Differential thermal analysis studies on the crystallization of strontium tungstate melts. Variation of rate constants with crystallization temperatures and cooling rates

Kinetics of strontium tungstate crystallization from sodium tungstate melts were studied in platinum crucibles (by DTA) by continuous cooling from initial crystallization temperatures T₀ = 800° to 1000° to below the eutectic temperature at cooling rates R_T = 0.67° to 3.3° min⁻¹. Heterogeneous nuclei first formed slowly onto metal platinate particles within the solution during induction periods (t ); the main crystal growth then started after the development of some exces solute concentration (ΔC ) at the induction temperature (T ). The actual growth after t was diffusion rate-controlled. The diffusion rate-constants (k_Dt) for growth after the induction periods along the major axis were estimated; the increased with T₀ and R_T. These values were higher than those for diffusion-controlled crystal growth of strontium tungstate from sodium tungstate melts in alumina crucibles but much smaller than the real diffusion rate-constants (k_Dl)_real.     

The Precipitation of Barium Chromate with Slow Development of Supersaturation. Kinetics of the Crystal Growth

Slow barium chromate precipitation was studied in well-stirred solutions — final concentration 0.002 mole 1⁻¹ — at 20°C at mixing rates varying from 0.2 to 2 · 10⁶ mole 1⁻¹ sec⁻¹; the kinetics of the crystal growth process were studied by chemical analysis and by optical microscopy. The crystal growth started after induction periods; regular growth then took place on the nuclei formed during these periods. For the main growth, up to about seventy percent precipitation time, growth rates at any time depended on the (residual excess solute concentrations in solution)². Immediately after the induction periods, crystal lengths varied with growth time according to the relation, for the main growth, crystal lengths varied with growth time according to a more complex relation, where k_l is the rate constant for surface growth, R_c is the rate of development of metal salt concentration and K is a constant that depends on the number of precipitate crystals. After some growth time τ = τ^*, when l_τ = l_τ*, all fresh solute added to the solution was utilised immediately and was deposited onto the growing crystals; then, for the final thirty percent precipitation, crystal lengths varied with growth time according to the relation, .     

Kinetics of crystal growth of strontium tungstate from solutions in sodium tungstate melts by continuous cooling

The crystallisation kinetics of strontium tungstate from unstirred saturated solutions in sodium tungstate melts was studied by continuous cooling from initial crystallisation temperatures T₀ = 1000° to 800°C to room temperature at cooling rates R_T = 0.67° to 3.3°C min⁻¹. The main crystal growth was diffusion rate-controlled; the final crystal growth was rate-controlled by the development rate of excess solute concentration. The estimated diffusion rate constant (k_D) values increased with cooling rates and initial crystallisation temperatures. They are higher than the rate constants for diffusion-controlled growth of calcium tungstate from sodium tungstate melts, but very much smaller than those for strontium tungstate from lithium chloride melts.     

On crystal chemistry and morphology of extended organic molecules

The present paper is concerned with the morphology and crystal structure of extended organic compounds in the space group P 2₁/c. In the structures with molecules in general position (Z = 4) the longitudinal axis of all molecules run parallel to a (h0l)-plane. The molecule arrangements are based on four different structure types. The planes through the molecule axis contain a) 2₁-axis and symmetry centres (l = 2n), b) 2₁-axis or symmetry centres (l = 2n + 1) and c) respectively d) no symmetry element (l = 2n resp. 2n + 1). In the last two cases the net plane distances are to be halved. As in P 2₁/c the a-und c-axis are not set, one can confine oneself to the examination of the net planes (1 02), (2 02), (2 04), and (4 04). In the cases of a) and b), only certain morphological lattices appear, which distinguish themselves through additional translations in three-dimensional space resp. in the projections. In the cases of c) and d) there are also found morphological lattices which generate additional “morphological extinctions” (consequently possessing a higher symmetry than the generating space group), but which contain no translationally higher symmetry. (h0l)-faces, to which the molecule axis run parallel, appear with preference on crystals. As a rule the first two and the last two cases can be differentiated on account of the position of the (h0l)-faces in the Donnay-Harker series. Some examples will show that the morphological lattice can be preserved through Fourier transformation of crystal morphology.     

