Characteristic crystal growth from amorphous WO3 film by vacuum heating

Selective growth of WO₂, W and WO_3−x crystals from amorphous WO₃ film by vacuum heating at 400–900°C was clarified. The grown WO_3−x crystals were incommensurate structure based on crystallographic share structure. The growth process of WO₂ crystal in the amorphous film was directly observed at high temperature in the electron microscope. The growth front of the WO₂ crystal consumes WO₃ microcrystallites with various orientations. The growth speed of the WO₂ depended on WO₃ microcrystallites orientation. The origin of the wavy growth front of WO₂ was due to an orientation dependence of the WO₃ microcrystallites.     

The kinetics of parasitic growth in GaAs MOVPE

Gallium arsenide (GaAs) deposition was carried out in a horizontal quartz reactor tube with trimethylgallium (TMGa) and arsine (AsH₃) as precursors, using a hydrogen (H₂) carrier gas. Temperatures were in the range 400–500 °C, where surface reactions limit deposition rate. Nucleation time and deposition rate were monitored using laser interferometry, optimum reflectance was gained by aligning a quartz wafer to back reflect the incident beam. The 980 nm infrared laser beam was sufficiently long in wavelength to be able to penetrate the wall deposit. Results showing the effect of temperature and V/III ratio on the nucleation time and deposition rate are presented, where with temperature the nucleation delay was observed to reduce and the growth rate to increase. The nucleation delay is consistent with a thermally activated surface nucleation for the parasitic GaAs. A theoretical growth rate model, based on a restricted set of reaction steps was used to compare with the experimental growth rates. Without any free parameters, the growth rates from theoretical calculation and experiment agreed within a factor of two and showed the same trends with V/III ratio and temperature. The non-linearity of the theoretical growth rates on an Arrhenius plot indicates that there is more than one dominant reaction step over the temperature range investigated. The range of experimental activation energies, calculated from Arrhenius plots, was 17.56–23.59 kJ mol⁻¹. A comparison of these activation energies and minimum deposition temperature with the literature indicates that the wall temperature measurement on an Aixtron reactor is over 100 °C higher than previously reported.     

Different shapes of spherical vaterite by photo-induced cis–trans isomerization of an azobenzene-containing polymer in a mixture of dimethyl sulfoxide and water

We studied the crystallization of CaCO₃ by the photoisomerization of azobenzene groups in poly[1-[4-[3-carboxy-4-hydroxyphenylazobenzenesulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) in a mixture of dimethyl sulfoxide and water at 30 °C. The products were characterized by scanning electron microscopy (SEM), FT-IR, and powder X-ray diffraction (XRD) analysis. We observed that the different shapes of spherical vaterite particles were produced by the changes of configuration and polarity of the azobenzene groups in the polymer which resulted from photo-induced isomerization. The results indicate that the nucleation of primary particles of CaCO₃ was inhibited by in situ photo-induced cis–trans isomerization of PAZO. Therefore, we suggest that the shapes of the spherical vaterite can be effectively modified by photoisomerization of the azobenzene groups in the polymer at the initial stage of CaCO₃ crystallization.     

Ambient-condition growth of superconducting YBa2Cu4O8 single crystals using KOH flux

YBa₂Cu₄O₈ is a stoichiometric oxide superconductor of T_c80 K. Unlike YBa₂Cu₃O_7−δ, this compound is free from oxygen vacancy or twin formation and does not have any microscopic disorder in the crystal. Doping with Ca raises its T_c to 90 K. The compound is a promising superconductor for technological application. Up to now, single crystals have not been grown without using specialized apparatus with extremely high oxygen pressure up to 3000 bar and at over 1100 °C due to the limited range of reaction kinetics of the compound. This fact has delayed the progress in the study of its physical properties and potential applications. We present here a simple growth method using KOH as flux that acts effectively for obtaining high-quality single crystals in air/oxygen at the temperature as low as 550 °C. As-grown crystals can readily be separated from the flux and exhibit a perfect orthorhombic morphology with sizes up to 0.7×0.4×0.2 mm³. Our results are reproducible and suggest that the crystals can be grown using a conventional flux method under ambient condition.     

A study of growth and morphological features of TiOxNy thin films prepared by MOCVD

The growth and morphological features of MOCVD TiO_xN_y films have been characterized to evaluate the effect of various process parameters on film growth. XRD analysis of the films deposited at 600°C on Si(1 1 1) and mica show a TiN(1 1 1) peak at 2θ=36.6°, but only anatase peaks are detected below 550°C. Above 650°C, both anatase and rutile peaks are detected. The presence of ammonia is not effective below 550°C as the deposited film is mostly TiO₂. Also, ammonia does not play any role in homogeneous nucleation in the gas phase, as evident by the deposition of anatase/rutile particles above 650°C. The following changes in the morphological features are observed by varying process parameters. By increasing the ratio of titanium-isopropoxide to ammonia flow, the cluster shape changes from angular to rounded; dilution of the flow results in larger elongated clusters; increase in flow rate at constant precursor to ammonia ratios, changes the cluster shape from rounded to elongated and the cluster size deceases. Deposition at higher temperatures results in finer clusters with a slower growth rate and eventually results in a very thin film with particle deposition at 650°C and above.     

