Epitaxial growth of the CoFe2O4 film on SrTiO3 and its characterization

Cobalt ferrite (CoFe₂O₄) thin film is epitaxially grown on (0 0 1) SrTiO₃ (STO) by laser molecular beam epitaxy (LMBE). The growth modes of CoFe₂O₄ (CFO) film are found to be sensitive to laser repetition, the transitions from layer-by-layer mode to Stranski–Krastanov (SK) mode and then to island mode occur at the laser repetition of 3 and 5 Hz at 700 °C, respectively. The X-ray diffraction (XRD) results show that the CFO film on (0 0 1) SrTiO₃ is compressively strained by the underlying substrate and exhibits high crystallinity with a full-width at half-maximum of 0.86°. Microstructural studies indicate that the as-deposited CFO film is c-oriented island structure with rough surface morphology and the magnetic measurements reveal that the compressive strained CoFe₂O₄ film exhibits an enhanced out-of-plane magnetization (190 emu/cm³) with a large coercivity (3.8 kOe).     

Solidification of superalloy in a SiO2–ZrO2–B2O3 coating mould

The preparation of glass-lined coating mould from gels in the ternary system of SiO₂–ZrO₂–B₂O₃ has been investigated. The crystallization characterization and high temperature structure stability of this coating mould are demonstrated. We can find that the crystallization of t-ZrO₂ as well as the tetragonal to monoclinic phase transformation are, respectively, retarded and impeded owing to the encasement of SiO₂ matrix. While the inhibitive effect of B₂O₃ on crystallization of the SiO₂–ZrO₂–B₂O₃ coating mould is explained. Finally, DD3 single crystal superalloy melt can realize highly undercooled rapid solidification by adopting this coating mould, which further evinces that SiO₂–ZrO₂–B₂O₃ coating mould has an ideal nucleation inhibition for superalloy.     

Effect of CaO on the surface morphology and strength of water soaked Na2O–B2O3–Al2O3–SiO2 vitrified bond

The surface morphology of Na₂O–B₂O₃–Al₂O₃–SiO₂ vitrified bond with and without calcium oxide was studied by soaking vitrified bonded microcrystalline alumina composites in water. The content of water introduced to the vitrified bond was determined by thermal gravity analysis, and the effects of water and calcium on the phase separation and nucleation of the vitrified bond were investigated using scanning electron microscope and energy-dispersive X-ray spectrometer. Soaked in water for 72 h, the Na₂O–B₂O₃–Al₂O₃–SiO₂ vitrified bond presented a porous surface, and its bending strength declined with increasing sintering temperature. However, the Na₂O–CaO–B₂O₃–Al₂O₃–SiO₂ vitrified bond was more durable against aqueous coolant even needle-shape crystals were found clustered on the surface of the vitrified bond. The crystals were enriched with aluminosilicate tested by energy-dispersive X-ray spectrums. The appearance of crystals lessened the dissolution of the vitrified bond and made the bending strength increase in the sintering temperature region between 870 °C and 930 °C.     

Surface and interfacial structure of epitaxial SrTiO3 thin films on (0 0 1) Si grown by molecular beam epitaxy

Effects of relaxation of interfacial misfit strain and non-stoichiometry on surface morphology and surface and interfacial structures of epitaxial SrTiO₃ (STO) thin films on (0 0 1) Si during initial growth by molecular beam epitaxy (MBE) were investigated. In situ reflection high-energy electron diffraction (RHEED) in combination with X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectrometry (XPS) and transmission electron microscopy (TEM) techniques were employed. Relaxation of the interfacial misfit strain between STO and Si as measured by in situ RHEED indicates initial growth is not pseudomorphic, and the interfacial misfit strain is relaxed during and immediately after the first monolayer (ML) deposition. The interfacial strain up to 15 ML results from thermal mismatch strain rather than lattice mismatch strain. Stoichiometry of STO affects not only surface morphology but interfacial structure. We have identified a nanoscale Sr₄Ti₃O₁₀ second phase at the STO/Si interface in a Sr-rich film.     

