In2O3 nanorod arrays grown at grain-boundary triple junctions of Cu–Sn alloy substrate

In this article, an alternative method for site-specific growth of In₂O₃ nanorod arrays, which relies on the vapor–liquid–solid growth mechanism, is demonstrated using Cu–Sn (5 at% Sn) alloy as substrate. By annealing Cu–Sn alloy slightly below the solidus line, grain-boundary triple junctions can be wetted preferentially. As a result, the catalyzing Cu droplets will be present at the sites of grain-boundary triple junctions, which will control the growth of In₂O₃ nanorods at defined locations. This growth technique provides a cost-effective and simple approach to fabricate ordered nanorod arrays with the sites controlled, which may benefit nanorod device applications.     

Non-isothermal crystallization kinetics of ZnO-BaO-B2O3-SiO2 glass

Glass of composition 40SiO₂-30BaO-20ZnO-10B₂O₃ (mol%) was made by conventional melting and casting process. Crystallization kinetics of above glass has been investigated under non-isothermal conditions, using the formal theory of transformations for heterogeneous nucleation. The procedure is applied to the experimental data obtained by differential thermal analysis (DTA), using continuous-heating techniques. The crystallization results are analyzed, and both the activation energy of crystallization process as well as the crystallization mechanism is characterized. Dilatometric measurement of this glass was also done and data obtained was used to calculate the viscosity of the formed glass. Development of crystalline phases on thermal treatments of the glass at various temperatures has been analyzed by X-ray diffraction. Microstructure of the crystalline phases was investigated by scanning electron microscopy (SEM) and the development of various structural features with variation in heat treatment cycle was observed. The nucleation and growth of these phases in the matrix of glass has been described and discussed.     

Precipitation of nanostructured calcite in a controlled multiphase process

The way of conducting the precipitation process is crucial for the final product properties and its further applications. In the presented experiments, CaCO₃ powders were produced by controlled fast precipitation through gaseous CO₂ absorption in Ca(OH)₂ slurry. This multiphase reaction was conducted in a new rotating disc reactor unit, which enables one to control inter- and intra-face mass and energy transfer as well as the macro- and micro-mixing effects in the reacting system. The effect of calcium hydroxide concentration, mixing conditions in the reactor and gas–liquid interface development at discs surface on precipitated CaCO₃ was investigated.     

Tin valence and local environments in silicate glasses as determined from X-ray absorption spectroscopy

X-ray absorption spectroscopy (XAS) was used to characterize the tin (Sn) environments in four borosilicate glass nuclear waste formulations, two silicate float glasses, and three potassium aluminosilicate glasses. Sn K-edge XAS data of most glasses investigated indicate Sn⁴⁺O₆ units with average Sn-O distances near 2.03 Å. XAS data for a float glass fabricated under reducing conditions show a mixture of Sn⁴⁺O₆ and Sn²⁺O₄ sites. XAS data for three glasses indicate Sn-Sn distances ranging from 3.43 to 3.53 Å, that suggest Sn⁴⁺O₆ units linking with each other, while the 4.96 Å Sn-Sn distance for one waste glass suggests clustering of unlinked Sn⁴⁺O₆ units.     

Decisive role of Au layer on the oriented growth of ZnO nanorod arrays via a simple aqueous solution method

Vertically aligned arrays of ZnO nanorod were synthesized on the Au/SiO₂/Si(1 0 0) substrate by a simple aqueous solution growth process, without pre-prepared ZnO seed layer. For comparison, glass and SiO₂/Si were also used as substrates, and the results show that the Au layer plays a decisive role in orienting the growth of the ZnO nanorod. The effects of other growth parameters, including Zn²⁺ concentration and growth time, on morphology, density, and orientation of the ZnO nanostructure were also studied and with longer reaction time, a new structure namely ZnO nanotip was obtained. Moreover, the growth mechanism of ZnO nanorod arrays grown on the Au/SiO₂/Si substrate was proposed.     

Influence of growth temperature on the selective area MOVPE of InAs nanowires on GaAs (1 1 1) B using N2 carrier gas

The influence of temperature on selective area (SA) InAs nanowire growth was investigated for metal-organic vapor phase epitaxy (MOVPE) using N₂ as the carrier gas and (1 1 1) B GaAs substrates. In contrast to the growth temperature range – below 600 °C – reported for hydrogen ambient, the optimal growth temperature between 650 and 700 °C was 100 K higher than the optimal ones for H₂ carrier gas. At these temperatures, nanowires with aspect ratios of about 80 and a symmetric hexagonal shape were obtained. The results found are attributed to the physical and chemical properties of the carrier gas.     