High-velocity banding structure in the laser-resolidified hypoperitectic Ti47Al53 alloy

Stability analysis of a growing solid/liquid interface is the fundamental concept of modern solidification theory. Here, serial laser rapid solidification experiments were performed on a hypoperitectic Ti₄₇Al₅₃ alloy to explore the dendritic growth behavior near the limit of high-velocity absolute stability. SEM and TEM techniques were carried out to investigate the microstructure and identify the phase composition. By adopting an improved sampling method of TEM, the growth morphology evolution of the laser-resolidified layer was observed directly and high-velocity banding structure was firstly detected in Ti–Al peritectic alloys. The high-velocity banding structures are parallel to the solid/liquid interface (normal to the growth direction) and made of the oscillation structures grown alternatively in modes of cell and plane morphologies. In light bands with cellular growth mode, all dislocation assembles are parallel to the growth direction and forms the cell boundaries, while all dislocation distributes randomly in dark bands. The determined growth velocity range for the appearance of high-velocity banding structures is about 0.51.1 m s⁻¹ according to the rapid solidification experiments, and the origin of the banding agrees well with the prediction of the CGZK phenomenological model (Acta Metal. Mater. 40 (1992) 983).     

Multiple-step annealing for 50% enhanced p-conductivity of GaN

In this article, multiple-step rapid thermal annealing (RTA) processes for the activation of Mg doped GaN are compared with conventional single-step RTA processes. The investigated multiple-step processes consist of a low temperature annealing step at temperatures between 350°C and 700°C with dwell times up to 5 min and a short time high temperature step. With optimized process parameters, and multiple-step processes, we achieved p-type free carrier concentrations up to 1–2×10¹⁸ cm⁻³. The best achieved conductivity, so far, lies at 1.2 Ω⁻¹ cm⁻¹. This is a 50% improvement compared to conventional single-step process at 800°C, 10 min.     

Influence of cooling rate on the liquid-phase epitaxial growth of Zn3P2

We report the liquid-phase epitaxial growth of Zn₃P₂ on InP (1 0 0) substrates by conventional horizontal sliding boat system using 100% In solvent. Different cooling rates of 0.2–1.0 °C/min have been adopted and the influence of supercooling on the properties of the grown epilayers is analyzed. The crystal structure and quality of the grown epilayers have been studied by X-ray diffraction and high-resolution X-ray rocking measurements, which revealed a good lattice matching between the epilayers and the substrate. The supercooling-induced morphologies and composition of the epilayers were studied by scanning electron microscopy and energy dispersive X-ray analysis. The growth rate has been calculated and found that there exists a linear dependence between the growth rate and the cooling rate. Hall measurements showed that the grown layers are unintentionally doped p-type with a carrier mobility as high as 450 cm²/V s and a carrier concentration of 2.81×10¹⁸ cm⁻³ for the layers grown from 6 °C supercooled melt from the cooling rate of 0.4 °C/min.     

Selective-area MOCVD growth for distributed feedback lasers integrated with vertically tapered self-aligned waveguide

The growth pressure and mask width dependent thickness enhancement factors of selective-area MOCVD growth were investigated in this article. A high enhancement of 5.8 was obtained at 130 mbar with the mask width of 70 μm. Mismatched InGaAsP (−0.5%) at the maskless region which could ensure the material at butt-joint region to be matched to InP was successively grown by controlling the composition and mismatch modulation in the selective-area growth. The upper optical confinement layer and the butt-coupled tapered thickness waveguide were regrown simultaneously in separated confined heterostructure 1.55 μm distributed feedback laser, which not only offered the separated optimization of the active region and the integrated spotsize converter, but also reduced the difficulty of the butt-joint selective regrowth. A narrow beam of 9° and 12° in the vertical and horizontal directions, a low threshold current of 6.5 mA was fabricated by using this technique.     

Solidification behavior of falling germanium droplets produced by pulsated orifice ejection method

In order to clarify containerless solidification mechanism of falling semiconductor microdroplets, the monosized droplets of germanium in the size range from 200 to 500 μm were ejected by pulsated orifice ejection apparatus method. The density of grains in the resultant particles was dramatically reduced by decreasing the ejection temperature, i.e. initial temperature. A surface observation and orientation imaging microscopy analysis proposed that such microstructural transition was derived from the dependency of preferred growth direction on the undercooling level: the initial temperature determined the solidification undercooling. Numerical calculation with the classical nucleation theory was performed to discuss this phenomenon, but could not sufficiently elucidate the effect of initial temperature obtained experimentally.     

