TiO2-SiO2 monolithic glass formation from sol-gel

This study demonstrates that hydrolysis should be carried out in a step manner in gel synthesis. The key to the increase in the amount of water added is the control of the hydrolysis rate of Ti(OC₄H₉)₄. The hydrolysis of Si(OC₂H₅)₄ can be carried out at about 75°C. The amount of added water (γ_WI), which varied with TiO₂ content (in mol%), was about 64–88% of the total amount of added water. The hydrolysis reaction should be performed at room temperature while Ti(OC₄H₉)₄ is added. The total amount of added water (γ_W) is related to the amount of solvent (R). For example, if TiO₂ is 40mol%, γ_W will vary from 3.2 to 8.0 when R varies from 0.8 to 2.0. The amount of added water was affected by the distribution of solvent in the metal alkoxides. The amount of added water can be increased when R_Si(OC2H5)4 = 1, R_Ti(OC4H9)4 > 1. The rate of rise in temperature of the thermolysis of the dried gel should be less than 10°C per hour, and the heat treatment temperatyre is related to the TiO₂ content (in mol%). Gel glasses without devitrification can only be obtained by thermolysis at 600°C from the gel with no less than 20 mol% TiO₂.     

Hydrogenated amorphous silicon with substrate-dependent structure

Hydrogenated amorphous silicon (a-Si:H) thin films grown at 250°C on (1 0 0) crystalline substrate using plasma-enhanced chemical vapor deposition (PECVD) with SiH₄/H₂ gas flow ratio equal to 5/1 (sccm) are investigated by transmission electron microscopy. It is found that the thin film is totally amorphous when grown on a glass substrate. But when the substrate is changed to crystalline silicon, some crystalline grains are found embedded in the amorphous structure in certain regions even if the thickness of the film reaches 600 nm. It is suggested that the amorphous silicon film grown on a crystalline silicon substrate at a temperature of 250°C without heavy H₂ dilution is a mixed network of a small amount of crystalline silicon and the major portion of amorphous silicon.     

The photoluminescence of ZnO thin films grown on Si (1 0 0) substrate by plasma-enhanced chemical vapor deposition

High-quality ZnO thin films have been grown on a Si(1 0 0) substrate by plasma-enhanced chemical vapor deposition (PECVD) using a zinc organic source (Zn(C₂H₅)₂) and carbon dioxide (CO₂) gas mixtures at a temperature of 180°C. A strong free exciton emission with a weak defect-band emission in the visible region is observed. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption peak in the absorption spectra, are closely related to the gas flow rate ratio of Zn(C₂H₅)₂ to CO₂. Full-widths at half-maximum of the free exciton emission as narrow as 93.4 meV have been achieved. Based on the temperature dependence of the PL spectra from 83 to 383 K, the exciton binding energy and the transition energy of free excitons at 0 K were estimated to be 59.4 meV and 3.36 eV, respectively.     

The preparation of boron-doped silicon carbide powder by the carbothermal reduction of oxides derived from the hydrolyzed methyltriethoxysilane

A precursor prepared from a methyltriethoxysilane ((CH₃)Si(OC₂H₅)₃, MTES)-B(OC₂H₅)₃-polyacrylonitrile (PAN) composition was used for the synthesis of boron-doped SiC by carbothermal reduction. Initially, MTES was hydrolyzed with HCl (MTES: H₂O: HCl = 1 : 1 : 0.01) for 1 h in a sealed vessel. The number-average molecular weight measurement and a NMR spectrum revealed that the species in the solution were mainly oligometric. With the addition of B(OC₂H₅)₃, no significant changes in the distribution of the Si containing species were detected. The mixing of the hydrolyzed solution with a PAN-dimethylsulfoxide solution led to a homogeneous solution. After the evaporation of the solvents and the subsequent heat treatment at 220° C, brown precursor powder was obtained. By the heat treatment at 1600° C in Ar, it was converted to boron-doped SiC powder.     

Synthesis of fluorine doped silica gel and its properties at high temperature

Fluorine doped silica gels were synthesized by using the sol-gel processes of (A) SiF₄(g) and H₂O(1) and (B) the mixed solution of Si(OC₂H₅)₄, C₂H₅OH, H₂O and H₂SiF₆. By the former process we obtained a gel of relatively high fluorine content (8–12 at.%F), while we could synthesize the gel of 0–12 at.% F by adjusting the F/Si ratio of the starting solution mixtures by the latter process.

