Kinetics of crystal growth of mirabilite in aqueous supersaturated solutions

The crystallization of sodium sulfate decahydrate (Na₂SO₄·10H₂O, mirabilite) from supersaturated solutions was investigated using stable supersaturated solutions seeded with mirabilite seed crystals. The experiments were done in batch, stirred reactors in which the supersaturated solutions were prepared either by dissolution of sodium sulfate anhydrous at 32 °C followed by cooling to 18 or 20 °C or by mixing equal volumes of equimolar ammonium sulfate and sodium hydroxide solutions at 20 °C. Inoculation of the solutions supersaturated only with respect to mirabilite with seed crystals was accompanied with temperature increase of the thermostated solution. Despite the fact that crystal growth was initiated with seed crystals, the process started past the lapse of induction times inversely proportional to the solution supersaturation. The rates of crystal growth were measured both from the temperature rise and from the concentration–time profiles, which were linearly correlated. The measured crystal growth rates showed a parabolic dependence on supersaturation at low supersaturations. For higher values this dependence changed to linear, a behavior consistent with the BCF spiral crystal growth model. The morphology of the crystals growing at 20 °C showed typical prismatic habit, while at 18 °C when crystallized from cooled sodium sulfate solutions changes in the crystal habit to a leaf like morphology were observed.     

Growth Kinetics of Barium Sulphate in Suspension

The growth rate of barium sulphate seed crystals from stirred solutions was studied conductometrically at 25°C by a stopped-flow technique. The supersaturation ranged from 3 × 10⁻⁷ to 3 × 10⁻⁸ mol BaSO₄/cm³. The seed crystals were grown in the system during the initial (steady-state) period of the experiment. Crystal size distributions were determined by optical microscopy. The growth rate of barium sulphate under the conditions of the experiments can be expressed by a quadratic function of supersaturation. The results, which suggest an interface rate-controlling mechanism, are discussed with respect to published data.     

AlxGa1−xAs LPE growth

Al_xGa_1−xAs LPE growth was studied within the temperature range of 930–900°C with Al concentrations in solutions from 0.04 to 2.4 at.%. AlAs concentration in layers has been shown to grow with the cooling rate increase of solution. Interface and volume nucleation parameter dependence of K_i and K_v and formation time t_f on Al concentration in Ga solution have been found. Addition of Al to Ga solution increases critical values of As supersaturation (supercooling) and, as a result, increase in thickness of Al_xGa_1−xAs layers compared with GaAs layers have been determined in spite of As concentration lowering in Ga solution.     

Effect of electrical field on growth of gallium arsenide layers from vapour phase

The effect of electrical fields on the growth rate and morphology of gallium arsenide layers in the GaAs AsCl₃ H₂ system is investigated. The fields both parallel and perpendicular to the substrate surface are used. It is found that application of the parallel field results n increase of growth rate of (111)A face but does not change that of 2° (001). The morphology of layers grown in such a field is better than that grown without any. The application of perpendicular field results in decrease of growth rate for both crystallographic orientations, the layer morphology worthening. In both cases the effect is greater when the substrate has a negative potential. Possible mechanisms of the field influence on the growth rates of gallium arsenide layers are discussed such as: supersaturation decrease because of nucleation in vapour phase and the change in the rates of surface processes.     

High efficiency GaAs thin film solar cells by peeled film technology

p-GaAs/n-GaAs thin film concentrator solar cells were fabricated by Peeled Film Technology. This is the first paper that reports the concentration characteristics of thin film solar cells. The energy conversion efficiency of thin film solar cells at a concentration ratio of 109 is 9.4% and the output power density is 0.82 W/cm² · n-Ga_1?xAlxAs/p-GaAs heterojunction thin film solar cells were also fabricated. The initial heterojunction thin film solar cell with a Al mole fraction of 0.5 showed an efficiency of up to 13.5% (AM 1.5). It is proposed that Multi-Peeled Film Technology will give numerous GaAs thin films by selective etching of (GaAl)As/GaAs multi-layered structures.     

