Quantum-chemical modeling of lithiation of a silicon–silicon carbide composite

With the aim of searching for promising anode materials for lithium-ion batteries, quantum-chemical modeling of the introduction of lithium into a silicon layer supported by nitrogen-doped silicon carbide at Li: Si ratios of 1: 1, 2: 1, and 3: 1 has been performed by the density functional theory method with inclusion of gradient correction and periodic boundary conditions. It has been demonstrated that the absorption of lithium by silicon is energetically more favorable than the formation of a metal layer on the silicon surface. As the lithium concentration increases, the energy difference decreases; i.e., the introduction of lithium into silicon becomes increasingly less favorable, the network of silicon atoms is broken down into smaller and smaller pieces, while the layer thickness increases threefold.     

Admittance studies of hydrogen-induced states at the silicon—silicon dioxide interface

The admittance of Pd-thin SiO₂Si MOSCAP devices was studied as a function of the following variables: temperature, measurement frequency, oxide preparation conditions, applied gate voltage and ambient atmospheres of 100 ppm hydrogen in nitrogen and pure oxygen. Transient current, capacitance and annealing studies were also conducted for many of these variables. It is shown that hydrogen atoms produced by the catalytic action of the Pd on hydrogen molecules can be injected into the oxide—semiconductor interface where, depending on the choice of oxidation conditions for growing the oxide, they modify the density and capture cross-sections of the hydrogen-induced interfacial states. It is also demonstrated that below 125 °C, the injected hydrogen can be reversibly removed by changing the ambient gas from the H₂/N₂ mixture to pure oxygen.     

Quantum-chemical modeling of lithium removal from lithium–silicon–silicon carbide composite

The quantum-chemical modeling of the delithiation-induced reorganization of a Li _m Si _n layer applied to the surface of nitrogen-doped silicon carbide is performed by means of non-empirical molecular dynamics in the frame of the gradient-corrected density functional method with the goal for finding promising anode materials for lithium ion batteries. The ratios Li/Si are considered from 8/3 to 1/4. Partial removal of lithium atoms from the surface of the Li _m Si _n layer and annealing at a moderate temperature (400 K) is found to recover rapidly (as soon as within 10 ps) the uniform metal distribution over the layer when the ratio Li/Si is at least 3/4. At lower values of this ratio, the equalization slows down dramatically.     

Antireflective sol–gel TiO2 thin films for single crystal silicon and textured polycrystal silicon

In this paper, antireflective TiO₂ thin films have been prepared on single crystal silicon, and textured polycrystal silicon by sol–gel route using the dip-coating technique. The thickness and the refractive index of the films have been optimised to obtain low reflexion in the visible region, by controlling both the concentration of the titanium isopropoxide (Ti(ⁱOPr)₄), and the annealing temperature. We showed that the use of a TiO₂ single layer with a thickness of 64.5 nm, heat-treated at 450 or 300 °C, reduces the reflection on single crystal silicon at a level lower than 3% over the broadband spectral ranges 670–830 nm and 790–1010 nm, respectively. In order to broaden the spectral minimum reflectance as much as possible, we have proposed to texture polycrystal silicon wafers, and to coat these wafers by a TiO₂ single layer with a thickness of 73.4 nm. In this case, the reflectance has been reduced from 27 to 13% in the spectral range 460–1000 nm.     

Influence of variation in the silicon content on the silicon precipitation in the Al–Si binary system

Ti-based amorphous alloys produced by ultra-rapid melt cooling represent an excellent option as biomaterials because of their mechanical properties and corrosion resistance. However, complete elimination of toxic elements is affecting the glass-forming ability and amorphous structure could be obtained only for thin ribbons or powders that are subsequently processed by powder metallurgy. Amorphous ribbons of special Ti₄₂Zr₄₀Ta₃Si₁₅ alloy, which is completely free of any toxic element, were produced by melt spinning, and the thermostability of resulting material was investigated in order to estimate its ability for further heat processing. Isochronal differential scanning calorimetry (DSC) was used to determine transformation points such as glass transition temperature T _g or crystallization temperature T _x. The activation energy for crystallization of amorphous phase was calculated based on Kissinger method, using heating rates ranging between 5 and 20 °C min^?1. Amorphous structure of resulting ribbon was evidenced by means of X-rays diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM). It was determined that amorphous Ti₄₂Zr₄₀Ta₃Si₁₅ alloy has a high activation energy for crystallization, similar to other Ti-based amorphous alloys, which provides good thermal stability for subsequent processing, especially by means of powder metallurgy techniques.     

