Crystal growth rate limited by step length — the case of oxygen-deficient TiO2 exposed to oxygen

We study how an oxygen-deficient crystal of TiO₂ crystal grows when exposed to O₂. While the O flux is external to the crystal, the Ti flux necessary for growth comes from internal (bulk) interstitials (Phys. Rev. Lett. 76 (1996) 791). We address where the reaction between O and Ti to form new crystal takes place in the regime of pure step flow (i.e., surface steps advancing without new-layers nucleating). The detailed partitioning of the growth flux among individual surface steps is studied using low-energy electron microscopy for two geometries on the (110) surface—an array of islands on a terrace and an island stack generated from a dislocation source. For both geometries, the areas of islands larger than the critical size grow at rates strictly proportional to their perimeter length, independent of the local step configuration. In addition, we find that the growth rate is proportional to the O₂ pressure. The step flow represents a simple limiting case of crystal growth (Phil. Trans. R. Soc. A. 243 (1951) 299)—only the growth species near a step edge becomes incorporated into the crystal. That is, only Ti and O reactions near the step edge lead to crystal growth. This case is in marked contrast to crystal growth controlled by species attaching to terraces and diffusing to steps, for which the growth rates depend upon the local step environment. Indeed, simulating the island array as if the growth flux was partitioned among the individual islands by concentration gradients (i.e., diffusion-controlled growth) totally failed to reproduce the experimental rates.     

Resistivity distribution of silicon single crystals using codoping

Numerous studies including continuous Czochralski method and double crucible technique have been reported on the control of macroscopic axial resistivity distribution in bulk crystal growth. The simple codoping method for improving the productivity of silicon single-crystal growth by controlling axial specific resistivity distribution was proposed by Wang [Jpn. J. Appl. Phys. 43 (2004) 4079]. Wang [J. Crystal Growth 275 (2005) e73] demonstrated using numerical analysis and by experimental results that the axial specific resistivity distribution can be modified in melt growth of silicon crystals and relatively uniform profile is possible by B–P codoping method. In this work, the basic characteristic of 8 in silicon single crystal grown using codoping method is studied and whether proposed method has advantage for the silicon crystal growth is discussed.     

Phase‐field simulation of dendrite growth under forced flow conditions in an Al–Cu welding molten pool

A quantitative phase‐field model for directional solidification is applied to study dendrite growth under forced flow conditions in an Al‐Cu Gas Tungsten Arc (GTA) welding molten pool. Evolution of the dendrite morphology and the solute field under forced flow conditions is simulated. Growth of columnar grains goes through three periods, including the initial instability period, the competitive growth period and the relatively stable period. The solute segregation, the solute redistribution and the solute concentration in the liquid side of the interface are investigated, respectively. For the given conditions, simulation results are in good agreement with experimental findings.     

Polyamorphism: Path to new high density glasses at ambient conditions

Polyamorphism is defined as the possibility for an amorphous material to exist with different structures. This has been demonstrated in solids for ice [O. Mishima, Y. Suzuki, Nature 419 (2002) 599], amorphous silicon [P.F. McMillan, M. Wilson, D. Daisenberger, D. Machon, Nature 4 (2005) 680], amorphous germanium and several oxide glasses [M. Grimsditch, Phys. Rev. 52 (1984) 2379, J.P. Itie, A. Polian, G. Calas, J. Petiau, A. Fontaine, H. Tolentino, Phys. Rev. 63 (1989) 398, C.H. Polsky, K.H. Smith, G.H. Wolf, J. Non-Cryst. Solids 248 (1999) 159, J. Nicholas, S Sinogeikin, J. Kieffer, J. Bass, Phys. Rev. Lett. 92 (2004) 215701, O. Majérus, L. Cormier, J.P. Itié, L Galoisy, D.R. Neuville, G. Calas, J. Non-Cryst. Solids 345&346 (2004) 34]: SiO₂, GeO₂, B₂O₃, SiO₂–GeO₂. Here we discuss the hysteresis curves corresponding to the evolution of the Raman bands as function of pressure for oxide glasses and compare it with ab-initio or molecular dynamics simulations [L. Huang, J. Kieffer, Phys. Rev. B 69 (2004) 224203, L. Huang, J. Kieffer, Phys. Rev. B 69 (2004) 244204, M. Durandurdu, Phys. Rev. B 73 (2006) 035209]. We show that these curves correspond for most of the glass studied to an irreversible change in the medium range order at ambient pressure. For a particular three component glass La₂O₃–B₂O₃–GeO₂ (LBG) we demonstrate that this irreversibility occurs if the pressure is much higher than the in situ phase transformation pressure. It is predicted that this behaviour is general for glasses, leading to the possibility to recover new high density glass polymorphs in ambient conditions of temperature and pressure.     

