An interface clusters mixture model for the structure of amorphous silicon monoxide (SiO)

The present state of research on the structure of amorphous silicon monoxide (SiO) is reviewed. The black, coal-like modification of bulk SiO is studied by a combination of diffraction, microscopy, spectroscopy, and magnetometry methods. Partial radial distribution functions of SiO are obtained by X-ray, neutron and electron diffraction. Disproportionation of SiO into Si and SiO₂ is verified. High resolution TEM gives an upper limit of less than 2 nm for the typical Si cluster size. The Si K-edge electron energy-loss near-edge structure (ELNES) data of SiO are interpreted in terms of the oxidation states Si⁴⁺ and Si⁰. X-ray photoelectron spectroscopy gives first details about possible stoichiometric inhomogeneities related to internal interfaces. The wipe-out effect in the ²⁹Si MAS NMR signal of SiO is confirmed experimentally. The new estimation of the wipe-out radius is about 1.1 nm. First-time W-band, Q-band, and X-band ESR and SQUID measurements indicate an interfacial defect structure. Frequency distributions of atomic nearest-neighbours are derived. The interface clusters mixture model (ICM model) suggested here describes the SiO structure as a disproportionation in the initial state. The model implies clusters of silicon dioxide and clusters of silicon surrounded by a sub-oxide matrix that is comparable to the well-known thin Si/SiO₂ interface and significant in the volume because of small cluster sizes.     

Nuclear magnetic resonance studies of alkaline earth phosphosilicate and aluminoborosilicate glasses

The ¹¹B, ²⁷Al, ²⁹Si and ³¹P magic angle spinning (MAS) NMR spectra of MO–P₂O₅, MO–SiO₂–P₂O₅ and MO(M^′₂O)–SiO₂–Al₂O₃–B₂O₃ (M=Mg, Ca, Sr and Ba, M^′=Na) glasses were examined. In binary MO–P₂O₅ (M=Ca and Mg) glasses, the distributions of the phosphate sites, P(Q_n), can be expressed by a theoretical prediction that P₂O₅ reacts quantitatively with MO. In the ternary 0.30MO–0.05SiO₂–0.65P₂O₅ glasses, the 6-coordinated silicon sites were detected, whose population increases in the order of MgOxCaO–0.05SiO₂–(0.95−x)P₂O₅ glasses, its population increases with an increase in f (=([P₂O₅]−[MO]−[B₂O₃]−[Na₂O])/[SiO₂]) and has maximum at f=9. The signal due to the 5-coordinated silicon atoms is also observed when x is smaller than 0.45. When three network-forming oxides such as SiO₂, Al₂O₃ and B₂O₃ coexist, Al₂O₃ reacts preferably with MO. The populations of 4-coordinated boron atoms, N₄, are expressed well with r/(1−r), where r=([Na₂O]−[Al₂O₃])/([Na₂O]−[Al₂O₃]+[B₂O₃]). The correlation of the Raman signal at 1210 and 1350 cm⁻¹ with the NMR signal of Si(Q₆) at −215 ppm is also seen.     

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.     

Structural difference of surface and sub-surface native oxides of evaporated amorphous silicon

Evaporated amorphous silicon (a-Si) films, oxidized in air or O₂ at room temperature, present two native oxides with different structures. The surface oxide is constructed from SiO₄-tetrahedron structural units with a 110° O---Si---O angle, which is the common structural unit of stable silicon oxides. The internal oxide has a different structure having a 120° O---Si---O angle. The results of molecular orbital (MO) calculations for (SiO₃)^m− and (SiO₄)ⁿ⁻ anionic clusters support the presence of the two stable structures of silicon oxides and also reveal the importance of the ionic character of the oxidized sites.     

Structural transformation of the TiO2---SiO2 system gel during heat-treatment

The gel formation of the (100-x)TiO₂·xSiO₂ (x = 0–10 mol%) system has been studied. The progressive elimination of residues was followed by DTA and TGA curves. DTA curves showed that the formation of anatase during heat treatment could be sensibly slowed down with the increase of SiO₂. The relationship between the gel composition and crystallization temperature of anatase has been systematically investigated. The X-ray diffraction spectra demonstrated that the crystallization temperature of anatase is 400°C for TiO₂ gel and 430°C for 90TiO₂ - 10SiO₂ gel. The infrared absorption spectra were used to follow the structural transformation of gels heat-treated at different temperatures. With the help of EPR it is evident that titanium ions exist only in tetravalence.     

