Synchrotron X-ray diffraction studies of heteroepitaxial ZnO films grown by pulsed laser deposition

Heteroepitaxial ZnO films were grown by pulsed laser deposition on various substrates such as GaN-buffered C-Al₂O₃, C-Al₂O₃, A-Al₂O₃, and R-Al₂O₃. The epitaxy nature of the films was investigated mainly by synchrotron X-ray diffraction. The results showed that the GaN interlayer plays a positive role in growing an unstrained, well-aligned epitaxial ZnO film on the basal plane of Al₂O₃. Importantly, the ZnO film grown on R-Al₂O₃ has two differently aligned domains. The dominant (1 1 0) oriented domain has much better alignment in the in-plane direction than the minor portion of (0 0 1) oriented domain, while in the out-of-plane direction the two domains have almost the same mosaic distribution.     

Study of the nucleation and growth of TiO2 and ZnO thin films by means of molecular dynamics simulations

The nucleation and growth of titanium dioxide (TiO₂) and zinc oxide (ZnO) thin films on Fe₂O₃ (hematite), Al₂O₃ (α-alumina) and SiO₂ (α-quartz) are studied by molecular dynamics simulations. The results show the formation of a strong interface region between the substrate and the film in the six systems studied here. A combination of polycrystalline and amorphous phases are observed in the TiO₂ films grown on the three substrates. ZnO deposition on the Fe₂O₃ and Al₂O₃ crystals yields a monocrystalline film growth. The ZnO film deposited on the SiO₂ crystal exhibits less crystallinity. The simulation results are compared with experimental results available in the literature.     

Orientation relationships of aluminium nitride on sapphire

Orientation relationships of aluminium nitride on sapphire (112 6) AlN/(011 2) Al₂O₃ have been defined more exactly by X-ray diffractometry techniques. It has been found that, depending on the substrate misorientation from the surface plane (011 2), there can exist two kinds of azimuthal orientation of the epitaxial layer of AlN, namely, the projection of [0001] AlN on plane (011 2) Al₂O₃ can coincide either with [2 110] Al₂O₃ or with [21 1 0] Al₂O₃ direction. The vector field of the epitaxial layer inclination relative to the substrate misorientation has been drawn. The symmetry of this field obeys Neumann's rule. The epitaxial layer orientation has been found to depend on the sapphire substrate misorientation in direction [21 1 0].     

On the origin of the (1216)-orientation in epitaxial AIN layers on R-plane sapphire

Epitaxial AIN grown by MOCVD on (011 2)Al₂O₃ substrates usually is (12 10)-oriented. Here for the first time (12 16)AIN was found in MOCVD layers. This AIN orientation is known from other growth techniques, its origin is generally not understood. An explanation is given based on twinning in the early growth stages which is also applicable to the growth of (12 16)ZnO on (011 2)Al₂O₃.     

Structure and properties of NaPO3–ZnO–Nb2O5–Al2O3 glasses

In an effort to design low-melting, durable, transparent glasses, two series of glasses have been prepared in the NaPO₃–ZnO–Nb₂O₅–Al₂O₃ system with ZnO/Nb₂O₅ ratio of 2 and 1. The addition of ZnO and Nb₂O₅ to the sodium aluminophosphate matrix yields a linear increase of properties such as glass transition temperature, density, refractive index and elastic moduli. The chemical durability is also significantly, but nonlinearly, improved. The glass with the highest niobium concentration, 55NaPO₃–20ZnO–20Nb₂O₅–5Al₂O₃ was found to have a dissolution rate of 4.5 × 10^? 8 g cm^? 2 min^? 1, comparable to window glass. Structural models of the glasses were developed using Raman spectroscopy and nuclear magnetic resonance spectroscopy, and the models were correlated with the compositional dependence of the properties.     

Interface and material characterization of thin Al2O3 layers deposited by ALD using TMA/H2O

Thin Al₂O₃ layers were grown by atomic layer deposition using trimethylaluminum (TMA) and water as precursors on 1.2 nm thermal SiO₂ and HF cleaned Si surfaces. The stoichiometry and the contamination (H, OH and C) of as-deposited and N₂ annealed thick Al₂O₃ layers were characterized by secondary ion mass spectrometry (SIMS), elastic recoil detection analysis (ERDA) and X-ray photoelectron spectroscopy (XPS). We show a perturbed region (≈5 nm thick) at the Al₂O₃/Si interface by XPS and Auger electron spectrometry (AES). Post-deposition annealings induced important interface oxidation, Si atoms injection and SiO₂/Al₂O₃ mixture whereas the initial interface was abrupt. Silicon oxidation before Al₂O₃ growth highly limits interfacial oxidation and improves interfacial quality. We proposed that OH groups may play a key role to explain silicon oxidation during post-deposition annealings in inert ambience with low oxygen contamination levels.     

