Inhibition of Calcium Oxalate Monohydrate Crystal Growth in High and Low Ionic Strength Solutions

The effect of additives on the kinetics of growth of calcium oxalate monohydrate crystals has been studied. Conductivity and potentiometry measurements have been compared. Growth rates were calculated from precipitate curves by a cubic spline method. An approach consisting on the calculation of rate constants and orders of reaction from logarithmic plots of growth rate versus supersaturation has been followed to study crystal growth kinetics. This method revealed that the presence of additives is causing not only a decrease on the rate constant but an increase on the order of reaction as well. The effect of additives (EDTA, citrate and phytate) was considerably weaker in high ionic strength media. Phytate produced a complete blockage of crystal growth in concentrations as low as 2 × 10^—6 mole/L in both methods.     

Effects of anions on rapid growth and growth habit of KDP crystals

The synthesis of KDP from its raw material has been found exist in the growth solution. In the crystal growth experiment, significant extension of specific faces was observed at low dopant concentration. At high doping concentration, the growth rate of the whole crystal decreased with no significant habit modification. The inhibiting effects of phosphite and other H-bonding anionic ions on the growth of pyramidal faces are discussed. Rapid growth rate experiments have been carried out with purified material and an averaged growth rate of 18.6mm/day was obtained.     

Electrocrystallization of silver: Growth kinetics of screw-dislocation-free (100) crystal faces

At given conditions, especially at higher supersaturation, the growth rate of a close packed, perfect crystal face depends on the formation rate of two-dimensional nuclei and on the propagation rate of the monoatomic layers. This multinuclear multilayer growth as well as the advancement rate of growth steps have been studied experimentally on electrocrystallization of silver. The advancement rate of mono- and polyatomic growth steps has been measured on screw dislocation-free (100) crystal faces. For low overvoltages a linear dependence of the rate on overvoltage has been found. A strong influence of the surface condition of the crystal face — “fresh” or “aged” on the step advancement rate has been established. It was also found that on a “fresh” surface mono- and polyatomic steps advance with the same rate. The average monoatomic step spacing of the polyatomic step has been determined. The kinetic constants of the step growth rate are established and a conclusion regarding the mechanism of electrolytic deposition of silver is drawn. The initial current—time curves were recorded on applying potentiostatic pulses on a perfect crystal face. The shape of these curves coincides very well with those theoretically calculated for the cases of multinuclear growth. On the basis of the theoretical dependences, one can determine from these curves the formation rate J of two-dimensional nuclei at a given overvoltage η since the rate of step advancement is known. A linear dependence of log J on 1/η has been established. The values of the pre-exponential term in Volmer's equation and the specific edge energy of the two-dimensional nucleus have been determined. The surface condition of the crystal face influences strongly also the process of two-dimensional nucleation.     

Morphological selection of Euclidean and fractal patterns of nonequilibrium growth of ice in supercooled water

A morphology diagram of Euclidean and fractal patterns of the nonequilibrium growth of ice in supercooled water has been constructed based on the experimental dependence of the growth rate of ice crystals of different shapes on the initial supercooling of water. An empirical morphological principle follows from this diagram: with an increase in water supercooling, the phase implementing the maximum volume growth rate of ice crystals is selected.     

Selective growth and other applications of hydrogen-assisted molecular beam epitaxy

The usefulness of atomic hydrogen in molecular beam epitaxy has been demonstrated, centering around selective growth. Atomic hydrogen is effective for low-temperature cleaning of substrates, surfactant effects such as restrain of island growth and suppression of the surface migration of the adatoms and selective growth on masked or V-grooved substrates. These effects are dependent on substrate temperatures. The selective growth of GaAs has been successfully demonstrated at the conventional growth temperature and growth rate with the aid of atomic hydrogen. The main mechanism of the selective growth is the re-evaporation of Ga and As from mask materials such as SiN_x or SiO₂. Selective growth has also been observed on low-index crystal facets. On (111)A and (110) facets, no GaAs was deposited in the presence of atomic hydrogen, the flux of which is approximately the same as that of Ga. GaAs quantum wire structures have been fabricated on the substrates with V-shaped grooves. The efficient capture and confinement of carriers into wire regions have been observed by photolumenescence.     

Acceptor incorporation in SiC epilayers grown at high growth rate with chloride-based CVD

A systematic p-type doping study has been performed on 4H- and 6H-silicon carbide (SiC) epilayers grown at high growth rate using chloride-based chemical vapor deposition. The effect of temperature, pressure, growth rate, C/Si-, Cl/Si-ratios and dopant flow on the incorporation of the acceptor atoms aluminum and boron has been studied. The C/Si-ratio on the aluminum incorporation has similar behavior to what has been reported for the standard non-chlorinated low growth rate process, while no clear effect of C/Si-ratio was observed for the boron incorporation. A higher Cl/Si-ratio seems to lead to lower the aluminum and boron incorporation either due to more effective silicon supply at high Cl/Si-ratio or due to removal of dopant atoms from the surface by chlorine. The doping concentration is stable to the variations in silicon molar fraction, growth pressure and growth temperature for the aluminum-doped layers. Also p-type doping with gallium was tested.     

