Nucleation of GaN on sapphire substrates at intermediate temperatures by Hydride Vapor Phase Epitaxy

A novel approach to deposit GaN layers directly on a sapphire substrate by Hydride Vapor Phase Epitaxy is presented. The two‐step deposition process includes the growth of GaN nucleation layers at intermediate temperatures in the range of 750 – 900 °C and subsequent high‐temperature overgrowth at about 1040 °C. Closed and non‐closed nucleation layers with a thickness of up to 2 μm were produced and characterized by scanning and transmission electron microscopy, micro‐Raman spectroscopy and X‐ray diffraction. A growth temperature of 780 °C is found to be optimal with respect to density and size distribution of nucleation islands. Raman measurements performed on the nucleation layers reveal nearly zero residual stress indicating effective stress relaxation on cooling down from growth temperature. The results of first overgrowth experiments demonstrate the possibility to grow 10 μm thick, crack‐free GaN layers of high crystalline quality on the nucleation layers. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Determination of the solid liquid interfacial energy and thereby the critical nucleus size of paracetamol in different solvents

The effect of the type of solvent on the solid liquid interfacial energy was determined by performing induction time measurements of paracetamol in methanol, 1‐propanol, acetone and water at a constant supersaturation temperature of 30 °C and different levels of supersaturation (a/a*) ranging from 1.03 to 1.24. At equal supersaturation level and temperature the induction time increases with decreasing solubility whereas the solid liquid interfacial energy decreases with increasing solubility. The interfacial energy has a minimum value of 1.45 mJ/m² in the solvent where paracetamol has a maximum solubility (methanol) whereas it has its maximum value of 2.91 mJ/m² in the solvent with minimum solubility. The interfacial energy is a function of the solubility has been established. The critical radius for homogeneous nucleation was found to be minimum in the solvent of highest solubility. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nucleation kinetics of the formation of low dimensional calcium sulfate dihydrate crystals in isopropyl alcohol medium

Calcium sulfate dihydrate, constituted as uniform crystals of low dimensions, is a potential biomaterial for clinical applications like bone graft substitution and drug delivery. In this work, isopropyl alcohol has been used as a solvent to obtain low dimensional calcium sulfate dihydrate crystals from calcium nitrate ‐ sulfuric acid system. Reactants in 0.5 molar concentration at ambient conditions generated uniform rod‐shaped crystals of length 3–5 µm. Analysis using X‐ray Diffractometry and Fourier Transform Infrared Spectrometry showed the material to be well crystallized, phase‐pure calcium sulfate dihydrate. The nucleation kinetics has been studied by observing the induction time of phase formation in solutions of millimolar concentrations through turbidimetry at 300 K. The data have been analysed using classical nucleation theory to deduce parameters like interfacial tension (or surface free energy), nucleation rate and critical radius. The surface free energy obtained (5.6 mJ/m²) is comparatively lower than that reported for aqueous precipitation, which could be attributed to the presence of isopropyl alcohol. On escalating the supersaturation ratio, the nucleation rate drastically increased and the critical radius decreased exponentially. Particles formed at supersaturation 1.39 showed a monomodal distribution centered at 8.2 nm in Dynamic Light Scattering analysis. Comparable particle sizes were obtained in Transmission Electron Microscopy.     

A study of primary nucleation of calcium oxalate monohydrate: I‐Effect of supersaturation

There are various organic and inorganic constituents in kidney stones. Among them, calcium oxalate monohydrate (COM) is the primary inorganic constituent of kidney stones. However, the mechanisms of formation of kidney stones are not well understood. In this regard, a basic study is carried out for better understanding of nucleation, crystal growth and/or aggregation of formed COM crystals. The primary nucleation of calcium oxalate monohydrate is studied at the laboratory scale using turbidity measurements. Calcium chloride and potassium oxalate solutions are mixed and then added to a Turbidimeter tube for continuous recording of turbidity. Induction time (time to induce formation of detectable crystals) is estimated from time‐turbidity graphs. The effect of some urinary species, such as oxalate and calcium, on nucleation and crystallization characteristics of COM is determined by particle size distribution analysis, measuring weight of crystals and calculation of relative supersaturation. The classical nucleation theory is applied at high supersaturation ratios (SR) ranging from 1.6 to 2.2. The results indicate that nucleation rate increases with increasing supersaturation ratio from 0.81 × 10²⁸ nuclei/cm³.sec at 1.6 SR, to 18.02 × 10²⁸ nuclei/cm³.sec at 2.2 SR. On the other hand, free energy change and radius of critical nucleus are decreased as supersaturation ratio is increased. The nucleation rates are higher than those reported in literature. Such discrepancy is discussed on the bases of differences in experimental techniques. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Nucleation Catalysis in Metastable Liquids: Inborn Active Sites