Effect of Supersaturation and Temperature on the Growth Morphology of Ammonium Oxalate Monohydrate Crystals Obtained from Aqueous Solutions

The experimental results of a study of the effect of supersaturation and temperature on the growth morphology of ammonium oxalate monohydrate [(NH₄)₂C₂O₄H₂O; AO] single crystals obtained from aqueous solutions at 30 and 40 °C and supersaturation up to 9% are presented. The observations are analysed in terms of theoretical morphology, growth models and attachment energy for growth units in steps of growing faces.     

Crystallization kinetics of MgSO4 · 7 H2O at higher ranges of the driving force

By means of batch crystallization technique the crystallization kinetics of MgSO₄ · 7 H₂O at 25 °C at higher ranges of the supersaturation from pure aqueous solutions was investigated. It was observed that the growth rate highly depends on the habit of crystals and on their ratio of length to width, respectively. This ratio is a function of the initial supersaturation of each crystal.     

Dislocation density in heteroepitaxial indium arsenide layers

In As layers have been grown by CVD on (111)B-oriented GaAs substrates. The dislocation density (N_D) distribution through the layer thickness has been studied. N_D is dependent on the mole fraction of AsCl₃ in the gaseous phase and, consequently, on the current carriers concentration. This results in the supposition that the decreasing of N_D in the layers after a “critical” thickness is due to the “pinning” of dislocations at impurity atoms which form stronger bonds with the host In or As atoms than the bond In–As, an effect which is known for bulk GaAs and InP crystals.     

Study of growth kinetics of ammonium oxalate monohydrate crystals from aqueous solutions

Experimental results of the dependence of linear growth rates of ammonium oxalate monohydrate [(NH₄)₂C₂O₄ · H₂O; AO] single crystals on solution supersaturation are presented. The AO crystals were grown by constant-temperature, constant-supersaturation method at 30 and 40 °C in the supersaturation range of 1–9%. It was observed that the supersaturation dependence of growth rates follows the parabolic growth law. Analysis of the supersaturation dependence of linear growth rates of AO crystals showed (1) that growth models involving surface diffusion and direct incorporation of growth units give kinetic parameters similar to those reported for other compounds grown from solutions, and (2) that the the BCF model of cooperating screw dislocations is also applicable. An inverse relationship between the estimated values of the length, L, of the line containing the dislocations and growth rate, R, and a direct relationship between L and interplanar distance, d_hkl, of the face {hkl} were found. Both these relationships are associated with the process of generation of screw dislocations in the growing layer.     

Crystallization kinetics of MgSO4 · 7 H2O in presence of tenside

The effect of sodium dodecyl sulfate (SDS) on crystallization kinetics and crystal habit of MgSO₄ · 7 H₂O from aqueous solutions at 25 °C was investigated in batch experiments. It highly depends on the supersaturation level. Both increasing supersaturation and rising concentration of the tenside promote the production of needle-like crystals but the influence of the driving force is much more pronounced. SDS increases the crystallization rate and the linear crystal growth rate in length direction of the crystals. To a high degree it also influences properties of the crystallizing solution such as surface tension and viscosity.     

Determination of Mass Transfer Coefficients for Crystal Growth of Nitrate Salts

In this paper, the crystal growth of sodium nitrate and potassium nitrate from aqueous solutions, in a perfectly stirred batch crystallizer, has been studied considering the effect of temperature, supersaturation degree, and the size of seed crystal growth rate. The mass transfer coefficients obtained correlated with Re, Sc and NL dimensionaless numbers. Supersaturation curve determination using a 0.5 mW He-Ne laser, connected to an automated data acquisition system, was the first stage of the study. The supersaturation and saturation curves were closely parallel with average DT value of 4.1 and 6.8 °C for KNO₃ and NaNO₃ respectively. For the growth kinetics order, unit values were found for both salts, with diffusion as a controlling stage.     

Kinetics of Mixed Crystal K2(SO4, CrO4) Growth from Aqueous Solution

The investigation of crystal growth kinetics and phase equilibria in the system K₂SO₄–K₂CrO₄–H₂O was carried out using the method for the determination of the saturation temperature and the growth rate by microscopic observation of the seed crystal behaviour. The kinetics of mixed crystal growth can be characterized by the expression V = 450.24σ^1,6,2, where σ is the value of effective supersaturation of the solution calculated by taking into account the specific features of the phase equilibria diagram. Use of this criterion allows the control of the rate of delta crystal growth from solutions of variable composition.     