Photoluminescence from E band centers in amorphous and crystalline SiO2

Photoluminescence (PL) originating from intrinsic defects in neutron-irradiated crystalline (x-) SiO₂ is observed and compared with that from amorphous (a-) SiO₂. The PL and photoluminescence excitation (PLE) spectra of x-SiO₂ are qualitatively similar to those of a-SiO₂. This suggests that PL centers, similar to those found in amorphous systems, are present in ordered systems. In addition, the PL and PLE spectra a-SiO₂ and a-As₂S₃ scale with energy band gap, suggesting that the radiative processes in a-SiO₂ and semiconducting chalcogenide glasses are alike. The similarity of the PL from x-SiO₂ to that from a-SiO₂ and the scaling of the PL from a-SiO₂ and a-As₂S₃ with energy band gap strongly suggest that PL centers are unique bonding configurations which primarily depend on the chemistry of the system rather than on the degree of long range order.     

Silicate groupings in glassy and crystalline 2PbO·SiO2

The type and the amount of silicate groupings existing in glassy and crystalline 2PbO·SiO₂ have been determined by direct chemical methods: paper chromatography, trimethylsilylation combined with gas-liquid partition chromatography and by the molybdate method. The results obtained by these three different methods are in good agreement and demonstrate, that glassy 2PbO·SiO₂ and each of the three main crystalline polymorphs are characterized by its own specific silicate anion distribution: the distribution in vitreous 2PbO·SiO₂ is of a polyanionic nature; in T---Pb₂SiO₄ dimetic groups [Si₂O₇]⁶⁻ prevail; M₁---Pb₂SiO₄ contains predominantly [Si₄O₁₂]⁸⁻ rings and H---Pb₂SiO₄ is a typical polysilicate with chain anions [SiO₃²⁻]_n. The results fit a structural model according to which glass is a random array of discrete polyatomic groupings; the gradual transition from the glassy state to the stablest crystalline structure is connected with degradation and polymerization of silicate anions.     

Electrical conductivities of mixed cation glasses

The electrical conductivities of (1−x) Li₂O · x BaO · 2 SiO₂, (1−x) Na₂O · x MgO ·2 SiO₂, (1−x) Na₂O · x CaO · SiO₂ and (1−x) Na₂O · x BaO · 2SiO₂ glasses were measured at temperature ranging from room temperature to 450°C. The transport numbers for Na⁺ ion in (1−x) Na₂O · x BaO · 2 SiO₂ glasses were measured. It was found that the alkali ion carried a significant part of the current in these glasses except one that had no alkali ions, and the conductivity decreased markedly as the alkali oxide was substituted by an alkaline earth oxide. The results of conductivity measurements combined with the data hitherto reported on mixed alkali glasses led to the proposal that the so-called mixed alkali effect could be explained on the basis of the independent path model in which it is assumed that cations can move only through vacant sites left by those of the same type.     

高性能刷状ZnO介晶的制备及其对复合树脂性能的增强作用

无机填料作为齿科复合树脂的主要成分,对其性能影响最为显著。本文以阿拉伯胶为结构导向剂,用热水解法合成了多孔、分级结构的刷状ZnO介晶,其厚度和直径分别为1.2 μm和1.0 μm。通过微流控制法在其表面包覆了4~6 nm无定形SiO₂,以利于其表面硅烷化。通过场发射扫描电镜(FE-SEM)、X射线衍射仪(XRD)、热重分析仪(TGA)等对其进行了表征。对ZnO@SiO₂进行硅烷改性处理后,将其作为辅助填料,与改性纳米SiO₂主填料一起添加到Bis-GMA/TEGDMA树脂体系中,光固化得到齿科复合树脂。力学测试表明,ZnO@SiO₂填充质量分数控制在5%以内时可有效提高复合树脂力学性能。与单一二氧化硅填料的复合树脂相比,添加填充质量分数3% ZnO@SiO₂,复合树脂的力学性能表现最佳,其弯曲强度、弯曲模量和压缩强度分别提高了12.9%、6.6%和3.7%,同时还表现出优良的抗菌活性,对变异链球菌抗菌率达98.7%。此外,添加了ZnO@SiO₂介晶填料的复合树脂还具备更好的耐磨性。     

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.     