A simple formalism is developed in order to analyze the nucleation activity of inborn “week” or “strong” active sites in metastable liquids which can play in nucleation kinetics a role, similar to this of heterogeneous nucleation cores. As examples are examined the influence of Bernal holes and fluctuatively formed Frenkel voids on bubble nucleation, of athermal supercritical nuclei and heterophase fluctuations, frozen‐in in the thermal prehistory of the system on any process of phase formation, and of structural defects, due to change of composition or created in redox processes on crystallization. The analysis is performed in analogy with the known treatment of the influence of heterogeneous foreign cores on nucleation kinetics. Different changes of the metastable liquid are investigated, considering both isobaric thermal quenches and change of pressure at isothermal conditions. The effect of inborn active sites on both steady nucleation rate Iss and on nucleation time lag τ^# is investigated. In this way the whole kinetics of nucleation is constructed using the known approximative solutions of the more general, transient theory of nucleation.     

Investigation of metastable zone width of ammonium oxalate aqueous solutions

The metastable zone width of pure ammonium oxalate aqueous solutions, as represented by maximum supercooling ΔT_max, is investigated as functions of cooling rate R and saturation temperature T₀ by the polythermal method. The experimental results are discussed by using two recently advanced approaches: (1) self‐consistent Nývlt‐like approach based on a power‐law relationship between nucleation rate J and maximum supersaturation lnS_max, and (2) a novel approach based on the relationship between J and lnS_max described by the classical three‐dimensional nucleation theory. Analysis of the experimental data revealed that both approaches describe the experimental data on metastable zone width by the polythermal method reliably and provide useful information about the physical processes and parameters involved in nucleation kinetics. The values of various physical quantities predicted by both of these approaches are reasonable for a fairly‐soluble compound. A careful examination of the data on ΔT_max as a function of T₀ obtained by polythermal method and from density measurements showed that ΔT_max has a slight tendency to decrease with increasing saturation temperature T₀. The values of lnS_max at saturation temperature 303 K suggest that the metastable zone width of ammonium oxalate aqueous solutions is determined by primary nucleation in the polythermal method and by secondary nucleation during density measurements. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystallization of silicalite‐1 from clear synthesis solutions: Effect of template concentration on crystallization rate and crystal size

Synthesis of silicalite‐1 powders and membranes from initially clear solutions with different tetrapropylammonium hydroxide or bromide concentrations was studied. While tetrapropylammonium bromide acts only as template, tetrapropylammonium hydroxide provides both the template and hydroxyl ions to the synthesis medium. The effects of template and hydroxyl ion concentration on the product yield, crystallization rate and crystal size were investigated. Pure and highly crystalline silicalite‐1 was obtained with all compositions. The nucleation time decreases from 100 h to 20 h and the crystal size decreases from 3.5 μm to 0.35 μm as the template amount x is increased from 5 to 30 moles at a batch composition of 80SiO₂.xTPAOH.1500H₂O at 95 °C. Yield of silicalite‐1 passes through a maximum at intermediate TPA concentration. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Metastable zone width for secondary nucleation and secondary nucleation inside the metastable zone

This study presents an evaluation of a new method, called zero growth activation free energy, used to determine the metastable zone width for the secondary nucleation case. It predicts the metastable zone width with a maximum error of 5‐10%. Estimation of the metastable zone width for different isothermal crystallization conditions can be modeled according to a chosen reference set of growth experiments carried out in the volume diffusion regime at different initial supersaturations, using seed crystals of a certain characteristic size. Moreover, the activation free energy of the secondary nucleation was estimated. The role of the enthalpy of immersion in the formation of secondary nucleation events inside the metastable zone was pointed out, as well as its effect in causing extra‐fast growth rate. Furthermore, sucrose crystal surface free energy was estimated. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystallization of vitamin C in a continuous DT MSMPR crystallizer – Size independent growth kinetic model approach

The experimental results concerning continuous mass crystallization process in L(+)‐ascorbic acid – water system are presented and discussed. Influence of L(+)‐ascorbic acid concentration in a feeding solution and mean residence time of suspension in laboratory DT MSMPR crystallizer on product crystal size distribution as well as nucleation and growth kinetics were determined. Kinetic parameter values were evaluated on the basis of size–independent growth (SIG) kinetic model (McCabe's ΔL law). It was observed, that within the examined range of crystallizer productivity (120–1600 kg LAA crystals m^–3h^–1) crystal product population of mean size L_m from 0.2 to 0.3 mm and CV from 66.6 to 49% is withdrawn. Linear growth rate values present decreasing trend (from ca. 7 · 10^–8 to ca. 6 · 10^–8 m s^–1) with the productivity increase (assuming constant mean residence time of suspension τ = 900 s). Occurrence of secondary nucleation within the circulated and mixed suspension, resulting from crystal attrition and breakage, was observed. The parameter values in design equation connecting linear growth rate and suspension density with nucleation rate were determined. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Two‐ and three‐dimensional growth modes of nitride layers