Nanocrystallization of fresnoite glass. I. Nucleation and growth kinetics

We determined the internal nucleation, crystal growth and overall crystallization kinetics of fresnoite crystal (2BaO · TiO₂ · 2SiO₂) in an almost stoichiometric fresnoite glass. Due to the extremely high nucleation rates (10¹⁷ m⁻³ s⁻¹) that limit the maximum crystal size to 700 nm the nucleation densities and crystal sizes were estimated by scanning electron microscopy (SEM). The volume fraction crystallized was measured by X-ray diffraction. The nucleation rates obtained directly from SEM measurements reasonably agree with those calculated from the combination of overall crystallization with crystal growth kinetics. The activation enthalpies for viscous flow, transport of structural units across the nucleus/melt interface (nucleation) and crystal growth: ΔH_η, ΔH_τ and ΔH_U respectively, follow a similar trend to that observed for other stoichiometric silicate glasses that nucleate internally: ΔH_η=294>ΔH_τ=87>ΔH_U=61 kJ/mol. Fresnoite glass displays the highest internal nucleation rates so far measured in inorganic glasses. These rates are comparable to some metallic glasses and can lead to nanostructured glass-ceramics.     

Dynamic process of crystallization of Sb2Se3 from Sb50Se50 amorphous film

Dynamics of crystallization of amorphous antimony-selenium film deposited on carbon substrate have been studied by the high-resolution transmission electron microscopy. The amorphous film was suddenly crystallized at 200°C by heating in vacuum. By the electron beam irradiation crystallization occurred at the focused electron beam region in the amorphous film. The growth process of crystallization by electron beam irradiation was recorded on a video image at the atomic resolution mode. The growth front of crystallization showed nano-concave and -convex shapes. The recrystallization with the different orientation at the first grown crystal have been found, and discussed as the influence of remaining antimony crystallites at the first crystallized film region.     

Growth of InAs on GaAs(1 0 0) by low-pressure metalorganic chemical vapor deposition employing in situ generated arsine radicals

InAs was grown by low-pressure metalorganic chemical vapor deposition on vicinal GaAs(1 0 0) substrates misoriented by 2° toward [0 0 1]. We observed InAs crystal growth, at substrate temperatures down to 300°C, employing in situ plasma-generated arsine radicals as the arsenic source. The in situ generated arsine was produced by placing solid arsenic downstream of a microwave driven hydrogen plasma. Trimethylindium (TMIn) feedstock carried by hydrogen gas was used as the indium source. The Arrhenius plot of InAs growth rate vs. reciprocal substrate temperature displayed an activation energy of 46.1 kcal/mol in the temperature range of 300–350°C. This measured activation energy value is very close to the energy necessary to remove the first methyl radical from the TMIn molecule, which has never been reported in prior InAs growth to the best of authors’ knowledge. The film growth mechanism is discussed. The crystallinity, infrared spectrum, electrical properties and impurity levels of grown InAs are also presented.     

Nucleation and ripening of seeded InAs/GaAs quantum dots

We have investigated the nucleation and ripening of pairs of InAs/GaAs quantum dot layers separated by thin (2–20 nm) GaAs spacer layers. Reflection high energy electron diffraction (RHEED) measurements show that the 2D–3D transition in the second layer can occur for less than 1 monolayer deposition of InAs. Immediately after the islanding transition in the second layer chevrons were observed with included angles as low as 20° and this angle was seen to increase continuously to 45±2° as more material was deposited. Atomic force microscopy showed the dot density in both layers to be the same. It is proposed that surface morphology can radically alter processes that determine the nucleation and ripening of the 3D islands.     

Crystallization kinetics of the borax decahydrate

The growth and dissolution rates of borax decahydrate have been measured as a function of supersaturation for various particle sizes at different temperature ranges of 13 and 50 °C in a laboratory-scale fluidized bed crystallizer. The values of mass transfer coefficient, K, reaction rate constant, k_r and reaction rate order, r were determined. The relative importances of diffusion and integration resistance were described by new terms named integration and diffusion concentration fraction. It was found that the overall growth rate of borax decahydrate is mainly controlled by integration (reaction) steps. It was also estimated that the dissolution region of borax decahydrate, apart from other materials, is controlled by diffusion and surface reaction. Increasing the temperature and particle size cause an increase in the values of kinetic parameters (K_g, k_r and K). The activation energies of overall, reaction and mass transfer steps were determined as 18.07, 18.79 and 8.26 kJmol⁻¹, respectively.     