Synthesis and microstructural properties of ZnO nanorods on Ti-buffer layers

This study examined the structural properties of ZnO nanorods grown on Ti-buffer layers with different surface roughnesses of 1.5 and 4.0 nm. Vertically aligned ZnO nanorods were synthesized on Al₂O₃ substrates with a Ti-buffer layer by metal-organic chemical vapor deposition. X-ray diffraction revealed the ZnO nanorods grown on a smooth surface to have higher quality and better alignment in the ab-plane than those grown on the rough surface. Field-emission transmission electron microscopy (FE-TEM) measurements revealed a disordered layer at the ZnO/Ti interface. FE-TEM demonstrated that the Ti-buffer layer contained a mixture of ordered and amorphous phases. Energy dispersive spectroscopy (EDS) analysis revealed the Ti-buffer layers to be entirely oxides.     

Correlation Between the Fiber Texture of Nickel Electrodeposits as Supports and the Reflected Light Band from Cholesteric Liquid Crystals

In previous works [Mol. Cryst. Liq. Cryst., 61, 31(1980); 95, 323 (1983)] the influence of the solid support sorptive properties on the color (reflected light band) of cholesteric liquid crystals was revealed. Qualitative and quantitative (visible diffuse reflectance spectroscopy) measurements at several temperatures on bare metal (Zn, Fe, Cu, Al) surfaces mechanically treated, on chemically and electrolytically prepared ZnO and Fe₃O₄, on electrolytically prepared γ₁,-and γ₂-Al₂O₃, on copper surfaces electroplated with copper and on electrolytically prepared γ₂-Al₂O₃ under several current densities, covered with a cholesteric mixture were carried out and correlated with the sorptive properties of the support. In the present work similar optical measurements at several temperatures with the same mixture of cholesterics as the one of the previous works on nickel electrodeposits with different fiber texture were carried out, compared each other and correlated with the deduced sorptive abilities of the deposits.     

Properties and structure of Yb3+ doped zinc aluminum silicate phosphate glasses

This study explores a series of optical, thermal, and structural properties based on 60P₂O₅–30ZnO–10Al₂O₃ (60P) glasses that doped with varied rare earth (RE) elements Yb₂O₃ and P₂O₅ components replaced by SiO₂. It was found that the glasses density decrease with SiO₂ concentration added to replace P₂O₅, whereas they increase with increased concentration of Yb³⁺-doped. Moreover, the glasses transition temperature, softening temperature, and refractive index increase with Yb³⁺ concentrations added, whereas the thermal expansion coefficient decreases. For the 60P glasses, 7 mol% Yb₂O₃ doped has the maximum fluorescence which is suppressed when Yb₂O₃ is doped up to 9 mol%. In addition, maximum lifetime was found to be 2.68 ms at an optimal Yb³⁺-doping at 1 mol% for 53P₂O₅–7SiO₂–30ZnO–10Al₂O₃ glass.     

The effect of different oriented sapphire substrates on the growth of polar and non-polar ZnMgO by MOCVD

Polar and non-polar ZnMgO were synthesized on different crystallographic planes (C-, R- and M-planes) of sapphire (Al₂O₃) substrates by metal organic chemical vapor deposition, respectively. Under the same experimental condition, polar ZnMgO nanorods were obtained on C-Al₂O₃ substrate whereas non-polar ZnMgO thin films were obtained on R- and M-Al₂O₃ substrates. The surface morphology was significantly influenced by the competition of the preferable growth directions on different sapphire substrates. On C-Al₂O₃ substrate, ZnMgO nanorods were vertically well-aligned with typical lengths in the range 330–360 nm. On R- and M-Al₂O₃ substrates, however, ZnMgO thin films with flat surfaces were obtained, whose thickness were 150 and 20 nm, respectively. Under the same condition, the C-ZnMgO deposited on C-Al₂O₃ substrate has the maximum growth velocity (11 nm/nim), followed by A-ZnMgO deposited on R-Al₂O₃ substrate (5 nm/min), and the M-ZnMgO deposited on M-Al₂O₃ substrate has the minimum one (0.67 nm/min). The Near-Band-Edge (NBE) emission in Photoluminescence (PL) spectra shows a clear blueshift and a slight broadening compared with that of pure ZnO samples, which suggest that the Mg content has successfully incorporated into ZnO. The different energy blueshifts (67 meV and 98 meV) of the NBE emission demonstrate that A-ZnMgO deposited on R-Al₂O₃ substrate has higher Mg incorporation efficiency than C-ZnMgO on C-Al₂O₃ substrate.     