The defluorination behavior and the structural change of these gels at high temperature were studied by heating-mass spectrometry, IR and ESR measurements. The results revealed the following: (1) defluorination by liberation of SiF₄(g) was admitted from temperatures at about 400°C and was controlled by the diffusion of fluorine in the gel bulk. (2) The peak separation analysis for the IR band of 1300-900 cm⁻¹, where the stretching vibrations of Si---O and Si---F appear, showed that the change of the band shape resulted from the increase or the decrease of the Si---F bonds and the change of the bond angle of Si---O---Si as well as the change of the force constant accompanied by fluorination or defluorination. (3) The defects of the Si E′ center were induced by X-ray irradiation depending on the degree of the defluorination, and were reduced by the heat treatment. However, with the heat treatment at temperatures higher than 1000°C, the E′ center increased again. The IR spectra suggest that this behavior might correspond to the gel-glass trasition.     

Preparation of alumina gels by a non-hydrolytic sol-gel processing method

Monolithic alumina gels were prepared by a novel non-hydrolytic sol-gel route based on the condensation reaction between aluminum alkoxides Al(OR)₃ and aluminum halides AlX₃, through the formation of alkyl halide RX(X = Br, Cl; R = iso-propyl, sec- or ter-butyl), around 100°C. Samples were then calcined and were found to be amorphous up to about 750°C; they kept a high specific surface area to about 900°C. This delayed crystallization is correlated with the large number of five-coordinate aluminum sites measured in dried gels by ²⁷Al NMR spectroscopy.     

r-GRIN glass rods prepared by a sol-gel method

Preparation of radial gradient refractive index (r-GRIN) glass rods has been undertaken by a sol-gel process using metal alkoxides. Two binary systems, Si(OCH₃)₄---Ge(OC₂H₅)₄ and Si(OCH₃)₄−Ti(O−n-C₄H₉)₄ have been investigated. It has been shown that immersion of rod-shaped wet gels in neutral or acidic water gives rise to leaching of the dopants (germanium and titanium components). Since this leaching is controlled predominantly by diffusion, the dopants remaining in the gels are expected to form concentration gradients. Optical measurements of the glass rods obtained after drying and sintering of the leached gels have shown that the concentration gradients are retained in the glass rods and they give r-GRIN profiles.     

CrO2 (1 0 0) and TiO2 (1 0 0) film heteroepitaxy on a BaF2 (1 1 1)/Si (1 0 0) substrate

Multi-domained heteroepitaxial rutile-phase TiO₂ (1 0 0)-oriented films were grown on Si (1 0 0) substrates by using a 30-nm-thick BaF₂ (1 1 1) buffer layer at the TiO₂–Si interface. The 50 nm TiO₂ films were grown by electron cyclotron resonance oxygen plasma-assisted electron beam evaporation of a titanium source, and the growth temperature was varied from 300 to 600 °C. At an optimal temperature of 500 °C, X-ray diffraction measurements show that rutile phase TiO₂ films are produced. Pole figure analysis indicates that the TiO₂ layer follows the symmetry of the BaF₂ surface mesh, and consists of six (1 0 0)-oriented domains separated by 30° in-plane rotations about the TiO₂ [1 0 0] axis. The in-plane alignment between the TiO₂ and BaF₂ films is oriented as [0 0 1] TiO₂ || BaF₂ or [0 0 1] TiO₂ || BaF₂ . Rocking curve and STM analyses suggest that the TiO₂ films are more finely grained than the BaF₂ film. STM imaging also reveals that the TiO₂ surface has morphological features consistent with the BaF₂ surface mesh symmetry. One of the optimally grown TiO₂ (1 0 0) films was used to template a CrO₂ (1 0 0) film which was grown via chemical vapor deposition. Point contact Andreev reflection measurements indicate that the CrO₂ film was approximately 70% spin polarized.     

Formation of LiNbO3 films by hydrolysis of metal alkoxides

Homogeneous, crack-free, thin films of crystalline LiNbO₃ were synthesized above 250°C on Si(100) substrates by the dip-coating method using a double alkoxide solution. The coating solution, which was prepared by the controlled partial hydrolysis of the double alkoxide, gave stoichiometric LiNbO₃ crystalline films at temperatures as low as 250°C. The concentration of the alkoxide solution influenced both of thickness and quality of films. Crystallinity of thin film top-coated directly on the substrate affected the crystallization state of films coated on the film remarkably. Films crystallized on -Al₂O₃(0001) showed preferred orientation along the c-axis, while the preferred orientation could not be observed on Si(100) substrates.     