Heteroepitaxial three dimensional (3D) and two dimensional (2D) growth modes of nitride layers on sapphire substrates are discussed. It is shown that the 3D or 2D growth mode of AlGaN layers depends predominantly on the growth conditions of the underneath low temperature (LT) nucleation layer. Commonly described in literature 3D growth mode is achieved on LT GaN or AlN nucleation layer grown relatively fast. Successive growth of secondary layer at high temperature begins from separated sites, where individual 3D crystallites are formed. Threading dislocations present in crystallites bend on their facets, which reduces the quantity of dislocations. However, slight crystallographic misorientations between crystallites lead to the creation of new dislocations during coalescence of the crystallites. As a result, edge and mix dislocations appear at similar densities of about 10⁹ cm^‐2. Modification of growth conditions of LT AlN nucleation layer, especially reduction of their growth rate, leads to drastic changes in properties of the layer. Successive growth of secondary AlGaN layer at high temperature starts evenly on whole surface retaining atomic flatness. Thus growth at high temperature occurs only by 2D mode. Therefore, it is possible to grow a very thin AlGaN layers directly on top of LT nucleation layer. Such layers contain large number (10¹⁰ cm^‐2) of edge dislocations, and relatively small number (less then 10⁸ cm^‐2) of mix dislocations. It is also shown that the decisive factor determining the growth mode of AlN nucleation layer is a growth of the first few atomic layers on substrate surface. The slow growth of these few first atomic layers decide about the 2D growth mode, and the fast one about the 3D one. The model explaining this difference is presented as well. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of nucleation kinetics and crystal defects of HMX

The nucleation kinetics of HMX (cyclotetramethylene tetranitramine, C₄H₈N₈O₈) in γ‐butyrolactone was studied in cooling process by induction time method. The laser scattering method was used to measure the solubility data and metastable region of HMX in γ‐butyrolactone. The induction time was measured over a range of supersaturation at different temperatures. Then, the nucleation mechanism of HMX in γ‐butyrolactone was investigated by analysis the relationships between induction time and supersaturation. The results indicated homogeneous nucleation dominated at high supersaturation of S >1.35, while the heterogeneous nucleation dominated at low supersaturation of S < 1.35. The values of interfacial tension at different final temperatures were calculated to indicate the ability of HMX to be crystallized. The growth mechanism of HMX was investigated by the data fitting applying different growth mechanism models and identified as two‐dimensional nucleation‐mediated (2D) growth. Finally, the effects of supersaturation and temperature on the crystal defects were analyzed based on the nucleation kinetics. When the temperature is below 303.15K, homogeneous nucleation dominated the nucleation process at higher supersaturation. Fine HMX crystals with more defects were produced. On the contrary, heterogeneous nucleation mechanism dominated at lower supersaturation. large regular HMX crystals with fewer defects were formed when the temperature is above 318.15K.     

A Calorimetric Measurement of Phase Transformation Kinetics in Solid Octaphenylcyclotetrasiloxane: Evidence for Nucleation as the Rate Determining Process

The kinetics of transformation from the metastable (at high temperature) solid 3-phase of octaphenylcyclotetrasiloxane to the stable 2-phase have been measured by a calorimetric technique. The results of the kinetic study and several related experiments are consistent with the view that nucleation is the rate determining process. Transformation time constants for large and small crystallites were found; the temperature dependence of each is in accord with the Turnbull-Fisher nucleation theory. From that theory γ, the interfacial energy between the 3- and 2-phases, has been found to be -3 ergs/cm², an order of magnitude smaller than that for typical liquid-solid interfaces. A study of the dependence of the transformation kinetics on crystallite size suggests that the phase change is surface nucleated.     

Broad near‐infrared fluorescence properties of Nd‐doped PbClF crystals

Nd‐doped PbClF crystals were grown with modified Bridgman method. Broad and flat emission band at 1.0 μm was observed. The FWHM value of 0.0091 wt.% Nd³⁺‐doped PbClF crystal at 1064 nm reached up to 30 nm with the peak emission cross‐section of 1.05×10^‐19 cm². All the results indicated that Nd‐doped PbClF crystal should be a promising tunable and ultrafast laser material. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of Cu vanadate nanorods for visible‐light photocatalytic degradation of gentian violet

Cu vanadate nanorods have been synthesized via the hydrothermal process using polymer polyvinyl pyrrolidone (PVP) as the surfactant. X‐ray diffraction (XRD) shows that the nanorods are composed of monoclinic Cu₅V₂O₁₀ phase. Scanning electron microscopy (SEM) observation shows that the diameter and length of the nanorods are 50–300 nm and 3 μm, respectively. PVP concentration, hydrothermal temperature and duration time play essential roles in the formation and sizes of the Cu vanadate nanorods. A PVP‐assisted nucleation and crystal‐growth process is proposed to explain the formation of the Cu vanadate nanorods. Gentian violet (GV) is used to evaluate the photocatalytic activities of the Cu vanadate nanorods under solar light. The GV concentration clearly decreases with increasing irradiation time, and content of the Cu vanadate nanorods. GV solution with the concentration of 10 mg L⁻¹ can be totally degraded under solar light irradiation for 4 h using 10 mg Cu vanadate nanorods. The Cu vanadate nanorods have good photocatalytic activities for the degradation of GV under solar light.     