Geschwindigkeitsoszillationen beim Wachstum aus der Schmelze mit komplizierten Erstarrungsflächen

Basing on a formerly described model, the fluctuation of the growth velocity is computed for the growth of a crystal with rotating seed and a solidification interface, which has an maximum at r = r_c = 0. The distribution of the velocity and the pattern of the resulting striations is discussed.     

The precipitation of barium-, strontium- and calcium molybdates from aqueous solution: Kinetics of the crystal growth

The kinetics of precipitation of barium, strontium and calcium molybdates, from supersaturated aqueous solutions of initial solute concentrations C₀ = 0.0004 to 0.003 M, C₀ = 0.002 to 0.015 M and C₀ = 0.1 to 0.06 M, respectively, were studied at 25° by conductivity measurements and chemical analysis. Nucleation occurred during induction periods and continuous crystal growth then took place onto the crystallites formed during the induction periods. The growth rates at any time were expressed, in terms of degree of crystallisation, by the relation . The rate constants (kα) for the crystal growth of barium, strontium and calcium molybdates at 25° were 7700, 200, and 8.7 sec⁻¹ M⁻², respectively.     

Spectroscopic properties of a Tm3+:Bi2TeO5 single crystal

Single crystal of bismuth tellurite Bi₂TeO₅ (BTO) doped with trivalent thulium (Tm³⁺) was grown by the Czochralski method and investigated by spectroscopic techniques (absorption, emission). Absorption and emission of the Tm:BTO crystal collected in the VIS‐IR spectral range are presented. Spectroscopic features were investigated as a function of the excitation light polarisation (E//X, Y, and Z axis of optical indicatrix) and sample temperature. The oscillator strength of the ³H₆ → ³F₄ transition at 1.7 μm was determined by numerical integration of the X, Y and Z polarised absorption spectra. The obtained values are: P_X = 4.7 × 10⁻⁶, P_Y = 6.8 × 10⁻⁶ and P_Z = 5.9 × 10⁻⁶ that gives a mean value P_mean = 5.8 × 10⁻⁶. Emission was observed from the ¹G₄ and ³H₄ levels. The ³H₄ and ¹G₄ excited state dynamics was studied. Decay curves and time constants of luminescence were collected at 5 and 300 K and analysed. The ³F₄ → ³H₆ luminescence at around 1.8 μm was too weak to be acquired from the low concentrated sample. However, based on optical data it was possible to estimate the radiative probability A_rad of this transition and the ³F₄ radiative lifetime. The resultant values are: A_rad = 668 ± 0.4 s⁻¹ and τ_rad = 1.5 ms. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Lattice Vibration and Transmissivity in Nd-Doped Yttrium Orthovanadate Crystals

Neodymium-doped yttrium orthovanadate Nd_xY_1—xVO₄(NYV), with x = 0.025, crystallizes with a zircon-type structure in the tetragonal system conforming to the space group I4₁/amd. The lattice constants are a = b = 0.7123 ± 0.0005 and c = 0.6292 ± 0.0005 nm at room temperature. There are the four formulas per unit cell. The lattice-vibration and transmissivity spectra show that the NYV crystal is a good laser host crystal, which provides a suitable crystal field for the active ions. A strong absorption at 808 nm and the stimulated emission at 1.06 μm have provided the practical application as a laser crystal. Also, a strong fluorescent radiation at 0.408 μm, corresponding to a transition ⁴D_3/2 → ⁴I_13/2, is observed.     