Growth of corundum single crystals by the top-seeded solution growth technique (TSSG)

Single crystals of corundum were grown by the top-seeded solution growth technique from a cryolite, Na₃AlF₆, solvent. The relationship between the growth rate (mg/h) of a crystal and the temperature difference (= supersaturation) or the rotation rate of a seed crystal was investigated, and optimum growth conditions for obtaining single crystals with good quality are discussed.     

Study of the Growth Morphology of Ammonium Oxalate Monohydrate Crystals Obtained from Aqueous Solutions

The experimental results of the growth morphology of ammonium oxalate monohydrate [(NH₄)₂C₂O₄ · H₂O; AO] single crystals obtained from aqueous solutions at 30 and 40 °C and supersaturation up to 9% are presented. The observations are compared with the theoretical morphology predicted by PBC analysis and Braivais-Donnay-Harker law.     

Epitaxial Deposition of GaAs in the Ga(CH3)3?AsH3?H2 System (III) Heteroepitaxy on Isolating Substrates

Epitaxial growth of GaAs has been achieved on CaF₂, α-Al₂O₃ and spinel substrates. X-ray investigations showed well defined relations between layer perfection and the quality of substrate material. The formation of epitaxial layers in pyrolytic deposition processes is discussed in terms of supersaturation and its influence on nucleation and layer growth.     

Molecular beam epitaxy as a growth technique for achieving free-standing zinc-blende GaN and wurtzite AlxGa1-xN

Currently there is a high level of interest in the development of ultraviolet (UV) light sources for solid-state lighting, optical sensors, surface decontamination and water purification. III-V semiconductor UV LEDs are now successfully manufactured using the AlGaN material system; however, their efficiency is still low. The majority of UV LEDs require Al_xGa_1-xN layers with compositions in the mid-range between AlN and GaN. Because there is a significant difference in the lattice parameters of GaN and AlN, Al_xGa_1-xN substrates would be preferable to those of either GaN or AlN for many ultraviolet device applications. However, the growth of Al_xGa_1-xN bulk crystals by any standard bulk growth techniques has not been developed so far.There are very strong electric polarization fields inside the wurtzite (hexagonal) group III-nitride structures. The charge separation within quantum wells leads to a significant reduction in the efficiency of optoelectronic device structures. Therefore, the growth of non-polar and semi-polar group III-nitride structures has been the subject of considerable interest recently. A direct way to eliminate polarization effects is to use non-polar (001) zinc-blende (cubic) III-nitride layers. However, attempts to grow zinc-blende GaN bulk crystals by any standard bulk growth techniques were not successful.Molecular beam epitaxy (MBE) is normally regarded as an epitaxial technique for the growth of very thin layers with monolayer control of their thickness. In this study we have used plasma-assisted molecular beam epitaxy (PA-MBE) and have produced for the first time free-standing layers of zinc-blende GaN up to 100 μm in thickness and up to 3-inch in diameter. We have shown that our newly developed PA-MBE process for the growth of zinc-blende GaN layers can also be used to achieve free-standing wurtzite Al_xGa_1-xN wafers. Zinc-blende and wurtzite Al_xGa_1-xN polytypes can be grown on different orientations of GaAs substrates - (001) and (111)B respectively. We have subsequently removed the GaAs using a chemical etch in order to produce free-standing GaN and Al_xGa_1-xN wafers. At a thickness of ～30 µm, free-standing GaN and Al_xGa_1-xN wafers can easily be handled without cracking. Therefore, free-standing GaN and Al_xGa_1-xN wafers with thicknesses in the 30–100 μm range may be used as substrates for further growth of GaN and Al_xGa_1-xN-based structures and devices.We have compared different RF nitrogen plasma sources for the growth of thick nitride Al_xGa_1-xN films including a standard HD25 source from Oxford Applied Research and a novel high efficiency source from Riber. We have investigated a wide range of the growth rates from 0.2 to 3 µm/h. The use of highly efficient nitrogen RF plasma sources makes PA-MBE a potentially viable commercial process, since free-standing films can be achieved in a single day.Our results have demonstrated that MBE may be competitive with the other group III-nitrides bulk growth techniques in several important areas including production of free-standing zinc-blende (cubic) (Al)GaN and of free-standing wurtzite (hexagonal) AlGaN.     