Low-pressure chemical vapor deposition of TaCN films by pyrolysis of ethylamido-tantalum

Thin films of Tantalum nitride (TaN) were deposited from tetra-ethylamido-tantalum (Ta (NEt₂)₄) by low-pressure chemical vapor deposition. Good-quality step coverage is achieved below 400°C, because the deposition rate is determined by the reaction rates on the surface. The film resistivity increases, however, as the substrate temperature decreases. In order to obtain the low resistivity of films deposited at lower temperatures, we have increased the amount of injected H₂ gas during the deposition. The resistivity decreases by the increase in the H₂ gas flow rate, and it is shown that a large amount of H₂ gas injection during the deposition is an effective method for obtaining both low resistivity and high-quality step coverage. The residual carbon concentration in the film is measured to be >10%, on the other hand, the concentration of N less than 1%. The microstructural investigation using transmission electron microscopy (TEM) reveals that crystalline structure of the deposited film has an amorphous phase.     

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.     

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.     

The growth kinetics of (SmY)3(FeGa)5O12 epitaxial layers in the 920–980°C range

The growth kinetics of (SmY)₃(FeGa)₅O₁₂ garnets obtained by liquid phase epitaxy on Gd₃Ga₅O₁₂ substrates are discussed in the 920 to 980°C. range. The experiments have been carried out with the substrates in a horizontal plane and with unidirectional rotation ranging from 30 to 300 rotations per minute (rpm). A sharp increase in the growth velocity at temperatures higher than 960°C is interpreted on the basis of a diffusion-reaction theory. It is found that the diffusion constant increases steeper at higher temperatures and that the linear law of the growth rate as a function of the square root of the rotation rate holds to much higher rotation rates at these temperatures. The influence of the surface incorporation is too small to be detectable. The results are compared with published data concerning other compositions.     

A simple method to synthesize single-crystalline β-wollastonite nanowires

The single-crystalline β-wollastonite (β-CaSiO₃) nanowires were prepared via a simple hydrothermal method, in the absence of any template or surfactant using cheap and simple inorganic salts as raw materials. Xonotlite [Ca₆(Si₆O₁₇)(OH)₂] nanowires were first obtained after hydrothermal treatment at a lower temperature of 200 °C for 24 h, and after being calcinated at 800 °C for 2 h, xonotlite nanowires completely transformed into β-wollastonite nanowires and the wire-like structure was preserved. The synthesized β-wollastonite nanowires had a diameter of 10–30 nm, and a length up to tens of micrometers, and the single-crystalline monoclinic parawollastonite structured β-wollastonite was identified by XRD with the space group of P2₁/a and cell constants of a=15.42 Å, b=7.325 Å, c=7.069 Å and β=95.38°. A possible growth mechanism of β-wollastonite nanowires was also proposed. The advantages of this method for the nanowire synthesis lie in the high yield, low temperature and mild reaction conditions, which will allow large-scale production at low cost.     

Homoepitaxial growth of 6H–SiC thin films by metal-organic chemical vapor deposition using bis-trimethylsilylmethane precursor

Homoepitaxial silicon carbide (SiC) films were grown on 3.5° off-oriented (0 0 0 1) 6H–SiC by metal-organic chemical vapor deposition (MOCVD) using bis-trimethylsilylmethane (BTMSM, C₇H₂₀Si₂). A pronounced effect of the growth conditions such as source flow rate and growth temperature on the polytype formation and structural imperfection of the epilayer was observed. The growth behavior was explained by a step controlled epitaxy model. It was demonstrated by high-resolution X-ray diffractometry and transmission electron microscopy that high-quality 6H–SiC thin films were successfully grown at the optimized growth condition of substrate temperature 1440°C with the carrier gas flow rate of 10 sccm.     