Synthesis of complex Si–O–N–H derivatives by molecular bombardment of silicon and silicon dioxide

Bombardment of a silicon target in a high vacuum with a molecular beam (mixture of high energy H₂+N₂, obtained by charge exchange) and a thermal beam of O₂ produces on the target a variety of compounds. The target is then bombarded by the same molecular beams which produce, extracted by an electrostatic field at an energy of about 10 keV, molecular ions due to the compounds thus formed. These ions are analysed (electromagnet) to give a primary spectrum of ions according to their mass, which are individually selected and dissociated in a collision cell (same H₂+N₂ mixture). Mass analysis of the dissociation fragments leads to the identification of silicon clusters (Si)_n and of Si–O–N–H derivatives, the fragmentations of which permit a definitive determination of their molecular complexity. Dissociation spectra have thus been obtained for some of the most intense peaks of the primary spectrum, on the one hand, and on the other hand for some peaks of lower intensity but of special interest to us (see below). The composition of the fragments is confirmed by the study of the satellite ions derived from the natural 28, 29 and 30 isotopes of silicon, and by the use of deuterium instead of hydrogen. None of the Si–O–N–H derivatives obtained was apparently known earlier. It is shown that some of these molecules (those ‘of special interest to us’) may be identical with sila-analogues of standard amino acids and of nucleic bases: the fact that their fragmentations are identical with those of the corresponding carbon analogues speaks in favour of a structural identity. However, one cannot yet distinguish between the various possible isomeric arrangements, as none of them has been independently prepared, which excludes a direct comparison with reference samples, and as these isomers might give identical fragments; we hope to be able to resolve this ambiguity later. Anyhow, the substances formed are the most complex molecular silicon derivatives so far produced: e.g. Si₂O₂NH₅, Si₃O₂NH₇, Si₄O₃NH₉, Si₄O₂N₂H₄, Si₄ON₃H₅, Si₅O₃N₂H₁₀, Si₅O₂NH₁₁, corresponding to sila-glycine, sila-alanine, sila-threonine, sila-uracile, sila-cytosine, sila-valine, sila-glutamine, – or isomers. Similar results have been obtained using a silicon dioxide target and high energy molecular beams of hydrogen and of nitrogen, without thermal oxygen, or with a carborundum target. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASmolecular impact / silicon derivatives / amino-acid silicon analogues     

Synthesis of silicon–nitrogen derivatives in quasi-interstellar conditions

At 2–4·10^–5 T, a silicon wafer is the target of a 5–10 keV molecular beam of dinitrogen. The products are extracted by an electric field, and analysed by mass. The ions of this primary spectrum are dissociated in a Kr collision chamber. From the fragments thus obtained, one deduces compositions for the secondary ions, and therefore for the primary products. This is helped by the presence, in silicon, of the isotopes ²⁸Si, ²⁹Si and ³⁰Si. Beside the clusters Si_n (n = 1–7), complex molecular species are thus obtained, such as Si₅N₄⁺, Si₅N₄H⁺, Si₅N₄H₂⁺. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASinterstellar dust / interstellar molecules / atomic impact / silicon / nitrogen derivatives     

The photometric determination of silicon as α-silicomolybdic acid

A photometric method for the determination of silicon based on the yellow color of α-silicomolybdic acid is described. The pH must be kept within the range 3.0–3.7, and the equilibrium state is established by beating the solution. Since the color of this modification is remarkably stable and reproducible, a high degree of precision can be attained.     

Self-assembled monolayers prepared from ω-thiophene-functionalized n-alkyltrichlorosilane on silicon substrates

Self-assembled monolayers (SAMs) of thienyl-functionalized n-alkyltrichlorosilane (11-(3-thienyl)undecyltrichlorosilane [TUTS]) have been prepared by adsorption from solution and characterized by using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), contact angle measurements, ellipsometry, and scanning electron microscopy (SEM). Using contact angle and SEM measurements, the film preparation protocol was optimized, resulting in reproducible SAM formation with no adverse deposition of polysiloxane particles. XPS and ellipsometry studies confirmed the existence of SAM formation. AFM results show a smooth and homogeneous SAM, with surface roughness of Ra≤0.2 nm, which is slightly higher than the corresponding values for octadecyltrichlorosilane (OTS) SAMs. Such thiophene-based SAM surfaces can be used for surface-initiated polymerization of thiophene. The resulting formed polythiophene layers at non-compatible surfaces offer some practical applications in manufacturing [W. Plieth, A. Fikus, D. Appelhans, H.-J. Adler, German Patent Application No. 2661977 (1998); D. Appelhans, D. Ferse, H.-J. Adler, A. Fikus, W. Plieth, B. Aldolphi et al., J. Electrochem. Soc. (accepted)].     