Porous crystal structures obtained from directionally solidified eutectic precursors

Interconnecting cage-like porous structures of several halide compounds were prepared by the selective leaching of one eutectic phase method. The binary eutectic precursors were prepared by directional solidification using the Bridgman crystal growth technique. Porous NaMgF₃ (40% pore volume), CaF₂ (57% pore volume) and BaF₂ (43% pore volume) crystals were obtained after water leaching the NaF component of the directionally solidified NaF/NaMgF₃, NaF/CaF₂ and NaF/BaF₂ eutectics with the appropriate entangled microstructure. The growth conditions for eutectic-coupled growth and the morphology of the eutectics have been determined. In the coupled growth regime, the size of the eutectic phases “λ” is fairly uniform and varies with the eutectic growth rate “v” as λ²v=constant, which allows us to control the pore size within the 0.5–10 μm range. The simplicity and versatility of the eutectic growth also allows us to fabricate highly aligned porous structures at relatively high production rates.     

Effects of growth temperature on the properties of ZnO/GaAs prepared by metalorganic chemical vapor deposition

A series of ZnO films were grown on GaAs(0 0 1) substrates at different growth temperatures in the range 250–720°C by metalorganic chemical vapor depostion. Field emission scanning electron microscopy was utilized to investigate the surface morphology of ZnO films. The crystallinity of ZnO films was investigated by the double-crystal X-ray diffractometry. The optical and electrical properties of ZnO films were also investigated using room-temperature photoluminescence and Hall measurements. Arrhenius plots of the growth rate versus reciprocal temperature revealed the kinetically limited growth behavior depending on the growth temperature. It was found that the surface morphology, structural, optical and electrical properties of the films were improved with increasing growth temperature to 650°C. All the properties of the film grown at 720°C were degraded due to the decomposition of ZnO film.     

Hydroxyapatite crystallization in the presence of acetaminophen

The effect of acetaminophen; a widely used analgesic and fever reducing medicine; in supersaturated solutions of calcium phosphate was investigated under plethostatic conditions, at 37 °C, 0.15 M NaCl, pH 7.40. The rates of crystal growth measured in the presence of acetaminophen 1.654×10⁻⁴ mol dm⁻³ to 6.616×10⁻⁴ mol dm⁻³ were reduced by 43% to 79%, respectively. The inhibition effect on the crystal growth rate may be explained through adsorption onto the active growth sites. Kinetic analysis suggested Langmuir-type adsorption of acetaminophen on the HAP surface with a affinity value of 2.4×10⁻⁴ dm³ mol⁻¹, for the substrate in the concentration range investigated. The electrophoretic mobility measurements showed that in the presence of acetaminophen the charge of the acetaminophen covered HAP particles was shifted to more negative values as compared to bare HAP. In the presence of acetaminophen no changes observed in the HAP overgrown morphology or in the apparent order of crystallization.     

Growth and characterization of epitaxial layers on aluminum nitride substrates prepared from bulk, single crystals

A comparative study of epitaxy of AlN, GaN and their alloys, grown on c-axis and off-axis substrates of single-crystal aluminum nitride has been carried out. Growth on off-axis (>30°) substrates appears to result in rough surfaces and the absence of two-dimensional electron gas (2DEG). However, smooth morphologies were demonstrated for both homoepitaxial and heteroepitaxial growth on on-axis (<2°) substrates. On one of these oriented substrates a 2DEG, with a mobility of 1000 cm²/V s and a sheet density of 8.5×10¹² cm⁻² at room temperature, was also demonstrated for the first time.     

Structure of nanocrystalline ammonothermal GaN in dependence of temperature and type of acidic mineralizer

This study investigated ammonothermal synthesis of nanocrystalline gallium nitride (GaN) in supercritical ammonia with acidic mineralizers NH₄X (X=Cl, Br, I) at 400–500 °C. Results showed that three types of acidic mineralizers could effectively accelerate the formation of GaN. The mixed hexagonal/cubic phase fractions and lattice parameters of nanocrystalline GaN were calculated by the Rietveld refinement method. SEM showed an agglomerate of nanocrystalline GaN. A considerable amount of GaN was synthesized using NH₄Cl as the mineralizer, however, there was no yield using NH₄Br or NH₄I at 400 °C. For acidic mineralizers, both hexagonal structures (wurtzite) and cubic structures (zincblende) were obtained in ammonothermal synthesis by XRD and Raman measurement. GaN synthesized with NH₄Br and NH₄I showed mixed phases of hexagonal-GaN (h-GaN) and cubic-GaN (c-GaN) at 450–500 °C. In the case of NH₄Cl mineralizer, GaN only exhibited mixed phases of h-GaN and c-GaN at 500 °C, but pure h-GaN at 400–450 °C. Based on the results, NH₄Cl favored pure h-GaN, and NH₄Br and NH₄I favored c-GaN at 400–450 °C.