Structural and electrical properties of CuGaSe2 thin films on GaAs substrates

CuGaSe₂ thin films with thicknesses in the range of 0.1 μm were deposited onto semiinsulating (111) A-oriented GaAs substrates by flash evaporation under controlled growth conditions. Epitaxial growth begins at a substrate temperature of T_sub = 835 K. Besides the chalcopyrite phase a hexagonal modification was observed in the range T_sub = 835 to 855 K. At T_sub ≧ 860 K the films have sphalerite structure. All epitaxial films were p-type conducting. Two acceptor levels with ionization energies of about 150 meV and 550 meV, respectively, were obtained from an analysis of electrical and photoluminescence measurements.     

The Crystallisation of Calcium Molybdate and Tungstate from Lithium Chloride Melts by Continuous Cooling. The Kinetics of Crystal Growth in Alumina Crucibles

The kinetics of crystallisation of calcium molybdate and tungstate from unstirred supersaturated solutions in lithium chloride melts — in alumina crucibles — was studied by continuous cooling from initial temperature T₀ = 800°C down to room temperature at cooling rates R_T = 20° to 200°C hr⁻¹. The solutions were analysed chemically and the crystals were examined by optical microscopy. Crystal growth started practically immediately after the onset of cooling: at first, the amount of material deposited onto crystals was far less than the amount of excess solute developed within the supersaturated solutions but crystallisation rates then increased as the crystal sizes increased. Then, after some time t* (at about seventy percent crystallisation), all excess solute was deposited onto growing crystals.     

Polymorphic single crystal ↔ single crystal transformations in Rb0.975Cs0.025NO3

The crystal growth morphology of modifications IV, III, II, and I during the IV ↔ III ↔ II ↔ I polymorphic transformations in Rb_0.975Cs_0.025NO₃ has been investigated by optical microscopy. The equilibrium temperatures between phases IV and III (T ₀ = 393 ± 0.5 K), III and II (T ₀ = 421 ± 0.5 K), and II and I (T ₀ = 497 ± 0.5 K) of the crystal studied have been determined. It is established that these transformations are of the single crystal ↔ single crystal type and occur with the formation and growth of new-crystal nuclei in crystalline matrices.     

The Precipitation of Strontium and Lead Sulphates from Aqueous Solution. Kinetics of the Crystal Growth

The precipitation of strontium and lead sulphates from well-stirred supersaturated aqueous solutions, of initial solute concentrations C₀ = 0.001 to 0.020 M and C₀ = 0.0002 to 0.003 M respectively, was studied at 20° and 40°C by chemical analysis and optical microscopy. Nucleation occurred during induction periods and continuous regular growth then took place onto the nuclei formed during these periods. Crystallisation was complete after 4 to 48 hr. The crystal growth was rate-controlled by the rate of deposition of metal salt ions onto the growing crystal surfaces. This rate (dC/dt), at any growth time, then depended on both the overall surface area (A_t) and on the residual excess solute concentration (ΔC_t) in solution according to the relation while the growth rate (dα/dt), expressed in terms of degree of crystallisation, was . The rate constants (k_α) for the crystal growth of strontium and lead sulphates at 20°C were 22 and 4200 sec⁻¹ M⁻² respectively — that is, greatest for the salt with least cation hydration –; these constants increased 4 to 6 times for 20°C temperature rise. The rate-determining process for the metal salt deposition was probably the ion dehydration.     

Epitaxial layers of CuGaTe2 on GaAs

CuGaTe₂ thin films with thicknesses in the range from 0.1 to 0.2 μm were deposited onto semi-insulating (111) A-oriented GaAs substrates by flash evaporation under controlled growth conditions. Epitaxial growth begins at a substrate temperature of T_sub = 695 K. In the range T_sub = 695 … 820 K the films have the chalcopyrite structure, at T_sub = 820 to 840 K a second phase was observed besides the chalcopyrite phase. At T_sub > 840 K the films become polycrystalline. All epitaxial films were p-type conducting and showed an increase of the hole concentration with rising substrate temperature. The measured mobilities indicate to the presence of a high concentration of neutral impurities or defects.     