Effect of Mn(II) ions on the growth of ammonium oxalate monohydrate crystals from aqueous solutions: I. Growth habit and surface morphology

The effect of concentration of Mn(II) ions on the growth habit and the surface micromorphology of different as‐grown faces of ammonium oxalate monohydrate (AO) single crystals grown from aqueous solutions was studied at a constant temperature of 30 °C and predefined supersaturations up to 20%. It was observed that the growth habit and the surface morphology of the crystals strongly depend on the supersaturation used for growth and the impurity concentration in the solution. The experimental results were analysed in terms of connected nets determined from different projections of the structure of AO crystals. Analysis of the observations revealed that: (1) the directions of connected nets corresponding to basic growth units composed of single (NH₄)₂C₂O₄ · H₂O molecules are in excellent agreement with the low‐index crystallographic directions of the orientations of growth layers, (2) all faces appearing in the growth morphology of AO crystals are F faces, and (3) the {001} face growing from pure aqueous solutions is essentially a kinetically rough face but the presence of Mn(II) impurity leads to their appearance in the morphology due to increase in the strength of bonds of the connected nets composing the surface graph.     

The dependence of surface morphology of GaSb- and AlxGa1–xSb epitaxial layers on the conditions of LPE growth

The present work shows the dependence of surface morphology of the GaSb and Al_xGa_1–xSb epitaxial layers on the conditions of LPE growth. It is found that for LPE growth at 500 °C a supersaturation of 5—10 °C and a cooling rate of 0.24—0.4°C/min for GaSb epitaxial layers and 0.8—1.2 °C/min for Al_xGa_1–xSb epitaxial layers is necessary to obtain a flat and smooth surface.     

Growth mechanism of crystals from aqueous solutions

Microscopic processes occurring on the surface of a growing crystal or a dissolving one were observed by microcinematography. The crystals under observation were grown either in a drop of solution by evaporation or in a constant-temperature microscope stage at a chosen supersaturation. Small (approx. 0.1 mm) and large (approx. 10 mm) crystals of NaCl, Pb(NO₃)₂, NaNO₃, CdI₂, KDP and ADP were studied. It is concluded qualitatively that the layers, in general polygonal, originating in one or several active centres, are formed on the crystal face, never at the corners or edges. – The average velocity of layer motion was studied quantitatively in dependence on their thickness and supersaturation. The layer motion at constant supersaturation considerably fluctuated. – Surface patterns created by moving layers agree in most cases with predictions of the dislocation theory. Two categories of steps were found on the surface: ”︁real”︁ macrosteps and shock waves. – The velocity of layer motion for most compounds lies within (1–10) · 10⁻⁴ cm · s⁻¹.     

Zum Wachstum von AIIIBV-Halbleitern aus nichtstöchiometrischen Schmelzen (II) Dotierung von GaAs und Ga1−xAlxAs mit Zink

Doping of GaAs and Ga_1−xAl_xAs with Zn in the LPE process was studied by a radioanalytical method. It is found that Zn diffuses from the Ga-(Al)-As-Zn-solution into the n-GaAs substrate before epitaxial growth starts. This “pre-diffusion” and the following diffusion of Zn out of the epitaxial layer into the substrate results in three regions with distinct Zn-graduation in the vicinity of the pn-junction. There are no striking differences for GaAs/GaAs and Ga_1−xAl_xAs/GaAs structures. The Zn concentration in GaAs epitaxial layers decreases exponentially from the substrate up to the layer surface. From this profile the temperature dependence of the Zn segregation coefficient is calculated. At 900°C a value k_eff = 5,2 · 10⁻² is found. The doping profile in Ga_1−xAl/As layers is more complex. It is influenced by the changings of temperature during the growth of the layer and by the nonuniform Aldistribution over the layer thickness.