Preparation of single-crystalline ZnO films on ZnO-buffered a-plane sapphire by chemical bath deposition

High-quality zinc oxide (ZnO) films were successfully grown on ZnO-buffered a-plane sapphire (Al₂O₃ (1 1 2¯ 0)) substrates by controlling temperature for lateral growth using chemical bath deposition (CBD) at a low temperature of 60 °C. X-ray diffraction analysis and transmission electron microscopy micrographs showed that the ZnO films had a single-crystalline wurtzite structure with c-axis orientation. Rocking curves (ω-scans) of the (0 0 0 2) reflections showed a narrow peak with full width at half maximum value of 0.50° for the ZnO film. A reciprocal space map indicated that the lattice parameters of the ZnO film (a=0.3250 nm and c=0.5207 nm) were very close to those of the wurtzite-type ZnO. The ZnO film on the ZnO-buffered Al₂O₃ (1 1 2¯ 0) substrate exhibited n-type conduction, with a carrier concentration of 1.9×10¹⁹ cm⁻³ and high carrier mobility of 22.6 cm² V⁻¹ s⁻¹.     

Fabrication of Sn-doped zinc phosphate glass using a platinum crucible

The authors investigate the structural change of a ZnO–P₂O₅ sintered matrix for the preparation of SnO-doped zinc phosphate (SZP) glass using a platinum crucible. Heat treatment of zinc oxide and ammonium phosphate at 800 °C causes the formation of a Zn₂P₂O₇-like species, which is effective in preventing damage to the platinum crucible. Although the thermal property of the glass was affected by added Al₂O₃, Al₂O₃ hardly affects the quantum efficiency of the SZP glass phosphor. This process is important for the fabrication of contamination-free phosphate glass using ammonium phosphate as a starting material.     

Leaching of some lithium silicate glasses and glass-ceramics by HCl

The leaching of some binary and ternary lithium silicate glasses and their respective glass-ceramics by HCl is reported.The leaching rate of lithium silicate glasses gradually decreases with the decrease of the percentage of Li₂O or by the introduction of small amounts of a third component, e.g. Al₂O₃, MgO, ZnO or B₂O₃. With a further increase in the proportions of B₂O₃ or ZnO the rate of leaching increases. The rate of leaching is also substantially modified by the conversion of glasses into glasses-ceramics.The results obtained are discussed in terms of the effects of the different ions on the rate of the interdifussion of the lithium and hydrogen ions in the glass and the leached layer, the phase separation developed in the glass, the type and concentration of crystalline phases developed in glass-ceramics and the composition of the residual glass phase.     

Strong biaxial texture and polymorph nature in TiO2 thin film formed by ex-situ annealing on c-plane Al2O3 surface

Many applications based on TiO₂ thin films are strongly influenced by the film crystalline quality, microstructure and surface morphology. We have utilized x-ray scattering methods for crystal structure study of TiO₂ films, grown by DC reactive magnetron sputtering without heating. We have observed the formation of ordered phases after post-deposition ex-situ annealing in air at 600 °C. The distinct biaxial texture with respect to the c-plane (0001) Al₂O₃ substrate surface, which developed during heating, shows remarkable patterns in pole figures. We have identified epitaxial relationships of anatase A(001)[110]6sub(001)[11?00] and rutile R(100)[001]6sub(0001)[100] within single TiO₂ layer. In addition, within the same sample, we have observed the anatase in (112) orientation with two in-plane relationship options A(112)[11?0]6sub(0001)[21?1?0] and A(112)[11?0]6sub(0001)[11?00].     