The influence of inhibitors on the growth of barium sulfate crystals in suspension: Scale prevention (II)

The inhibiting influence of four organic bisphosphonates with different substituents on the growth rate of barium sulfate crystals, suspended in a supersaturated solution, has been investigated. The growth process has been studied conductometrically. Plots of both the relative supersaturation versus time and the mean linear rate versus the growth affinity have been given. — The results have been interpreted using a hypothesis, stating that growth inhibition occurs due to simultaneous coordination of the cations and hydrogen bonding of the anions at the active growth spots on the crystal surface.     

The Oscillations of Crystal Growth Rates at their Formation in the Regime of free Convection of a Solution; Statistical Investigation

The growth rate oscillations of {101 ) NaNO₃ crystal face have been measured at certain range of supersaturation of a water solution. It has been found, that root-mean-square amplitude of the oscillations of rates increases linearly with the growth of the mean growth rate. The supposition has been made that observed oscillations belong to flicker noise.     

Heat transfer and mass transport in a multiwafer MOVPE reactor: modelling and experimental studies

An improved detailed model for the calculation of the temperature distribution in a multiwafer Planetary Reactor™ has been developed. The temperature field of the reactor has been calculated in dependence of the reactor parameters for (Al,Ga)As growth as well as on the kind and the thickness of the wall and susceptor deposits. The amount of parasitic wall deposits can be minimized by a proper tuning of the reactor temperature distribution. Calculated GaAs growth rate profiles on 3 inch wafers show a strong dependence on the temperature field in the reactor and the amount of parasitic deposits. These predicted relationships have been used to optimize the reactor temperature distribution in order to minimize parasitic wall depositions. By this procedure a growth rate uniformity of < 1% on 3 inch wafers can be reproducibly achieved.     

Optimization of the crystallization rate in growing Bi4Ge3O12 crystals by the LTG CZ technique

The influence of the growth rate on the shaping and quality of Bi₄Ge₃O₁₂ (BGO) crystals during their growth by the low-thermal-gradient Czochralski technique has been studied. Several series of BGO crystals have been grown with the rate varying from 0.3 to 15 mm/h. The limited growing rates at which the crystal quality is not deteriorated are established. The results of the study make it possible to increase the growth rate in commercial systems by a factor of 1.5–2 and thus significantly increase the growth efficiency.     

In-situ doping of LPCVD poly silicon (II). Temperature influence

Poly silicon deposition by pyrolysis of silane under low pressure conditions has been investigated with respect to the influence of temperature when simultaneously in-situ doping of the deposited layer takes place. The growth rate of poly silicon is retarded in the presence of phosphine provided that a certain lower PH₃/SiH₄-ratio has been exceeded. It has been shown how that lower ratio depends on temperature. Increasing PH₃/SiH₄-ratio not only slows down layer growth rate but also the apparent activation energy of the layer forming reaction. An empirical equation describing the temperature dependence of that activation energy has been derived. Phosphine adsorption has been discussed as a cause of both layer growth rate and activation energy reduction. Additionally, incorporation of phosphorus during layer growth has been investigated with respect to the total amount and the electrically active concentration, the latter measured after a postdeposition anneal at 1000 °C.     

Modelling crystal growth rate of barium chromate precipitated from homogeneous solution

An empirical power law type model, used for modelling crystal growth rate of barium chromate, when precipitation was carried out from homogeneous solution, has been applied to the re-analysis of experimental data, based on which an unusual inverse size dependence on growth rate had been claimed previously. It is shown that the current empirical model provides a more realistic explanation of the data. The weaknesses of the previous approach are discussed in comparison with this new model.     

Concentration oscillations at doped crystal growth from solutions

A mathematical model of two-component crystal growth from solutions has been developed. The growth rate and component concentration are shown to oscillate near the growth front at certain parameters in the growth system; these oscillations lead to corresponding spatial changes in the grown crystal composition: oscillatory zoning.     

The growth kinetics of barium sulphate crystals in suspension: Scale prevention (I)

The growth process of barium of sulfate crystals suspended in a supersaturated solution has been studied conductometrically. The mean linear rate R̄ has been plotted as a function of the growth affinity — Δμ/RT. A first attempt has been made to fit the experimental growth data in the highest supersaturation range with surface nucleation models.     

Study of the chemical reactions' influence on semiconductor films structure formation by the Monte-Carlo method

The investigation by the Monte-Carlo method of the growth of the silicon epitaxial film at a chloride CVD system has allowed to find out the composition of adsorption layer, the micromechanism of the reactions of Si atoms building-in into the growing crystalline layer and the growth conditions influence on the growth rate and film surface roughness. The change of adsorptive layer composition in the system SiCl₄—HCl—H₂ (fraction of adaatoms, silicon atoms built-in a crystal and molecules SiCl₂) depending on temperature has been determined. The change of silicon film growth rate depending on temperature and concentration change of SiH₂Cl₂ has been established and the contribution of growth mechanism (with participation of adatom, silicon atoms and molecules SiCl₂) into the total rate of film growth has been shown.     