Synthesis of Y2O3:Eu phosphors by bicontinuous cubic phase process

A novel approach for preparation of red-emitting europium-doped yttrium oxide phosphor (Y₂O₃:Eu) by using the bicontinuous cubic phase (BCP) process was reported in this paper. The BCP system was composed of anionic surfactant sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and aqueous yttrium nitrate/europium nitrate solution. Energy dispersive spectrometer analysis revealed the homogeneous precipitation occurred in the BCP structure. Thermogravimetric analysis measurements indicated the precursor powder was europium-doped yttrium hydroxide, Y_1−xEu_x(OH)₃. Scanning electron microscopy micrographs showed the precursor powder had a primary size about 30 nm and narrow size distribution. After heat treatment in furnace above 700 °C for 4 h, high crystallinity Y₂O₃:Eu phosphors was obtained. However, the primary size of particles grew to 50–200 nm and the dense agglomerates with a size below 1 μm were formed. X-ray diffraction patterns indicated the crystal structure of precursor powders and Y₂O₃:Eu phosphors were amorphous and body-centered cubic structure, respectively. The photoluminescence analysis showed that the obtained Y₂O₃:Eu phosphor had a strong red emitting at 612 nm and the quenching started at a Eu concentration of 10 mol%. This study indicated that the BCP process could be used to prepare the highly efficient oxide-based phosphors.     

Structure and thermal stability of MOCVD ZrO2 films on Si (1 0 0)

The structure and thermal stability of ZrO₂ films grown on Si (1 0 0) substrates by metalorganic chemical vapor deposition have been studied by high-resolution transmission electron microscopy, selected area electron diffraction and X-ray energy dispersive spectroscopy. As-deposited films consist of tetragonal ZrO₂ nanocrystallites and an amorphous Zr silicate interfacial layer. After annealing at 850°C, some monoclinic phase is formed, and the grain size is increased. Annealing a 6 nm thick film at 850°C in O₂ revealed that the growth of the interfacial layer is at the expense of the ZrO₂ layer. In a 3.0 nm thick Zr silicate interfacial layer, there is a 0.9 nm Zr-free SiO₂ region right above the Si substrate. These observations suggest that oxygen reacted with the Si substrate to grow SiO₂, and SiO₂ reacted with ZrO₂ to form a Zr silicate interfacial layer during the deposition and annealing. Oxygen diffusion through the tetragonal ZrO₂ phase was found to be relatively easier than through the monoclinic phase.     

Correlation between interfacial structure and c-axis-orientation of LiNbO3 films grown on Si and SiO2 by electron cyclotron resonance plasma sputtering

Thin films of crystalline lithium niobate (LN) grown on Si(1 0 0) and SiO₂ substrates by electron cyclotron resonance plasma sputtering exhibit distinct interfacial structures that strongly affect the orientation of respective films. Growth at 460–600 °C on the Si(1 0 0) surface produced columnar domains of LiNbO₃ with well-oriented c-axes, i.e., normal to the surface. When the SiO₂ substrate was similarly exposed to plasma at temperatures above 500 °C, however, increased diffusion of Li and Nb atoms into the SiO₂ film was seen and this led to an LN–SiO₂ alloy interface in which crystal-axis orientations were randomized. This problem was solved by solid-phase crystallization of the deposited film of amorphous LN; the degree of c-axis orientation was then immune to the choice of substrate material.     

Toughened glass-ceramics containing ZrO2 and Al2O3 prepared by the sol-gel process from metal alkoxides

Glasses of compositions 5ZrO₂·5SiO₂(ZS), 5ZrO₂·Al₂O₃·4SiO₂(ZAS) and 5 5ZrO₂·0.5Al₂O₃·0.5Na₂O·4SiO₂(ZANS) were prepared by the sol-gel process from metal alkoxides and sintered to make glass-ceramics. Tetragonal ZrO₂ was precipitated by heat treatment at 900 to 1300°C. The activation energy for tetragonal ZrO₂ crystal growth was extremely high in Al₂O₃ containing glasses. ZAS and ZS were sintered to the near theoretical densities above 1200°C, at which the predominant phase was tetragonal ZrO₂. On the other hand, for ZANS, high densification was not attained owing to the large pores enclosed by the glass phase. Strength and fracture toughness increased with the densification and the crystal growth of tetragonal ZrO₂, reaching 450 MPa and 9 MN/m^1.5, respectively.     