Crystal growth and characterization of GaCrN nanorods on Si substrate

GaCrN nanorods were grown on GaN nanorods by RF-plasma-assisted molecular beam epitaxy. GaN nanorods were grown on Si (0 0 1) substrates with native SiO₂. Cr doping into GaCrN nanorods was conducted at substrate temperatures of 800 and 550 °C. Cross-sectional transmission electron microscopy images revealed that the diameter of GaCrN nanorod gradually increases with growth proceeding at 550 °C, while the growth at 800 °C does not change the nanorod diameter. Low-temperature growth enhances the growth perpendicular to the c-axis and decreases the growth along the c-axis. It was found that the solubility limit of Cr atoms in GaCrN is much higher for the low-temperature growth than for the high-temperature growth. It was also found that the highest saturation magnetization is obtained at some optimum Cr cell temperature.     

Synthesis of crystalline TiO2 nanostructure arrays by direct microwave irradiation on a metal substrate

We report a method for synthesizing TiO₂ nanostructures by applying microwave irradiation (1200 W, 2.45 GHz, single-mode) to a Ti substrate under an atmosphere comprising of O₂ and Ar. After 1200 W microwave irradiation, one-dimensional (1D) nanostructure arrays were synthesized on the surface of the substrate. The average dimensions of the 1D structures were 200 nm in length and 30 nm in diameter. The structures were single crystalline. The EDX elemental maps of the areas examined using HAADF-STEM demonstrated that Ti and O were distributed homogeneously throughout the nanostructure. Quantitative analysis of the mean atomic ratios in the nanostructures disclosed a Ti:O ratio of 0.331:0.669. XPS analysis demonstrated that the predominant oxidation state of Ti in the samples was +4. On the basis of these results, we propose a possible mechanism for the formation of the TiO₂ nanostructures via microwave irradiation.     

Templated cocrystallization of cholesterol and phytosterols from microemulsions

A major cause of cardiovascular disease is high cholesterol (CH) levels in the blood, a potential solution to which is the intake of phytosterols (PS) known as CH-reducing agents. One mechanism proposed for PS activity is the mutual cocrystallization of CH and PS from dietary mixed micelles (DMM), a process that removes excess CH from the transporting micelles. In this study, microemulsions (MEs) were used both as a model system for cocrystallization mimicking DMM and as a possible alternative pathway, based on the competitive solubilization of CH and PS, to reduce solubilized CH transport levels from the ME. The effects of different CH/PS ratios, aqueous dilution, and lecithin-based MEs on sterol crystallization were studied. The precipitated crystals from the ME-loaded system with PS alone and from that loaded with 1:1 or 1:3 CH/PS mixtures were significantly influenced by ME microstructure and by dilution with aqueous phase (X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC) results). No new polymorphic structures were detected apart from the corresponding sterol hydrates. Mixed crystal morphology and the habit of the precipitated sterols were strongly affected by the CH/PS ratio and the structures of the diluted ME. As the amount of PS in the mixture increased or as the ME aqueous dilution proceeded, precipitated crystal shape became more needle-like. The mixed sterols seemed to be forming eutectic solids.     

Structural and optical properties of single-crystal ZnMgO thin films grown on sapphire and ZnO substrates by RF magnetron sputtering

High-quality ZnMgO films were grown by the radio frequency (RF) magnetron sputtering technique in pure oxygen ambient. Single-crystal films were obtained, when the Mg concentration was Zn_0.87Mg_0.13O or lower in the case of ZnMgO/Al₂O₃ and when it was Zn_0.65Mg_0.35O or lower in the case of ZnMgO/ZnO. Polycrystalline films were obtained when the growth temperature was lower than 500 °C, regardless of the Mg concentration. Position of the photoluminescence (PL) ultraviolet (UV) peak of the ZnMgO film shifted with the addition of Mg, from 3.33 eV (ZnO) to 3.51 eV (Zn_0.87Mg_0.13O) and 3.70 eV (Zn_0.65Mg_0.35O). It was also observed that growth of the ZnMgO films at higher temperature resulted in higher band-gap energy. It was proposed that this phenomenon is because concentration of the substitutional Mg atoms occupying Zn site is increased as the growth temperature increases.     