New analysis of neutron-lifetime experiments

The experiments on measuring the neutron lifetime have been analyzed. The newest and most exactly measured neutron lifetime [Phys. Lett. B 605, 72 (2005)] (878.5 ± 0.8 s) differs from the world average value [Phys. Lett. B 667, 1 (2008)] (885.7 ± 0.8 s) by 6.5 standard deviations. In this context, an analysis and Monte Carlo simulation of the experiments [Phys. Lett. B 483, 15 (2000)] and [Phys. Rev. Lett. 63, 593 (1989)] have been performed. Systematic errors of about −6 s are found in both experiments. A table with the results of measuring the neutron lifetime is presented with corrections and additions. The new world average value for the neutron lifetime is found to be 880.0 ± 0.9 s.     

Growth and photoluminescence properties of vertically aligned SnO2 nanowires

Vertically aligned SnO₂ nanowires (NWs) were grown for the first time by a vapor–liquid–solid method on c-sapphire with gold as a catalyst under Ar gas flow. Electron backscatter diffraction analysis indicated the NWs are single crystalline having the rutile structure, grow vertically along the [1 0 0] direction, and exhibit a consistent epitaxial relationship where lattice mismatch is estimated to be 0.3% along the SnO₂ [0 1 0] direction. The growth of these NWs is sensitive to many parameters, including growth duration, substrate type, source vapor concentration, and the thickness of the catalyst layer. Photoluminescence measurements at room temperature showed that the vertically aligned NWs exhibit an intense transition at 3.64 eV, a near band-edge transition which is rarely observed in SnO₂.     

Modulation of dendrite growth of cuprous oxide by electrodeposition

Cuprous oxides with different dendrite morphologies were formed on F-doped tin oxide (FTO) covered glass substrates by potentiostatic deposition of cupric acetate. The effects of pH value (varied from 5.00 to 5.80) of electrolytes on the crystal morphologies of cuprous oxide were studied. Different crystal morphologies of cuprous oxides were obtained by the change of velocity of vertical growth and lateral growth through varying the pH value of electrolyte. The processes of Cu₂O dendrite crystal growth were analyzed through SEM images at different deposition times. Photoelectrochemical properties of the Cu₂O thin films prepared in the system are also studied.     

The growth of mixed alkaline-earth fluorides for laser host applications

A comprehensive analysis is implemented concerning the growth, properties, and applications of doped-co-doped single and mixed alkali earth fluoride systems. Calcium-strontium fluoride solid solutions with a Sr content proportion varying widely between 0.007 and 0.675 mol.% are obtained as a batch of axis-symmetrical boules grown by a Bridgman-Stockbarger (BS) method. The crystallization front (CF) can be controlled to retain a convex CF-shape that is favourable for normal growth of single crystals. This achieved using a broad adiabatic furnace zone (AdZ) independently of the boules’ composition. The influence of the thermal field distribution on the CF and the real crystallization rate (CR), which are both critically decisive in controlling crystal quality, were originally assessed using empirically derived formulas. The optical characteristics of the grown boules were monitored by measuring the external transmittance t and calculating the total losses following light irradiation of optical windows that were prepared from sections of the boules that had been cut parallel to one another. The t-measurements were performed by two different techniques and the comparative analysis of the results reliably indicates any inhomogeneity in the grown boules. A simple supercooling criterion proved to closely relate the morphological stability of the CF enabling one to set up the optimum growth conditions. Thus the normal growth criterion outlines the concentration bounds where the isotropic growth mechanism is replaced by cellular anisotropic growth. A procedure has been established for provisioning researchers with optical quality calcium-strontium fluoride crystals with widely varying composition grown under practically identical conditions. As a consequence one can explore possible reasons that can affect the growth mechanism for this or any other systems with a fluoride structure and so provide scope aimed at the future improvement of the crystal quality thereby enlarging the field of mixed fluoride systems’ applications.     

Effect of a vertical magnetic field on the dendrite morphology during Bridgman crystal growth of Al–4.5 wt% Cu

The effect of a vertical high magnetic field (up to 10 T) on the dendrite morphology has been investigated during Bridgman growth of Al–4.5 wt%Cu alloys experimentally. It is found that the field causes disorder in dendrites and their tilt in orientation. Along with the increase of the magnetic field and decrease of the growth velocity, the dendrites became broken and orientated in 1 1 1 along the direction of solidification instead of 1 0 0. The field also enlarged the primary dendrite spacing and promoted the branching of the dendrites to form high-order arms. Above phenomena are attributed to the thermoelectromagnetic convection effect and orientation caused by the high magnetic field.     