Oscillation of Y2BaCuO5 particle concentration in the melt-grown YBaCuO bulk superconductors

The oscillation of Y₂BaCuO₅ (2 1 1) particle concentration in form of bands parallel to the growth front was observed in top-seeded melt-grown (TSMG) single-grain YBa₂Cu₃O₇/Y₂BaCuO₅ bulk superconductors. The formations of these bands have been associated with temperature fluctuations at the growth front, which induce the fluctuation of the growth rate of the YBa₂Cu₃O₇ (123) crystal and consequently also the fluctuation of the amount of trapped 211 particles. We have shown that the oscillation of 211-particle concentration does not occur when the growth front is horizontal and the crystal solidifies from below upwards. In the a-growth sector (a-GS) the oscillation was observed only in the nests with very small 211 particles.     

The crystallisation of the yttrium–sialon glass: Y15.2Si14.7Al8.7O54.1N7.4

The development of microstructure during crystallisation of a glass with composition Y_15.2Si_14.7Al_8.7O_54.1N_7.4 has been studied by analytical and high resolution transmission electron microscopy. Crystal nucleation at temperatures in the range 965–1050°C occurs by the heterogeneous nucleation of lenticular-shaped yttrium, silicon and aluminium containing crystals on silicon-rich clusters that formed during glass preparation. The lenticular crystals have a wide range of composition after heat treatment at 1050°C; the yttrium cation percentage varies around that of the expected B-phase composition Y₂SiAlO₅N but the aluminium content is lower and the silicon content generally significantly higher than that. The crystals display the hexagonal crystal structure of B-phase, although the results from EDX analysis imply that the atomic arrangement of the lattice is not the previously proposed B-phase structure. Crystal growth during prolonged heat treatment at 1050°C occurs to a significant extent by coalescence.     

Selective epitaxial growth by UHV-CVD using Si2H6 and Cl2

The conditions under which selective epitaxial growth (SEG) is achieved in UHV-CVD with Si₂H₆ are determined by the amount of Si₂H₆ molecules being supplied, and there is a critical gas supply amount (F_c) beyond which SEG will break down and lose its selectivity. The value of F_c is itself determined by two factors, growth temperature and the material used for masking, i.e. SiO₂, Si₃N₄. We found that this limiting factor of F_c was increased through the addition of a small amount of Cl₂, and that after such addition, the resulting decrease in growth rate is minimal.     

Hydrolytic resistance of Na2O---B2O3---SiO2 gels prepared by sol-gel process

Alkoxide derived gels were prepared in the system Na₂O---B₂O₃---SiO₂. The gel compositions were situated in the liquid-liquid immiscibility area of the phase equilibrium diagram.

Hydrolytic resistance tests were performed on the gels heat-treated at temperatures ranging between 120 to 850 °C. The Na₂O, B₂O₃ and SiO₂ extracted from the attack gels were analyzed. The experimental results indicate that the amount of B₂O₃ has a significant influence on the chemical durability of the heat-treated gels. At temperatures of 850 °C the greater the B₂O₃ mol% the greater are the amounts of Na₂O and B₂O₃ extracted. Different behaviour was observed for gels heat-treated at 600 °C where the amounts of B₂O₃ and Na₂O extracted slightly increases as the B₂O₃ mol% increases. Small amounts of extracted SiO₂ were always observed.

These results are complemented with other measurements so that an explanation of the controlling mechanism is given.     

A structural study of Y2O3---Al2O3---SiO2 glass employing partial RDFs obtained by anomalous scattering

A structural study of Y₂O₃---Al₂O₃---SiO₂ glass has been performed using the partial radial distribution function (RDF) obtained by anomalous scattering at the Y absorption edge. The partial RDF consists of contributions from atom pairs, such as Y---O, Y---M(Si, Al) and Y---Y, related to the local arrangements around the Y atoms, while those of all of the constituent atom-pairs are convoluted into the ordinary RDF. The M(Si, Al)---O, Y---O, M---M, Y---M, and Y---Y interatomic distances and the coordination numbers around the Al and Y atoms are obtained from the two RDFs. The local structures around the Al and Y atoms in the glass are discussed.     

