Study of the evaporation mechanism in silicon carbide crystals growth from vapour phase

Investigation of the thermal etching (evaporation) of the source material in the process of silicon carbide crystal growth from the vapour phase by the sublimation method has been carried out. It has been established that silicon carbide etching in the temperature interval (2200–2600) °C takes place with the formation of whiskers of evaporation. The mechanism of their formation has been examined and the character of the whisker distribution in the charge of the source silicon carbide has been studied.     

Understanding the growth mechanism of CuI crystals during gel growth experiments

Cuprous iodide crystals have been grown with decomplexation method in silica gel. Various crystal morphologies, such as polycrystalline aggregate, skeletal, dendrite, hopper crystals and regular tetrahedron crystals, were observed in different growth regions with an optical microscope. Their surfaces were photographed using a binocular metallographic microscope and the results were explained with the crystal growth mechanism which was determined by supersaturation. These observations support the general hypothesis that the concentration of reactant affects the relative growth rate by controlling the nucleation and diffusion. The mutual influence of the crystals grown in different regions was also discussed. Additionally, the suitable condition for getting regular tetrahedron crystals or large hopper crystals was obtained by changing the concentration of CuI·HI complex in the later period of crystal growth. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The inhibitory growth mechanism of saccharides on the growth of ice crystals from aqueous solutions

The inhibitory growth mechanism controlling the growth of ice crystals due to the presence of saccharides, as in plant cells, was experimentally studied at low temperature. As a result, it was found that the growth rate of ice crystals in saccharide solutions depended on the type and concentration of the saccharides. The experimental facts can be explained by the concept that giant hydrated clusters of saccharides create the framework that causes a resistance to the volume diffusion of water molecules.     

Investigations of the growth mechanism and morphology of silver crystals grown electrolytically in gels

Gel medium has been used for the electrolytic growth of silver dendrites and single crystals of a variety of morphological features and forms. Microtopographic studies of the crystals have been carried out using optical and scanning electron microscopes. Some unusual growth surface morphologies have been observed. The surfaces of some of the crystals have a high degree of perfection. Sufficient experimental evidences are obtained for the striated growth of crystals and twin plane re-entrant edge (TPRE] mechanism of growth. The formation of tertiary three-dimensional (T3D) dendrites and dendrites with obliquely forward and backward branchings at different stages of growth have been investigated.     

On the growth mechanism of polycrystalline snow crystals with a specific grain boundary

Observed frequently in a natural snowfall at temperatures lower than -20°C, the crossed-plate crystal is an assemblage of two to four thin basal plates, each plate extending along a CSL grain boundary with a relation of 70.3°/[11$\text{2}$0]. A possible growth mechanism is proposed to account for the characteristics growth in the direction of the axis [11$\text{2}$0]. If two or more grain boundary dislocation (GBD) structures are contained at a CSL grain boundary, growth layers will overflow alternately on the (10$\text{1}$0) planes of each component crystal at the intersection of these planes. Thus, the distinctive structure of the CSL grain boundary, like the feature of a screw dislocation step, will induce the preferential growth in this direction.     

On the mechanism of trace-element uptake during the hydrothermal growth of sulfide mineral crystals

The stable species of cadmium and mercury are formed in iron and lead sulfides at elevated temperatures and pressures under hydrothermal conditions. Their formation proceeds through different mechanisms. The most general mechanism involves the uptake of trace elements in the form of structural species due to isomorphous exchange. The results obtained for cadmium in pyrrhotite indicate that structural defects substantially affect the incorporation of impurities into the crystal structure. It is found that trace elements are accumulated on the surface in the absence of defects and are incorporated into the crystal bulk in the form of structural impurities in the presence of defects. Moreover, at elevated temperatures and pressures, trace elements can form their own (surface nonautonomous) phases. These phases are formed not only at trace-element concentrations close to saturation (Cd in Fe_1.0S) but also under conditions far from saturation as a result of the interaction of trace elements with the oxidized surface of the mineral (the cadmium uptake by galena with the formation of either a sulfate surface phase or a sulfate-chloride surface phase). An important mechanism of trace-element uptake by sulfides during the hydrothermal growth of crystals is associated with external and internal adsorption of impurities by defects. This adsorption manifests itself both in an increase in the content of sorbed mercury in galena at a high sulfur activity due to the interaction of mercury with lead vacancies and in the formation of dislocation cadmium species, which results in an increase in the coefficient of cadmium distribution in the crystal-solution system.     

Experimental investigation of different configurations for the seeded growth of SiC crystals via a VLS mechanism

The growth of SiC crystals or epilayers from the liquid phase has already been reported for many years. Even if the resulting material can be of very high structural quality and the possibility to close micropipes was demonstrated, handling the liquid phase still is a challenge. Moreover, it is highly difficult to stabilize the C dissolution front and then to stabilize the growth front over a long growth time. Based on the Vapour‐Liquid‐Solid (VLS) mechanism, we present a new configuration for the growth of SiC single crystal which should allow first to simplify the liquid handling at high temperature and second to precisely control the crystal growth front. The process consists in a modified top and bottom seeded solution growth method, in which the liquid is held under electromagnetic levitation and fed from the gas phase. 3C‐SiC crystals exhibiting well‐faceted morphology were successfully obtained at 1100‐1200 °C with exceptional growth rates, varying from 1 to 1.5 mm/h in Ti‐Si melt. It was shown that the nucleation density decreases simultaneously with increasing propane partial pressure. At 1200‐1400 °C, thick homoepitaxial 6H‐SiC layers were successfully obtained in Co‐Si and Ti‐Si melts, with growth rate up to 200 µm/h. Large terraces with smooth surfaces are observed suggesting a layer by layer growth mode, and the influence of the system pressure was demonstrated. It was shown that the terrace size decrease simultaneously with increasing propane partial pressure which suggests the beginning of a two dimensional to three dimensional growth mode transition. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Transient regimes in the growth of large-diameter crystals

The behaviour of crystallization rate and interface position under the change of Czochralski growth system parameters is theoretically and experimentally investigated for the case of large diameter crystals growth. It is shown that the large value of crystal diameter leads to the inertia and nonmonotonic character of system relaxation after the perturbation. The possibility of hesitative nonstability is discussed. The transient regimes in the growth of 30 cm diameter KCl single crystals are investigated experimentally. The behaviour of crystallization rate differs from the case of small diameter crystals and corresponds to the results of theoretical analysis.     