Oscillator strength of the infrared absorption band near 1080 cm in SiO2 films

It has been well known that the absorption maximum of the peak near 1080 cm⁻¹ in amorphous SiO₂ films shifts continuously with variation of thickness and properties such as stress. This is a first report on the oscillator strength of the absorption against frequency at the absorption maximum. SiO₂ films on silicon wafers were prepared by thermal growth in either dry O₂ or an O₂/H₂ mixture or liquid-phase deposition in HF saturated with silica gel. The oscillator strength continuously decreased from 1×10⁻⁴ down to 1×10⁻⁵ with the frequency shift from 1099 to 1063 cm⁻¹.     

Fabrication of fluorine-doped silica glasses by the sol-gel method

Fluorine-doped silica glasses are produced by the sol-gel method for optical fiber preforms. In order to dope fluorine into silica glass, fluorinated silicon alkoxide, Si(OC₂H₅)₃F, is titrated into SiO₂ sol solutions. The fluorine content in silica glass depends on: the fluorine concentration in the gel, the specific surface area of SiO₂ particles and the heating rate in the sintering process. Fluorine-doped silica glass with a maximum relative refractive index difference of −0.93% is obtained. Using this technique, optical fibers with a triangular refractive index profile are fabricated with a minimum optical loss of 1.6 dB/km at 1.69 μm wavelength.     

Calculation of NMR shieldings and other properties for three and five coordinate Si, three coordinate O and some siloxane and boroxol ring compounds

Valuable information on the geometric and electronic structure of both predominant and defect species in the bulk and on the surface of amorphous SiO₂ can be obtained from solid state ²⁹Si and ¹⁷O NMR. Most previous NMR.studies have made assignments of structure types to NMR signals by relying on a comparison to crystalline reference materials. Using the quantum mechanical technique of Coupled Hartree-Fock Perturbation Theory (CHFPT) we can directly calculate NMR shielding tensors, σ, for Si and O and electric field gradients tensors, q for O in silicates. Previous CHFPT calculations on (SiH₃)₂O at Si---O---Si = 180° to 140° semiquantitatively reproduced observed trends in σ for SiO₂ polymorphs. These calculations have been improved and extended to Si---O---Si = 120° in (SiH₃)₂O and to the small siloxane rings H₄Si₂O₂, H₆Si₃O₃, H₈,Si₄O₄ which are models for the ring structures which may occur in the bulk and surface of amorphous SiO₂. Thus, predictions can be made of the ¹⁷O and ²⁹Si NMR characteristic of such species. We have also calculated NMR shieldings and other properties for three and five coordinate Si and for three coordinate O. The ²⁹Si NMR shielding increases with coordination, as expected, and five coordinate Si shows an anisotropy which although large is still smaller than that inferred from spin-lattice relaxation times in silicate melts. O q values are also calculated for (BH₂)₂O and H₃B₃O₆. The results are consistent with O EFGs and Raman frequencies observed in B₂O₃ glass, supporting a boroxol ring model.     

Vibrational spectroscopy of LaBSiO5 glass and glass–crystal composites

Infrared (IR) reflectivity and Raman scattering spectra of LaBSiO₅ glass and glass–crystal composites were studied in the temperature range 25–260 °C. Using an analogy with the LaBGeO₅ crystal it was possible to assign the main spectral features of the LaBSiO₅ glass and glass–crystal composites. The BO₄ chain arrangement and the bending vibrations of SiO₄ are influenced by the loss of the long-range order in the glass whereas the stretching vibrations of the SiO₄ groups are practically unaffected. The structural disorder in LaBSiO₅ crystallites is caused by rotation of BO₄ tetrahedra.     

Electronic structure and charge transport properties of amorphous Ta2O5 films

Amorphous Ta₂O₅ films were deposited by sputtering Ta onto silicon substrates with reactive ion beam. Electron energy loss spectroscopy measurements on the film found that the plasma oscillation energy is 23.1 eV. The refractive index and the extinction coefficient were measured with spectroscopic ellipsometry over the spectral range of 1.9–4.9 eV. The optical band gap is found to be 4.2 ± 0.05 eV. The valence band consists of three bands separated by ionic gaps. The values of electron effective masses were estimated with DFT quantum-chemical calculation. Experiments on injection of minority carriers from silicon into oxide were also conducted and we found that the electron component of conduction current governed by the electron current in the amorphous Ta₂O₅.     