CVD Processes with Direct and Indirect Incorporation

Indirect incorporation via adsorption, surface diffusion, and reaction at half crystal sites can be treated by the BCF theory of layer-by-layer growth in simple cases of CVD, even if there is strong surface coverage by adsorbed species. I that case, however, the parallel path by direct reactive incorporation of atoms into half crystal sites from the gas phase may play an important role. In any case, direct incorporation becomes the sole possibility for (normal) growth if the surface fraction y_k of half crystal sites (kinks) becomes I. The continuous transition from singular faces (y_k = 0) to half crystal faces (y_k = l) is covered by a simplified analytical expression and can be included into an overall circuit representation of stationary CVD processes which holds for in-situ doping, too. The model results in a good compromise between the conventional BCF treatment and Chernovs treatment of CVD surface processes.     

Structure of sodium perchlorate·diethylene glycol

The crystal structure of the 2:1 sodium perchlorate · diethylene glycol complex has been determined by single crystal X-ray diffraction. It crystallizes in space group P2₁2₁2 with a = 7.853(3), b = 7.900(2), c = 10.120(2) Å and Z = 2. Both the sodium ion and the diethylene glycol molecule are disordered, and were modeled with partial site occupancy factors. One sodium position is 7-coordinate and the other is 8-coordinate. The sodium perchlorate ions pack in layers parallel to [100] and [010], with the glycol molecules in channels between layers.     

LPE growth and characterization of InP/InGaAsP ridge-waveguide lasers at 1.3 μm-wavelength

This paper presents the fabrication and the lasing characteristics of 1.3 μm-wavelength ridge-waveguide laser. The epitaxial material used in this study was grown applying the step-cooling technique of liquid phase epitaxy (LPE). The growth conditions for InGaAsP layers lattice-matched to the (001) InP-substrate are reported for lattice compositions corresponding to photoluminescence peak wavelengths of 1.07, 1.14, and 1.31 μm. We have used a conventional multiple-bin sliding boat to grow the LPE layers and a second apparatus for achieving batches of melts of uniform compositions. In the LPE apparatus the various batch melts (In–Sn In–Zn; In–Ga–As of different composition) were saturated with phosphorus using the seed dissolution technique. The epitaxial layers were grown by a single phase technique at a constant temperature. This LPE growth technique is useful for the fabrication of double-heterostructure wafers with an uniform alloy composition and a well-defined layer thickness. Using these epitaxial materials, metal-clad ridge-waveguide (MCRW) lasers have been prepared with stripe widths of 3.5 μm. CW threshold currents of 18 mA at room temperature are achieved for 200 μm long cavities. These lasers have T₀ values ranging from 50 to 70 K and well linear L-I-characteristics.     

On voids in InxGa1−xSb crystals grown by an ultrasonic- vibration-introduced Czochralski method

The shape and size of voids, and the grown region surrounding a large void were investigated in In_xGa_1–xSb crystals, which were pulled under the introduction of ultrasonic vibrations into the source melt by using a modified Czochralski apparatus. The presence of voids in crystals resulted from (1) atmosphere gas was confined beneath the growth interface of a seed crystal during the seeding procedure, and (2) many bubbles–generated by the cavitation effect due to ultrasonic vibrations–were caught in the growing crystal. Voids were circular, deformed trapezoid, and complex in shape, and were in a range of 20 μm to 3 mm in size. Even in case of a void with the diameter as large as 2 mm, the grown region surrounding it was in the single crystalline state. In this interesting region, the microscopic variation of In concentration and the abrupt change of growth rate were observed.     

Growth and structure of epitaxial Pb1 − x Mn x Se(Ga) films

The growth and structure of Pb_{1 ? x} Mn _x Se (Ga) (N_Ga = 0.8 at %) films with thicknesses of 0.3–0.5 μm, grown on single-crystal PbSe_{1 ? x} S _x (100) substrates by molecular-beam epitaxy, have been studied. It is established that films grow in a face-centered cubic lattice with the (100) orientation, reproducing the substrate orientation. The optimal conditions for obtaining photosensitive epitaxial films with perfect crystal structure are determined (W _1/2 = 70–80″).