Morphology and growth mechanism of vapor grown Cd crystals as affected by Bi impurity

The effects of Bi impurity on the morphology and growth mechanism of (physical) vapor-deposited Cd crystals were investigated. Scanning electron microscopic observation revealed, for the first time, hexagonal prismatic Cd crystals which were grown on the Bi contaminated pyrex glass tube wall. This kind of morphology does not appear in the case of pure Cd without the impurity Bi. The top of the hexagonal prismatic crystal was usually rounded hemispherically. X-ray microprobe investigations showed that the tip of the crystals contained about 57 wt% Bi. It was concluded that the Cd hexagonal prismatic crystals grow by the mechanism of vapor-liquid-solid with the impurity Bi.     

Study on rapid growth of highly‐deuterated DKDP crystals

Highly‐deuterated potassium dihydrogen phosphate (DKDP) crystals were grown rapidly from point seeds under high supersaturation in a temperature range of 40‐60 °C. The growth rate was about 1‐2 order of magnitude higher than that of the traditional temperature reduction method. It was found that highly pure raw materials, overheating at high temperature, ultrafine filtration and supersaturation stability were needed to keep the solution from spontaneous nucleation at high overcooling. The effect of growth conditions on pyramid faces was different from that of prismatic faces. The tetragonal to monoclinic phase solubility transition scarcely occurred in our experiments even though the overcooling of monoclinic phase was as high as 10 °C in some cases. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Iso-epitaxial growth of n-octacosane crystals

Iso-epitaxial(epilayer)growth of n-octacosane crystals is reported. The morphology of the epilayers is in the form of triangular growth islands with or without truncature. Epilayer growth precedes spiral growth mechanism which occurs at medium and low supersaturations, respectively. The occurrence of triangular and truncated rhombic platelets is found to be a manifestation of growth at medium supersaturations.     

Dendritic growth of snow crystals

The hypothesis that allows the interpretation of dendritic growth of a snow crystal in terms of diffusion-limited aggregation is criticized. The results of simulation of growth of quasi-two-dimensional crystals in two-and three-dimensional media based on the classical two-parametric model of diffusion-limited aggregation are used as an argument in this criticism. It is established that the model dimensionality considerably influences morphology of the grown crystal. The mechanism of dendritic growth of a snow crystal in which the main part is played by the surface processes at the ice/water interface is suggested.     

Fluctuations in growth rate of gypsum crystals

Growth of needlelike gypsum crystals from highly supersaturated aqueous solutions has been studied by the methods of the optical and electron microscopies. The average growth rates of the end faces and their fluctuations are determined. It is shown that the fluctuations in the growth rates of end faces are described by the Fokker-Planck equation and that the end faces of gypsum crystals grow by the layer mechanism with the layer nucleation in the vicinity of one of the crystal vertices.     

On the mechanism of chemical polishing of GaAs crystals

In order to establish reproducible conditions for chemical lap polishing of GaAs with NaOCl solutions, containing also OH⁻- and CO -ions, the mechanism of dissolution was investigated using the rotating disk arrangement. In solutions with excess OCl⁻ concentrations likewise diffusion and a reaction of the first order with respect to OH⁻ and CO, complexing agents for Ga-ions, control the dissolution rate, and the surfaces of the wafers are polished. OH⁻ and CO₃^2– concentrations in excess with respect to OCl⁻ lead to rate determining OCl⁻ diffusion and to irregularly polished or film covered surfaces. Diffusion constants for OH⁻, CO and OCl⁻ are given.     

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.     

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.     

Growth mechanism of stearic acid single crystals

Micro-morphological observation of the growth patterns on the (001) surfaces of large single crystals of stearic acid grown from solution under moderate growth conditions was carried out by optical and electron microscopy. Two typical growth features, namely, growth spiral steps and two-dimensional (2-D) nucleation-like steps, were identified optically. Then, these patterns were observed in more detail by the replica method of electron microscopy and it was found that the steps are usually two to four times the length of the bimolecular growth unit. These growth units also revealed spiral growth and 2-D nucleation growth patterns.     

Growth of borax crystals by spiral mechanism

Borax crystals grown at low supersaturation values are described. A brief report about microtopographical studies of these crystals is presented. Growth spirals observed on almost all the habit faces except those in contact with the bottom of the nucleation cell are described and discussed. It is established that all these crystals have platelet form in the initial stages of crystallization and as growth proceeds they develop and grow by spiral mechanism. The conditions under which the screw dislocations play the role in the development and growth of the crystals have been worked out.     

Study of inclusions and growth bands in potassium bichromate crystals grown from aqueous solutions

The nature of inclusions and growth bands in potassium bichromate crystals obtained from aqueous solutions and their formation in relation to growth temperature and supersaturation are investigated. It is observed that impurities present in solution, fluctuations in growth temperature and high growth rates are responsible for their formation.