Development of dendrite array growth during alternately changing solidification condition

To investigate competitive growth in a dendrite array a directional solidification study was carried out on a succinonitrile–acetone alloy. In the experiment the temperature gradient G applied is alternately altered over a wide range, increased from a lower to a higher limit, and then decreased back to the lower one. It was found that source dendrites, i.e. parent dendrites, are not superior to derived dendrites in terms of growth competition. The orientation deviation between neighbouring dendrites impacts both local dendrite creation and elimination. At lower gradients, the new dendrites grow out from the ternary arms, while at the higher gradients new dendrites originate directly from the secondary arms. During increasing and decreasing G, average primary dendrite spacing λ measured traces out different paths, revealing an unclosed hysteresis loop in the λ–G-diagram.     

Growth of equiaxed dendritic crystals settling in an undercooled melt,Part 1: Tip kinetics

Experiments are conducted to measure the dendrite tip growth velocities of equiaxed crystals of the transparent model alloy succinonitrile–acetone that are settling in an undercooled melt. The tip velocities are measured as a function of the crystal settling speed and the Eulerian angle between the dendrite arms and the flow direction relative to the crystal. The ratio of the settling speed (or flow velocity) to the tip growth velocity ranges from 62 to 572. The ratio of the measured tip velocity to that predicted from a standard diffusion theory for free dendritic growth ranges from almost zero for dendrite tips growing in the wake of the crystal, about unity for dendrite tips with an orientation close to normal to the flow direction, and up to two for dendrite tips growing into the flow. Despite the relatively strong flow relative to the crystal, the average tip growth velocity of the six primary dendrite arms of an equiaxed crystal is found to be in excellent agreement with the standard diffusion theory result. The individual tip velocities are correlated using a boundary layer model of free dendritic growth in the presence of melt flow that is modified to account for the flow angle dependence. Using the same dendrite tip selection parameter, σ^*, as established previously under purely diffusive conditions (0.02), good agreement is achieved between the measured and predicted tip velocities. The model is also found to predict well the variations in the tip velocity that occur during settling due to crystal rotation and settling speed changes.     

Shape evolution of zinc oxide from twinned disks to single spindles through solvothermal synthesis in binary solvents

Shape evolution of ZnO crystals from twinned disks to single spindles was studied through solvothermal synthesis in binary solvents N,N-diethylformamide (DEF) and methanol (MeOH). The MeOH content in DEF had large influence on the morphology of the obtained ZnO crystals. In MeOH-free DEF, well-shaped ZnO twinned disks with perfect mirror symmetry could be formed through the assembly of ZnO₄⁶⁻–julolidinium–ZnO₄⁶⁻ growth units on the (0 0 0 1) growth interfaces. For small amounts of MeOH (MeOH/DEF=0.04), elongated twinned disks were formed since the growth along the polar c-axis was enhanced. With increasing MeOH content (MeOH/DEF=0.1), twinned rods with reduced mirror symmetry were formed. When a large amount of MeOH was added to DEF (MeOH/DEF=0.5), single spindles rather than twinned disks or twinned rods were obtained. A similar shape evolution of zinc oxide was observed in binary solvents DEF and N,N-dimethylformamide (DMF), suggesting that the growth of ZnO crystals with tuneable shape and size can be controlled by the composition of the binary solvent mixture.     

Columnar grain growth pattern with fluid flowing in molten pool

A coupled model was used to simulate columnar grain growth in TIG (tungsten inert‐gas) molten pool of nickel base alloy. The cellular automaton algorithm for dendritic growth is incorporated with solute transport model to take fluid flow into consideration. The results indicate that shear flow changes the solute distribution at the S/L (Solid/Liquid) interface, leading to asymmetrical growth of columnar grains. The dendrite arms on the upstream side grow fast, while the growth of dendrite arms on the downstream side is much delayed. However, dendrite arms on both sides are not as well‐developed as the grain growth without flow. With inlet flow velocity increasing, the phenomenon becomes more obvious. In addition, shear flow also results in more severe coring segregation. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optimization of the mineral content in polymeric gels: The effect of calcium to phosphate molar ratio