MOCVD growth of GaN on Si(1 1 1) substrates using an ALD-grown Al2O3 interlayer

GaN thin films have been grown on Si(1 1 1) substrates using an atomic layer deposition (ALD)-grown Al₂O₃ interlayer. This thin Al₂O₃ layer reduces strain in the subsequent GaN layer, leading to lower defect densities and improved material quality compared to GaN thin films grown by the same process on bare Si. XRD ω-scans showed a full width at half maximum (FWHM) of 549 arcsec for GaN grown on bare Si and a FWHM as low as 378 arcsec for GaN grown on Si using the ALD-grown Al₂O₃ interlayer. Raman spectroscopy was used to study the strain in these films in more detail, with the shift of the E₂(high) mode showing a clear dependence of strain on Al₂O₃ interlayer thickness. This dependence of strain on Al₂O₃ thickness was also observed via the redshift of the near bandedge emission in room temperature photoluminescence (RT-PL) spectroscopy. The reduction in strain results in a significant reduction in both crack density and screw dislocation density compared to similar films grown on bare Si. Screw dislocation density of the films grown on Al₂O₃/Si substrates approaches that of typical GaN layers on sapphire. This work shows great promise for the use of oxide interlayers for growth of GaN-based LEDs on Si.     

Fabrication and characterization of transparent conductive ZnO:Al thin films prepared by direct current magnetron sputtering with highly conductive ZnO(ZnAl2O4) ceramic target

Using a highly conductive ZnO(ZnAl₂O₄) ceramic target, c-axis-oriented transparent conductive ZnO:Al₂O₃ (ZAO) thin films were prepared on glass sheet substrates by direct current planar magnetron sputtering. The structural, electrical and optical properties of the films (deposited at different temperatures and annealed at 400°C in vacuum) were characterized with several techniques. The experimental results show that the electrical resistivity of films deposited at 320°C is 2.67×10⁻⁴ Ω cm and can be further reduced to as low as 1.5×10⁻⁴ Ω cm by annealing at 400°C for 2 h in a vacuum pressure of 10⁻⁵ Torr. ZAO thin films deposited at room temperature have flaky crystallites with an average grain size of ∼100 nm; however those deposited at 320°C have tetrahedron grains with an average grain size of ∼150 nm. By increasing the deposition temperature or the post-deposition vacuum annealing, the carrier concentration of ZAO thin films increases, and the absorption edge in the transmission spectra shifts toward the shorter wavelength side (blue shift).     

Growth of oxide fibers by the internal crystallization method

A new approach is developed for growing relatively inexpensive single-crystal and eutectic oxide fibers suitable for the fabrication of high-temperature composite materials. Sapphire (Al₂O₃), YAG (Y₃Al₅O₁₂), mullite (3Al₂O₃ · 2SiO₂), YAP (YAlO₃), and eutectic (Al₂O₃-Y₃Al₅O₁₂, Al₂O₃-ZrO₂ (Y₂O₃), and Al₂O₃-Gd₂O₃) fibers are produced by the internal crystallization method, and their mechanical strength and micro-structures are studied.     

Effect of Al2O3 on the viscosity and structure of calcium silicate-based melts containing Na2O and CaF2

The effect of Al₂O₃ on viscosity in the calcium silicate melt-based system containing Na₂O and CaF₂ was investigated and correlated with the melt structure using FTIR (Fourier transform infrared) spectroscopy, XPS (X-ray photoelectron spectroscopy), and Raman spectroscopy. Substituting SiO₂ with Al₂O₃ modified the dominant silicate network into a highly structured alumino-silicate structure with the aluminate structure being particularly prevalent at 20 mass% of Al₂O₃ and higher. As the melts become increasingly polymerized with higher Al₂O₃ content, the fraction of symmetric Al–O⁰ stretching vibrations significantly increased and the viscosity increased. XPS showed a decrease in the amount of non-bridged oxygen (O^?) but an increase in bridged oxygen (O⁰) and free oxygen (O^2?) with higher Al₂O₃. Although changes in the structure and viscosity with higher CaO/(SiO₂ + Al₂O₃) were not significant, the symmetric Al–O⁰ stretching in the [AlO₄]^5?-tetrahedral units decreased. The apparent activation energy for viscous flow varied from 118 to 190 kJ/mol.     

Influence of Al2O3 addition on the properties of Bi2O3–BaO–SiO2–RxOy (R = K,Zn, etc.) glass sealant

A series of Bi₂O₃–BaO–SiO₂–R_xO_y (designated BiBaSi glass) glass sealants doped with different contents of α-Al₂O₃ have been investigated. Al₂O₃ was added as a modifier to affect the structure and the behavior of the glass. The thermal properties such as glass transition temperature (Tg), softening temperature (Tf) and coefficient of thermal expansion (CTE) were measured by a dilatometer. The sealing performance was investigated by sealing a SOFC single cell stack and measuring its open circuit voltage (OCV). Tg, Tf and suitable usage temperature of the sealants increased with increasing Al₂O₃ content in the glass, while CTE decreased. When the Al₂O₃ content was lower than 10 wt.%, excellent sealing performance was observed.