Correction to: Research progress of nano‑silicon‑based materials and silicon‑carbon composite anode materials for lithium‑ion batteries

Journal of Solid State Electrochemistry - In order to solve the energy crisis, energy storage technology needs to be continuously developed. As an energy storage device, the battery is more widely...     

Direct electrochemistry behavior of Cytochrome c on silicon dioxide nanoparticles-modified electrode

A newfangled direct electrochemistry behavior of Cytochrome c (Cyt c) was found on glassy carbon (GC) electrode modified with the silicon dioxide (SiO2) nanoparticles by physical adsorption. A pair of stable and well-defined redox peaks of Cyt c′ quasi-reversible electrochemical reaction were obtained with a heterogeneous electron transfer rate constant of 1.66×10-3 cm/s and a formal potential of 0.069 V (vs. Ag/AgCl) (0.263 V versus NHE) in 0.1 mol/L pH 6.8 PBS. Both the size and the amount of SiO2 nanoparticles could influence the electron transfer between Cyt c and the electrode. Electrostatic interaction which is between the negative nanoparticle surface and positively charged amino acid residues on the Cyt c surface is of importance for the stability and reproducibility toward the direct electron transfer of Cyt c. It is suggested that the modification of SiO2 nanoparticles proposes a novel approach to realize the direct electrochemistry of proteins.     

High electrophilicity at silicon in η3-silane σ-complexes: Lewis base adducts of a silane ligand, featuring octahedral silicon and three Ru-H-Si interactions

New η(3)-silane σ-complexes [PhBP(Ph)(3)]RuH(η(3)-H(2)SiRR') (RR' = PhMe, Ph(2)) were synthesized. Lewis bases [THF, 4-(dimethylamino)pyridine, and PMe(3)] coordinate to the silicon centers of these complexes to form stable adducts. The base adducts, [PhBP(Ph)(3)]Ru(μ-H)(3)SiRR'(base), feature three nonclassical Ru-H-Si interactions and hexacoordinate silicon centers, as determined by multinuclear NMR spectroscopy, X-ray crystallography, and computational investigations.     

Nano-sized polycrystalline bismuth silicon oxide powder by sol–gel technique

Bismuth silicon oxide (Bi₁₂SiO₂₀, BSO) nano crystalline powder was prepared by sol–gel technique using bismuth nitrate and tetraethyl orthosilicate as starting materials. The prepared samples were sintered at various temperatures (750 °C maximum) and characteristic sillenite single cubic phase with crystallite size ~38 nm (calculated from room temperature powder XRD measurements) was realized at 750 °C sintering temperature. SEM analysis showed that the powder contains the nano-sized particles with almost spherical morphology. The observed frequencies in room temperature FTIR spectrum could be assigned to Bi–O, Si–O and Bi–O–Si bonds. The FWHM (full width at half maximum) of the diffraction peaks decreased while the intensity of FTIR absorption lines increased with the increase in the sintering temperature indicating better bond formation and crystallization. The thermograph of the samples recorded in the temperature range 50–1,000 °C showed almost no weight loss after ~575 °C further confirmed the conclusion arrived at from XRD and FTIR analysis. The samples sintered at 750 °C showed about 50% absorbance in 400–600 nm region which was consistent with the pale yellow color of the sample. Broad blue emission centered ~478 nm was observed when excited by 350 nm radiation from a Xe-lamp. The intensity of this broad emission band increased while its FWHM decreased with the increase in sintering temperature. Self-trapped excitons could be responsible for this emission.     