Effect of annealing and composition on crystal structure,surface morphology and optical absorption of chemically deposited Cd1‐xSnxS films

Cd_1‐xSn_xS thin films were successfully deposited on suitably cleaned glass substrate by chemical bath deposition method at 74 °C. Hydrated Stannous Chloride (SnCl₂.2H₂O) in aqueous solution was added to the CdS growing solution in different proportions. The experimental results indicate, a successful doping for lower concentration of Sn, saturation for intermediate doping levels, and a degradation of the doping process for higher concentration of Sn. Indirect (X‐ray diffraction) and Direct (Scanning electron microscopy) measurements were performed to characterize the growth and the nature of crystallinity of the different Cd_1‐xSn_xS films. The effect of annealing on the crystal structure and morphology of the deposited films has also been discussed. The X‐ray diffraction spectra show that the thin films are polycrystalline and have both cubic and hexagonal structure. The Interplanar spacing, lattice constant, grain size, strain, and dislocation density were calculated for as‐deposited and annealed films. The grain size was found to decrease from 5 nm to 0.89 nm with doping concentration of Sn. The grain size further decreased due to annealing at 400 °C. SEM studies show layered growth and long needle like structures along with some voids. After annealing the densification and smaller size of the particles was also observed. The optical absorption spectra show shifting of absorption peaks towards lower wavelength side (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Fabrication and photocatalytic property of ZnO/SrTiO3 core/shell nanorod arrays

ZnO/SrTiO₃ core/shell nanorod arrays were fabricated by a facile two‐step method. ZnO nanorod arrays were first hydrothermally grown on Si substrate. Then, using liquid phase deposition method, SrTiO₃ were deposited onto the ZnO nanorods to form core/shell nanorod structures. The morphologies and structures of the products were characterized by scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction. The photocatalytic behavior of the nanorod arrays was also examined through the photodegradation of methylene blue solution under UV irradiation. It was found that the core/shell nanorod arrays with deposition time of 10 min showed higher photocatalytic activity than bare ZnO nanorod arrays. This enhancement was attributed to the efficient charge separation at the ZnO/SrTiO₃ interface.     

Structural characterization of phosphate glasses doped with silver

The present paper reports the influence of silver oxide addition on the local structure of 2P₂O₅ · CaO · 0.05ZnO glass matrix. The glass samples were investigated through several methods: X-ray powder diffraction (XRD), scanning electron microscopy (SEM), infrared absorption (FT-IR) and Raman scattering. The X-ray diffraction patterns confirm the vitreous character of these samples over the explored compositional range and the SEM pictures confirm this information. The phosphate structural units of the network former are assessed from FT-IR and Raman spectra as ultra-, meta-, pyro- and orthophosphate units. A slight structural depolymerization process of these phosphate-based glasses was evidenced for higher silver oxide content. In vitro behavior of the bulk glass sample with the highest silver oxide content was tested by immersion in simulated body fluid (SBF). X-ray diffraction and SEM measurements made on the SBF treated sample revealed growth of a crystalline phase on the surface sample.     

Growth temperature dependence in molecular beam epitaxy of gallium arsenide

Epitaxial layers of GaAs were grown on GaAs(100) at substrate temperatures ranging from 400° to 600°C by molecular beam epitaxy. Surface structures of the substrate and the epitaxial layers were investigated by means of low-energy electron diffraction. Two new structures of c(4 × 4) and c(8 × 8) were observed from layers grown at the low temperature of 400°C. The electrical and optical properties of layers doped with Si were investigated by measurement of Hall effect and photoluminescence as a function of growth temperature. It is found that a semi-insulating layer is grown below a critical temperature, and the layer is useful as a buffer layer for GaAs FET's. Variation of carrier concentration was observed near the interface between layers grown at different temperatures under a constant Sn beam flux. The effect is attributed to defect-induced segregation of Sn.     

Irradiation-induced changes in the local environment of Si and Al in LnSiAlON glasses as probed by Al and Si NMR

Two compounds have been studied: an oxide glass from the Y-Si-Al-O system and an oxynitride glass from the Y-Si-Al-O-N system, both bombarded with Sn-ions (975 MeV, fluences ranging from 10¹² to 2.7 × 10¹³ Sn/cm²). The changes in the environment of the silicon and the aluminium were investigated using NMR spectroscopy. Irradiation by Sn ions leads to a loss of nitrogen in the silicon and probably the aluminium environments. Part of the aluminium changes from a network former coordination to a network modifier coordination while the oxide silicate network exhibits a higher cross-linking due to an increase of the population of bridging oxygen. Part of the aluminium in five-fold coordination is formed at the expense of aluminium in six-fold coordination in the case of the oxynitride glass and the changes in the silicon environment occur at lower fluences than for the oxide glass.     