The influence of calcium to phosphate (Ca/P) molar ratio on the extent of mineralization in a model (poly)acrylamide gel was investigated under simulated physiological conditions. We hypothesized that the optimal growth of hydroxyapatite crystals will take place at the stoichiometric Ca/P molar ratio of 1.67. Phosphate ions were incorporated during the polymerization of the gel and mineralization was initiated by submersion of the gel in calcium acetate solution. Ca/P molar ratios were varied in the range of 0.5–5.0. The mineralized gel was characterized by Raman spectroscopy, scanning electron microscopy (SEM) and mineral weight fraction analysis via ashing. Raman spectra captured across the bulk of the gels indicated the presence of mineral at the core section. The phosphate symmetric stretching peak was observed in the range of 955–960 cm⁻¹ which is characteristic of hydroxyapatite. SEM images showed that crystals formed at Ca/P=2.0 were denser and larger in size than at other molar ratios. In agreement with SEM images, the dry weight fraction of mineral reached the maximum at the molar ratio of 2.0 and the extent of mineralization rapidly declined as the molar ratio diverged from 2.0. Also, the crystallinity of the mineral was optimum at the molar ratio of 2.0. Thus it appears that for effective mineralization, the molar ratio of the two ions needs to be in excess of the stoichiometric requirement, suggesting that ions are expended in processes other than the formation and growth of hydroxyapatite crystals. Therefore, the optimal level of mineralization in biomimetic-based growth of calcium phosphate crystals in sol–gel environment requires consideration of a range of molar ratios as opposed to using the molar ratios corresponding to that of the crystal species intended to grow.     

Effect of NH3 on the growth characterization of TiN films at low temperature

Titanium nitride (TiN) films were obtained by the atmospheric pressure chemical vapor deposition method of the TiCl₄–N₂–H₂ system with various flow rates of NH₃ at 600°C. The growth characteristics, morphology and microstructure of the TiN films deposited were analyzed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Without NH₃ addition, no TiN was deposited at 600°C as shown in the X-ray diffraction curve. However, by adding NH₃ into the TiCl₄–N₂–H₂ system, the crystalline TiN was obtained. The growth rate of TiN films increased with the increase of the NH₃ flow rate. The lattice constant of TiN films decreased with the increase of the NH₃ flow rate. At a low NH₃ flow rate, the TiN (2 2 0) with the highest texture coefficient was found. At a high NH₃ flow rate, the texture coefficient of TiN (2 0 0) increased with the increase of the NH₃ flow rate. In morphology observation, thicker plate-like TiN was obtained when the NH₃ flow rate was increased. When the flow rate of NH₃ was 15 sccm, Moiré fringes were observed in the TiN film as determined by TEM analysis. The intrinsic strain was found in the TiN film as deposited with 60 sccm NH₃.     

In-situ visualization of a super-accelerated synthesis of zinc oxide nanostructures through CO2 laser heating

A simple growth technique capable of growing a variety of zinc oxide (ZnO) nanostructures with record growth rates of 25 μm/s is demonstrated. Visible lengths of ZnO nanowires, nanotubes, comb-like and pencil-like nanostructures could be grown by employing a focused CO₂ laser-assisted heating of a sintered ZnO rod in ambient air, in few seconds. For the first time, the growth process of nanowires was videographed, in-situ, on an optical microscope. It showed that ZnO was evaporated and presumably decomposed into Zn and oxygen by laser heating, reforming ZnO nanostructures at places with suitable growth temperatures. Analysis on the representative nanowires shows a rectangular cross-section, with a [0 0 0 1] growth direction. With CO₂ laser heating replacing furnace heating used conventionally, and using different reactants and forming gases, this method could be easily adopted for other semiconducting inorganic nanostructures in addition to ZnO.     

Analysis of SiC crystal sublimation growth by fully coupled compressible multi-phase flow simulation

A fully coupled compressible multi-phase flow solver was developed to effectively design a large furnace for producing large-size SiC crystals. Compressible effect, convection and buoyancy effects, flow coupling between argon gas and species, and the Stefan effect are included. A small and experimental furnace is used to validate the solver. First, the essentiality of 2D flow calculation and the significance of incorporating buoyancy effect and gas convection, the Stefan effect, and flow interaction between argon gas and species were investigated by numerical results. Then the effects of argon gas on deposition rate, growth rate, graphitization on the powder source, and supersaturation and stoichiometry on the seed were analyzed. Finally, the advantages of an extra chamber design were explained, and improvement of growth rate was validated by the present solver.     

MOVPE growth of grade-strained bulk InGaAs/InP for broad-band optoelectronic device applications

In this paper we present a novel growth of grade-strained bulk InGaAs/InP by linearly changing group-III TMGa source flow during low-pressure metalorganic vapor-phase epitaxy (LP-MOVPE).The high-resolution X-ray diffraction (HRXRD) measurements showed that much different strain was simultaneously introduced into the fabricated bulk InGaAs/InP by utilizing this novel growth method. We experimentally demonstrated the utility and simplicity of the growth method by fabricating common laser diodes. As a first step, under the injection current of 100 mA, a more flat gain curve which has a spectral full-width at half-maximum (FWHM) of about 120 nm was achieved by using the presented growth technique. Our experimental results show that the simple and new growth method is very suitable for fabricating broad-band semiconductor optoelectronic devices.