Polymeric complex micelle loaded with axially substituted silicon（IV） phthalocyanine

A novel axially substituted silicon(IV) phthalocyanine, namely di-pyridyloxy axially substituted silicon(IV) phthalocyanine 2 was synthesized and characterized by UV/vis, IR, elemental analysis, MS as well as ¹H NMR spectroscopy. Hydrophobic 2 was encapsulated by amphiphilic triblock copolymer poly[N^ε-(benzyloxycarbonyl-lysine]-poly(ethylene glycol)-poly[N^ε-(benzyl oxycarbonyl) (PLL(Z)-b-PEG-b-PLL(Z)) to form hydrophobic 2-loaded polymeric complex micelle (PIC) (2-loaded PIC). Atom force microscopy (AFM) image showed that 2-loaded PIC formed a spherical nanocarrier with approximately 35-50 nm in diameter. The fluorescence intensity and lifetime of 2-loaded PIC was significantly enhanced by the incorporation 2 into PIC nanocarrier.     

Polymer brushes on hydrogen-terminated silicon substrates via stable Si—C bond

A universal and straightforward method for the preparation of polymer brushes via the formation of Si-C bond on silicon substrates through the UV-induced photopolymerization is demonstrated.     

Polymeric complex micelle loaded with axially substituted silicon(Ⅳ) phthalocyanine

A novel axially substituted silicon(Ⅳ)phthalocyanine,namely di-pyridyloxy axially substituted silicon(Ⅳ)phthalocyanine 2 was synthesized and characterized by UV/vis,IR,elemental analysis,MS as well as ~1H NMR spectroscopy.Hydrophobic 2 was encapsulated by amphiphilic triblock copolymer poly[N~ε-(benzyloxycarbonyl-lysine]-poly(ethylene glycol)-poly[N~ε-(benzyl oxycarbonyl) (PLL(Z)-b-PEG-b-PLL(Z))to form hydrophobic 2-loaded polymeric complex micelle(PIC)(2-loaded PIC).Atom force microscopy(AFM)image showe...     

Sol–gel derived ZnO/porous silicon composites for tunable photoluminescence

ZnO/porous silicon nanocomposites were fabricated by spin-coating the sol?Cgels of zinc acetate onto the top surface of porous silicon films. The photoluminescent properties of ZnO/porous silicon nanocomposites were investigated as a function of the concentration of zinc cations in the sol?Cgels. Characterizations with scanning electron microscopy, X-ray diffractometry and photospectroscopy indicated that ZnO nanocrystals were embedded into the spongy nanostructures of porous silicon after heat treatment at 245?°C for 20?min in air. The recorded photoluminescence exhibited that orange to green?Cblue emissions were achieved for the ZnO/porous silicon nanocomposites as the concentration of zinc cations in the sol?Cgels increased from 4 to 260?mM. The mechanisms on the tunability of the photoluminescence were discussed for the ZnO/porous silicon nanocomposites. Our results have demonstrated that the incorporation of green?Cblue phosphors into the porous matrix of porous silicon represents one endeavor to tune the photoluminescence of porous silicon across the visible spectral region.     

Synthesis and pharmacological activity of a silicon—zinc—boron-containing glycerohydrogel

Russian Chemical Bulletin - A new pharmacologically active nanostructured silicon—zinc—boron-containing glycerohydrogel was synthesized by the sol—gel method using silicon, zinc,...     

The determination of a π-sigma constant for substituents attached to silicon

The proton, ¹³C, and ²⁹Si chemical shifts and the ¹³C¹H coupling constants of a series of compounds of the type (CH₃)₃SiX were measured and correlated with inductive and resonance σ constants. In order to provide a comparison with a homologous series in which π-bonding is absent, shifts and coupling constants were obtained for the t-butyl series, (CH₃)₃CX. Only the coupling constants gave significant correlations with σ_I. A series of σ constants, presumably reflective of the amount of π-bonding, were obtained from the deviations from the J vs. σ_I plot. The magnitudes of these values indicate that oxygen is a better π-donor than nitrogen and chlorine.     

π-Relaxation of the ring strain: design of polycyclic unsaturated silicon molecules

Introduction of a double bond into cyclic silanes lowers the ring strain by the cyclic delocalization of π-electrons through the hyperconjugation with the σ bonds, which is favored by the high π-orbital energy of the SiSi bond and the low σ*-orbital energy of the Si-H bonds. The π-relaxation of strains significantly occurs in the small rings. Unsaturated small silicon ring molecules are less strained than the saturated ones and the unsaturated carbon congeners. We calculated a series of polycyclic silicon molecules to confirm the π-relaxation and suggested that some unknown molecules could be prepared due to the low strain.