大尺寸HVPE反应器寄生沉积的数值模拟研究

在氢化物气相外延(HVPE)生长GaN厚膜中,反应腔壁面总会产生大量的寄生沉积,严重影响薄膜生长速率及质量.本文针对自制的大尺寸垂直式HVPE反应器,通过数值模拟与实验对比,研究了反应腔壁面沉积以及GaN生长速率的分布规律,特别是寄生沉积分布与载气流量的关系.研究发现:在基准条件下,顶壁寄生沉积速率由中心向边缘逐渐降低,与实验结果吻合;侧壁沉积出现8个高寄生沉积区域,对应喷头边缘处排布的GaCl管,说明沉积主要取决于GaCl的浓度输运;模拟得出的石墨托表面生长速率低于实验速率,但趋势一致.保持其他条件不变,增大NH3管载气N2流量,顶壁和侧壁的寄生沉积速率及分布区域均随之增大,石墨托表面生长速率随之减小而均匀性却随之提高;增大GaCl管载气N2流量,顶壁和侧壁的寄生沉积速率及分布区域均随之减小,石墨托表面生长速率随之增大而均匀性却随之降低.研究结果为大尺寸HVPE反应器生长GaN的工艺优化提供了理论依据.     

Temperature dependence of grain growth in zone-refined tin containing large additions of zinc in solid solution

Grain growth in zone-refined tin containing high concentrations > 0.05 < 0.40 wt% Zn in solid solution have been investigated in the temperature range 70–160°C. It has been found that increasing the zinc content by a factor of 8 decreased the rate of grain growth by ∼ 30% at all annealing temperatures, and this was attributed to small variations of grain boundary mobility. In addition, the increase of annealing temperature from 70 to 160°C resulted in the increase of grain growth by a factor of ∼ 50 at any given concentration, which shows that the rate of grain growth is not strongly influenced by increasing the zinc concentration. The energy activating the growth process was calculated for all concentrations investigated and had a nearly constant value of ∼ 1 eV. An empirical formula was proposed relating the rate of grain growth and the solute concentration.     

On chemical kinetics of silicon deposition from silane (I). The first order chemical reaction

Theoretical expressions for silicon layer deposition in consequence of silane decomposition within an open isothermal reaction tube has been derived for the case of homogeneous as well as heterogeneous gas reaction. Layer growth distribution along reaction tube axis has been taken into consideration as well as average layer growth rate related to silane consumption during its passage through the tube on the one hand and to growth rate distribution along the tube on the other. Comparing the theoretical results with experimentally based data homogeneous rather than heterogeneous reaction mode might be preferred. In consequence, however, layer growth rate should be linearly effected by the ratio of reactor gas volume to total substrate surface area. In a practical sense average growth rate, and so axial growth homogeneity, should be expected the higher the lower silane consumption efficiency would be adjusted.     

Determination of linear growth rates of crystals (I). Calculation of linear growth rates of individual crystal faces from overall rates

The presented paper (Part I and II) is devoted to the fundamental principles of the kinetics of crystal growth. The number of studies in this field has been increasing and some authors have introduced different terms and definitions. To avoid possible mistakes and confusions, the individual definitions of the rate of crystal growth are specified and their interrelations are discussed in detail. Basic methods for measuring the kinetics of crystal growth are described. The rate of growth of individual crystal faces or the average rate of crystal growth can be determined using the selected experimental method. The presented study demonstrates that the results obtained by either of the two measuring methods (linear rate of growth of crystal faces and average rate of crystal growth) can be interrelated. The established method of calculating linear growth rates of individual crystal faces is based on an analysis of the time dependence of the volume of a growing crystal. The relationship between the linear growth rates of individual crystal faces and the over-all crystal growth rate is presented and a method for assessing the linear growth rates of individual crystal faces from over-all growth rate data, which can be measured readily, is suggested.     

三氯氢硅和氢气系统的气相沉积三维模拟

建立了氢气和三氯氢硅系统的多晶硅气相沉积反应模型,通过Chemkin4.0耦合气相反应、表面反应机理,利用流体力学软件Fluent 6.3.26数值求解.根据模拟结果绘制了进气温度、进气组成、沉积表面温度以及反应压力与硅沉积速率的关系曲线,阐述了这些条件对于硅沉积速率的影响,同时把模拟结果与文献中的实验数据和计算结果进行对比.结果表明,硅沉积速率随反应温度和反应压力的提高而提高,随进气温度的提高而提高,当氢气摩尔组成低于0.8时,与氢气物质的量组成成正比,氢气物质的量组成大于0.8时,与氢气摩尔组成成反比.