Surface modification of SiO2 glass by laser processing

Various oxide films on SiO₂ glass substrates were irradiated by a laser beam. A continuous CO₂ laser source (wavelength 10.6 μm) was used for this purpose; the composition change at the surface layer was determined by Rutherford backscattering spectrometry (RBS). All the alkaline-earth oxides as well as those of lanthanum and yttrium, entered the glass after treatment. ZrO₂ and CeO₂, however, did not enter the SiO₂ glass due to laser irradiation. It is interesting, however, that a film of ZrO₂ + Al₂O mixture easily entered into the SiO₂ glass by laser processing. The conditions and mechanism of laser-enhanced interaction of ZrO₂ or other oxide films with SiO₂ glass surfaces are discussed especially in view of their structural behaviour in glass.     

Some characteristics of glass in the Al2O3---B2O3---SiO2 system from the gel

The colorless and transparent glasses in the Al₂O₃---B₂O₃---SiO₃ system with high B₂O₃ and SiO₂ content were prepared from gels at low temperature. Their IR spectra not only revealed the evolution of the gel to glass conversion, but also showed that the formation of mixed bonds in the glasses obtained did not show any effect due to the B₂O₃ content. The accuracy of the glass composition is dependent upon the SiO₂/B₂O₃ molar ratio. The higher the ratio, the less the deviation of the analyzed compositions of the resulting glasses from their original calculated values. It is obvious that the higher the ratio, the lower the thermal expansion coefficient and the higher the transformation temperature of the glass, and the temperature at which the thermal contraction reaches an equilibrium is higher.     

Model for defect-free epitaxial lateral overgrowth of Si over SiO2 by liquid phase epitaxy

A growth model for defect-free epitaxial lateral overgrowth by liquid phase epitaxy is presented. Growth in the pure step flow mode and a preferential development of (111) planes in liquid phase epitaxy permit one to quantitatively predict the overgrowth. The shape and size of the Si lamellae which grow over SiO₂ depend on the crystallographic orientations of the substrate growth face and of the seeding windows. Overgrowth experiments with Si on oxidized, (111)- and (100)-oriented Si wafers serve to verify the model. Growth experiments from In and Bi solutions in temperature intervals between 950 and 800°C yield overgrowth widths up to 120 μm and aspect ratios of 40:1 on (111) oriented wafers.     

Effect of Al2O3 on phase separation and crystallization in ZnO---Al2O3---B2O3---SiO2 glasses

The effect of alumina on the phase separation and the crystallization of the glasses of composition (mol%) 18ZnO·30B₂O₃·52SiO₂ and O-40 Al₂O₃ was studied using an electron microscope and IR spectroscopy. The main crystalline phase appears in the microphase for which the compositions are not nearer to the crystal stoichiometry than the mean. The addition of Al₂O₃ suppresses the immiscibility but enhances the crystallizability.     

Growth of pure and RE-doped Y2O3 single crystals by LHPG technique

High-quality and crack-free Y₂O₃ single crystals containing low concentrations of Tm³⁺, Tb³⁺ and Yb³⁺ were obtained. The crystals were grown in the form of monocrystalline fibers by using a floating zone method with laser heating (laser-heated pedestal growth).     

Surface modification of a TiO2 film electrode prepared by the sol-gel method and its effect on photoelectrochemical behavior

The surface of a TiO₂ film electrode, about 1 μm thick, prepared by the sol-gel method, was modified by being additionally coated with about 0.1 μm thick TiO₂---SiO₂, TiO₂---ZrO₂ or TiO₂---Al₂O₃ films. The effect of the additional coating on the photoelectrochemical properties of a TiO₂ film electrode was investigated in detail. On addition of the second additive to TiO₂, the flat band potential was shifted toward negative potential for SiO₂ and positive potential for ZrO₂ and Al₂O₃, which is attributed to the change in the point of zero zeta potential (pzzp), not in the electron affinity (EA). However, enhancement in photocurrent was not observed for all the cases.     

NMR studies of Na2O---B2O3---SiO2 glasses of mid-alkali content

¹¹B Fourier transform spectra have been used to study the structure of Na₂O---B₂O₃---SiO₂ glasses of mid-alkali content. Based on the measurements of the fraction N₄ of four-coordinated borons, it has been found that for K = mol.% SiO₂/mol.% B₂O₃ 8 and R = mol.% Na₂O/mol.% B₂O₃ = 1, N₄ is obviously smaller than 1 rather than equal to 1 as assumed in the relevant literature. Only when R reaches a value appropriately greater than 1, can the case where N₄ = 1 occur. A structural model suggested in this paper can satisfactorily explain the fact.