An infrared study of crystallization in sodium-disilicate glasses containing iron oxides

The infrared absorption spectra of sodium-disilicate glasses containing various amounts of Fe₂O₃ ([Na₂O · 2 SiO₂]_1−x [Fe₂O₃]_x, where X = 0.05, 0.1 and 0.2) were investigated in the wavenumber range from 200–2000 cm⁻¹. The addition of Fe₂O₃ to the sodium-disilicate glass does not seem to introduce any new absorption band as compared with the spectrum of a pure sodium-disilicate glass; nevertheless, a general shift of the existing absorption bands toward lower wavenumbers is observed. The amount of shift is, in fact, proportional to the content of Fe₂O₃ in the glass. This observation is consistent with the recently proposed structural model for the bonding of Fe³⁺ ions in the iron-sodium-silicate glass system.

Annealing of 20 mol% iron oxide glasses at 550 and 580°C produced an extra sharp infrared absorption peak at about 610 cm⁻¹ wavenumber. This new peak is believed to be related to the crystallized particles of the glass as concluded from both a scanning electron micrograph and an electron diffraction pattern.     

Cracking assisted nucleation in chemical vapor deposition of silicon nanoparticles on silicon dioxide

Deposition of sub-monolayer silicon on SiO₂/Si(1 0 0) greatly facilitates nucleation in subsequent thermal chemical vapor deposition (CVD) of silicon nanoparticles. Sub-monolayer seeding is accomplished using silicon atoms generated via disilane decomposition over a hot tungsten filament. The hot-wire process is nonselective towards deposition on silicon and SiO₂, is insensitive to surface temperature below 825 K, and gives controlled coverages well below 1 ML. Thermal CVD of nanoparticles at 1×10⁻⁴ Torr disilane and temperatures ranging from 825 to 925 K was studied over SiO₂/Si(1 0 0) surfaces that had been subjected to predeposition of Si or were bare. Seeding of the SiO₂ surface with as little as 0.01 ML is shown to double the nanoparticle density at 825 K, and densities are increased twenty fold at 875 K after seeding the surface with 30% of a monolayer.     

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.     

Radiation-induced trapping centers in thin silicon dioxide films

In this paper the technological and scientific aspects of radiation-related charge trapping in thin SiO₂ films are reviewed. These films are amorphous in nature and are thermally grown on single crystal silicon substrates serving as the insulating layer in metal-oxide-semiconductor (MOS) capacitors and transistors. The structure and operation of these devices are reviewed with special emphasis on the effect of charges trapped in the oxide. The technical importance of understanding the interaction of ionizing radiation with thin SiO₂ films is illustrated with two practical examples. The first involves the operation of MOS transistors in environments where ionizing radiation is present, leading to an accumulation of positive space charge in the oxide. The second deals with process-induced defects generated by radiation encountered during the fabrication of devices by processes such as electron beam lithography or electron gun metallization. Unannealed traps of this type capture hot electrons producedin the substrate during the operation of the MOS transistor. In both these examples, the charging of the oxide results in instabilities which degrade operation.

Its sensitivity to charge trapped in the insulator makes the MOS system an ideal vehicle for scientific study of these phenomena. The basic techniques for characterizing the density, capture cross-sections, and location are briefly discussed and applied to the problem of radiation-induced defects in thin SiO₂ films. Ionizing radiation is shown to interact with the SiO₂ in two modes. In the first it supplies carriers to fill pre-existing hole traps at the interfaces. In the second it creates electron and hole traps in the bulk of the thin film. These latter defects are in a neutral state after irradiation and are detectable only when either electrons or holes are subsequently injected into the oxide. The capture cross-sections, trap densities and location of these centers in the film are presented. The annealing treatments required to remove these traps from aluminium and polysilicon gate devices are also discussed. The number traps produced by an incident 25 KV electron beam is found to depend weakly on the dosage. A dipolar defect, produced by the ionizing radiation, seems to explain the behavior of the neutral centers.     

Characteristic crystal growth from amorphous WO3 film by vacuum heating

Selective growth of WO₂, W and WO_3−x crystals from amorphous WO₃ film by vacuum heating at 400–900°C was clarified. The grown WO_3−x crystals were incommensurate structure based on crystallographic share structure. The growth process of WO₂ crystal in the amorphous film was directly observed at high temperature in the electron microscope. The growth front of the WO₂ crystal consumes WO₃ microcrystallites with various orientations. The growth speed of the WO₂ depended on WO₃ microcrystallites orientation. The origin of the wavy growth front of WO₂ was due to an orientation dependence of the WO₃ microcrystallites.