Preparation, phase transformation and microstructure of ZrxTi1−xO2 (x = 0.1-0.9) fine fibers

Zr_xTi_1−xO₂ (x = 0.1-0.9) fibers were prepared by the sol-gel dry-spinning method. Polyacetylacetonatozirconium (PAZ) and tetrabutyl titanate (C₁₆H₃₆O₄Ti) were used as raw materials. The green fibers were obtained from the amorphous spinnable solution and then heat-treated to convert into polycrystalline fibers. The main phase changes from TiO₂ to zirconium titanate (ZT) and then tetragonal ZrO₂ with increasing ZrO₂ content. The crystallization temperature varied with the molar ratio of Zr:Ti. The heat-treated fibers at 1050 °C have few pores and no cracks with diameters of 10-20μm and lengths of 1-5 cm.     

Influence of metal organic and inorganic precursors on spray pyrolyzed ceramic MgO (2 0 0) thin films for epitaxial over layers

The MgO (2 0 0) surface is widely used as a substrate for epitaxial growth of superconducting and ferro-electric films. Highly oriented, single crystalline, extremely flat and transparent MgO films have been successfully deposited on quartz substrates by the chemical spray pyrolysis technique using economically viable metal organic and inorganic precursors under optimized conditions at the substrate temperature of 600 °C. Thermal analysis (TGA/DTA) in the temperature range 30-600 °C with the heating rate of 10 °C/min revealed the decomposition behavior of the precursors and confirmed the suitable substrate temperature range for film processing. The heat of reaction, ΔH due to decomposition of metal organic precursor contributed additional heat energy to the substrate for better crystallization. The intensity of the (2 0 0) peak in X-ray diffraction (XRD) measurements and the smooth surface profiles revealed the dependency of precursor on film formation. The compositional purity and the metal-oxide bond formation were tested for all the films. UV-Vis-NIR optical absorption in the 200-1500 nm range revealed an optical transmittance above 80% and the absorption edge at about 238 nm corresponding to an optical band gap E_g = 5.25 eV. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) micrographs of MgO films confirmed better crystallinity with larger grain size (0.85 μm) and reduced surface roughness (26 nm), respectively.     

Effect of BaO on the crystallization kinetics of glasses along the Diopside-Ca-Tschermak join

We report on the effect of BaO on the crystallization kinetics of glasses in the diopside (CaMgSi₂O₆)-Ca-Tschermak (CaAl₂SiO₆) system. Partial substitution (i.e. 5%, 10% and 20%) of Ba²⁺ for Ca²⁺ was attempted in composition CaMg_0.8Al_0.4Si_1.8O₆, in three different glasses while partial substitution of B³⁺ for Al³⁺ was made in the fourth glass. Structural investigations on the glasses have been made by density measurements, molar volume and Infra-red spectroscopy (FTIR). Non-isothermal crystallization kinetic studies have been employed to study the mechanism of crystallization in all the four glasses. The Avrami parameter for the glass powders is ∼2, indicating the existence of intermediate mechanism of crystallization. Crystallization sequence in the glasses has been followed by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and FTIR. Augite crystallized out being the dominant phase in all the glass-ceramics, while different polymorphs of BaAl₂Si₂O8 were present as secondary or minor phases.     

Stacking pattern of multi-layer InAs quantum wires embedded in In0.53Ga0.47−xAlxAs matrix layers grown lattice-matched on InP substrate

Multi-layer InAs quantum wires were grown on, and embedded in In_0.53Ga_0.47−xAl_xAs (with x=0, 0.1, 0.3 and 0.48) barrier/spacer layers lattice matched to an InP substrate. Correlated stacking of the quantum wire arrays were observed with aluminum content of 0 and 0.1. The quantum wire stacks became anti-correlated as the aluminum content was increased to 0.3 and 0.48. The origin of such stacking pattern variation was investigated by finite element calculations of the chemical potential distribution for indium on the growth front surface of the capping spacer layer. It is shown that the stacking pattern transition is determined by the combined effect of strain and surface morphology on the growth front of the spacer layers.     

Synthesis and characterization of Bi3.15Nd0.85Ti3O12 nanotube arrays

Nd-substituted bismuth titanate (Bi_3.15Nd_0.85Ti₃O₁₂, BNT) nanotube arrays are fabricated by means of a sol–gel method utilizing porous anodic aluminum oxide (AAO) template. The morphologies and structures have been determined by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The diameter and length of these nanotubes are about 200 nm and 60 μm, respectively, and their wall thickness is about 30 nm. The average grain size is around 40 nm. XRD data show that the BNT nanotubes possess bismuth-layered perovskite structure. High-resolution electron microscopy (HRTEM) image demonstrates that the BNT nanotubes are polycrystalline. Polarization–electric field (P–E) response curves of BNT nanotube arrays were measured, and a size induced polarization reduction phenomenon is observed.