The preparation and characterization of silica gels doped with copper complexes

Silica gels doped with [Cu(C₅H₅N)₄]²⁺ (C₅H₅N = Py), CuCl₂-HOCH₂CH₂OH and Cu(CH₃COO)₂-NH₂(CH₂)₃Si-(OC₂H₅)₃ (CH₃COO = OAc, C₂H₅ = Et) have been prepared and examined by X-ray diffraction, electron spin resonance, transmission electron microscopy (TEM), thermal gravimetric analysis and Fourier transform infrared spectroscopy. Different dopants have different interactions with the silica alcogels depending on the chemistry of the dopants: [Cu(Py)₄]²⁺ forms chemical bonds with the hydroxyl oxygens on the surface of the silica matrix; in Cu(OAc)₂-NH₂(CH₂)₃Si(OEt)₃-doped alcogels, the siloamine enters into the sol-gel reaction and Cu(OAc)₂ coordinates to the -NH₂(CH₂)₃ ligand of the precursor. However, there is no evidence for bond formation between copper and the hydroxyl groups on the silica surface in the CuCl₂-HOCH₂CH₂OH-doped alcogels. The TEM images show a homogeneous and uniform distribution of copper particles on the reduced CuCl₂-HOCH₂CH₂OH- and Cu(OAc)₂-NH₂(CH₂)₃Si(OEt)₃-doped xerogel surface. The type of nitrogen adsorption isotherms of doped silica xerogels are unaffected by the dopant concentration. However, their surface areas do depend on the level of dopant. The microstructure of the silica matrix is primarily determined by the pH of the initial reactants, at least in the [Cu(Py)₄]²⁺-doped case.     

Novel single source precursors for MOCVD of AlN, GaN and InN

The MOCVD of AlN, GaN and InN thin films using the novel single source precursors (N₃)₂Ga[(CH₂)₃NMe₂] (1), (N₃)In[(CH₂)₃NMe₂]₂ (2), (N₃)Al[(CH₂)₃NMe₂]₂ (3) and (N₃)AlMe₂(H₂N^tBu) (4) is reported. The compounds are non-pyrophoric. Compound 3 is air stable. No additional N-sources were used for the growth of the nitrides. We achieved epitaxial (AlN, GaN) or polycrystalline (InN) growth at least 200°C below the decomposition temperature of the respective nitride. Some aspects of the reactivity of the precursors with ammonia and the resulting influence on the deposition process were investigated.     

Preparation of nanoscaled BaTiO3 powders by DSS method near room temperature under normal pressure

A new method of direct synthesis nano-BaTiO₃ powders from solution was developed in this study. Dissolving Ba(OH)₂·8H₂O into water as base solution, nanocrystalline BaTiO₃ powders can be obtained by mixing ethanol solution of tetrabutyl titanate with hot base solution under normal pressure. When the temperature of the base solution was 60°C, we obtained crystalline powders with average particle size of about 25 nm. The activity of the powders can be held up because the calcination at high temperature is not necessary using this method.     

Hydrolysis and condensation reactions of Si(OC2H5)4 related to silica fiber drawing

The hydrolysis and condensation reactions of Si(OC₂H₅)₄ (TEOS) at 80°C in the TEOS---H₂O---C₂H₅OH---HCl solutions with H₂O/TEOS molar ratios (r) from 1.0 to 2.0 were followed by gas chromatography (GC) and measurement of molecular weight ( ) of the hydrolyzates, in order to explain the viscosity change of the solutions. It has been found that the siloxane oligomers with average polymerization degree (n) from 2 to 7 are formed in the early stage of reaction and undergo condensation to form higher polymers. The n and the number of silanol groups of the oligomers are increased with increasing r. The fact that the solution viscosity increased once rapidly around the so-called gelation point followed by a sluggish increase with the increase of reaction time for an r of 1.7, while it increased rapidly without a break till gelation for an r of 2.0, was attributed to fewer silanol groups and higher steric hindrance as a result of more −OC₂H₅ groups remaining in the oligomers for an r of 1.7.     

Study on the Ce substitution effects of BiFeO3 films on ITO/glass substrates

Ce substituted Bi_1−xCe_xFeO₃ (BCFO) films with x=0–0.15 were deposited on indium tin oxide (ITO)/glass substrates by sol–gel process annealed at 500 °C. Rhombohedral phase was confirmed by XRD study and no impure phases were observed till x=0.15. Substantially enhanced ferroelectricity was observed at room temperature due to the substitution of Ce. In the films with x=0.05 and 0.10, the double remnant polarization are 75.5 and 57.7 μC/cm² at an applied field 860 kV/cm. Moreover, the breakdown field was enhanced in the films with Ce substitution.