Crystallization kinetics of ZnS precipitation; an experimental study using the mixed‐suspension‐mixed‐product‐removal (MSMPR) method

The precipitation kinetics of zinc sulfide were studied using a lab scale mixed‐suspension‐mixed‐product‐removal (MSMPR) precipitation reactor. The vessel was operated at different feed concentrations, molar ratios, stirrer speeds, pH‐values, feed injection positions and residence times. Primary nucleation and volume average crystal growth rates as well as agglomeration kernel were determined. Relationships were found between the rates of the different crystallization steps on the one hand and supersaturation, stirrer speeds, pH‐values, Zn²⁺ to S^2‐ ratio, feed positions on the other. These show that larger crystals are obtained at high supersaturation, moderate stirrer speeds, small residence times, a pH‐value of around 5 and high Zn²⁺ to S^2‐ ratios. One should realize though that the applied MSMPR method is not the most optimal technique for examining fast precipitation reactions. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

In situ AFM investigation of 2D nucleation on the (100) face of KDP

Surface morphology of the (100) face of potassium dihydrogen phosphate (KDP) crystals which were grown at different supersaturations at 25 °C was investigated by in situ atomic force microscopy (AFM). Various AFM images of 2D nucleation under different growth conditions were presented. It is found that the growth of KDP is controlled by polynuclear nucleation mechanism at the high supersaturation. With reduction of the supersaturation, the growth velocity of 2D nuclei becomes very slow and shows typical anisotropy. It is found that the process of coalescence of 2D nuclei does not lead to defect. The experiments show that the growth mechanism for KDP at 25 °C changes between step flow and 2D nucleation in the supersaturation range of 4.5‐5%. The triangular nuclei which are close to equilateral triangle are observed in the experiment at the supersaturation σ = 6% for the first time, showing typical anisotropic growth. Through observing the dissolution of 2D nuclei, the dissolving process can be regarded as the reverse process of growth. We also find that the microcrystals landing on the surface at σ = 9% would grow and coalesce with each other and there is no observable defect in the coalescence. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

添加CaSO4·2H2O为晶种制备磷石膏半水硫酸钙晶须

以固体废弃物磷石膏为原料,在传统常压醇水热法的基础上添加CaSO₄·2H₂O为晶种制备半水硫酸钙晶须。采用单因素试验法探究了晶种含量、丙三醇含量和磷石膏质量分数对晶须结构和形貌的影响,确定晶须的最佳制备工艺条件。采用SEM和XRD对样品进行表征分析,实验结果表明:添加CaSO₄·2H₂O晶种制备晶须的长径比(49.29)比只添加丙三醇的样品的长径比(30.99)提高了近60%;当丙三醇与水的体积比(V)为1、晶种含量为1%、磷石膏质量分数为5%时制备的晶须的平均直径为0.65 μm,长径比达到了62.15,晶须的尺寸均匀。这说明添加1%CaSO₄·2H₂O晶种、V为1的丙三醇和质量分数为5%的磷石膏在常压下能制备出高长径比和尺寸均匀的半水硫酸钙晶须。     

Determination of nucleation parameters and the solid liquid interfacial energy of the KCl‐ethanol‐water system

The kinetic parameters of homogeneous nucleation of KCl in different ethanol‐water solvent mixtures were determined at 25°C from the experimental measurements of the width of the metastable zone at different cooling rates. The ethanol mass ratio in the ethanol water solvent mixture was varied from 0‐0.9 and the metastable zone width for each solvent mixture was measured under the cooling rates of 10, 20 and 30 K/h. The influence of ethanol ratio on the activity coefficient was calculated. It was found that increasing the ethanol ratio in the solvent mixture leads to an increase in the mean molal activity coefficient. The experimental results obtained showed that the increase in the ethanol ratio in the solvent widens the metastable zone for the crystallization of KCl. Also it has inferred from the calculations based on the classical nucleation theory that increasing of the ethanol ratio in the solvent mixture resulted in an increase of the nucleation rate order, increase of the critical size of nuclei and increase of the solid liquid interfacial energy. It has been found that the solid liquid interfacial energy can be good correlated with inversely proportionality to the solubility. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)