Ultra Fine Layered Silicate Synthesis from Synthetic Silicate Raw Material

This paper reports the results of experiments on ultra fine layered silicates Na-fluorotaeniolite and Na-fluorotetrasilicic mica synthesis in the melts prepared from reaction blends based on synthetic silicate raw material, namely synthetic magnesium silicate dihydrate (MSDH, MgO·SiO₂·2H₂O). The MSDH–Na₂SiF₆–LiF, MSDH–Na₂SiF₆–MgF₂ and MSDH–Na₂SiF₆–NaF blends, whose compositions are close to the stoichiometry of the Na-fluorotaeniolite (NaMg₂Li[Si₄O₁₀]F₂) and Na-fluorotetrasilicic mica (NaMg_2.5[Si₄O₁₀]F₂) were studied in the temperature range 1080–1225°C. Magnesium silicate dihydrate, the phase composition of synthesis products and layered silicates (Na-fluorotaeniolite and Na-fluorotetrasilicic mica) were examined using the crystal optical, X-ray diffraction at room and high temperatures, differential thermal and chemical analyses. It has been shown that studied blends possessed a high reactivity, owing to which the layered silicates were synthesized at lower temperatures (～180–300°C) and the duration of the synthesis was shortened severalfold. The maximal yield of the Na-fluorotetrasilicic mica was observed in the reaction blend with the Na₂SiF₆ and NaF as halogen-containing compounds. The specific effects of MSDH on the physicochemical processes proceeded during heat treatment of the reaction blends were described.     

A new method for determining relaxation energies by means of aes and xps and its application to silicon compounds

A new method is presented for the determination of the absolute dynamic relaxation energy R_D from experimental Auger parameters, the static dielectric constant and the plasmon energy of the solids. The relaxation energies of the Si 1s and 2p core levels in Si, SiC, SiO₂, Si₃N₄ and Na₂SiF₆ are investigated by comparing the experimental values with theoretical results from a semiempirical dielectric theory. Both the experimental and theoretical results are valid only for the least-bound Si 2p state. The calculated relaxation shifts ΔR_D^ea(1s) and ΔR_D^ea(2p) are in reasonable agreement with the experimental values, and describe the extraatomic polarization effect well also for a deep level.     

Etching of SiC by energetic F2: Molecular dynamics simulation

Molecular dynamics (MD) simulations were performed to investigate F₂ continuously bombarding silicon carbide (SiC) surfaces with energies in the range of 50-200 eV at normal incidence and room temperature. The Tersoff-Brenner form potential was used. The simulation results show that the uptake of F atoms, the etch yields of C and Si from the initial substrate, and the surface structure profile are sensitive to the incident energy. Like occurrence in Si etching, steady-state etching is observed and an F-containing reaction layer is formed through which Si and C atoms are removed. A carbon-rich surface layer after bombarding by F₂ is observed which is in good agreement with experiments. In the reaction layer, SiF in SiF₂ species are dominant; with increasing incident energy, the total fraction of SiF and SiF₂ increases, while the amount of SiF₃ and SiF₄ decreases. Finally, etching mechanisms are discussed.     

F原子与SiC(100)表面相互作用的分子动力学模拟

本文采用分子动力学模拟方法研究了F原子(能量在0.5—15 eV之间)与表面温度为300 K的SiC(100)表面的相互作用过程. 考察了不同能量下稳定含F反应层的形成过程和沉积、刻蚀过程的关系以及稳定含F反应层对刻蚀的影响. 揭示了低能F原子刻蚀SiC的微观动力学过程. 模拟结果表明伴随着入射F原子在表面的沉积量达到饱和,SiC表面将形成一个稳定的含F反应层. 在入射能量小于6 eV时,反应层主要成分为SiF₃,最表层为Si-F层. 入射能量大于6 eV时,反应层主要成分为SiF. 关键词： 分子动力学 刻蚀 能量 SiC     

Isotopically selective CVD of silicon by IRMPD of Si2F6

The IRMPD of Si₂F₆ by a CO₂ TEA laser was applied to isotopically selective CVD of silicon. A white film, probably consisting of polymers of SiF₂, was deposited on a metal foil during the irradiation of natural Si₂F₆ with the laser radiation at 951.19 cm^–1 and about 1.5 J cm^–2. Upon heating, the film became dark brown, evolving SiF₄. The³⁰Si content was found to be as high as about 20%.     

Practical separation of silicon isotopes by IRMPD of Si2F6

Large-scale silicon isotope separation based on the IRMPD of natural Si₂F₆ has been carried out using a commercially available high power CO₂ TEA laser and a flow reaction system. The decomposition product SiF₄ containing 19–33% of ³⁰Si was obtained at a production rate of 1.5×10^–2–2.6×10^–2 mol·h^–1, depending on experimental parameters such as laser wavelength, laser fluence, pressure, and flow rate. SiF₄ containing 12% of ²⁹Si was obtained under slightly different conditions, i.e., at a shorter wavelength than that for ³⁰Si. When 39% of Si₂F₆ was decomposed at a slow flow rate, residual Si₂F₆ was found to have 99.7% of ²⁸Si. The production rate was 4.2×10^–2 mol·h^–1.     

First principles study of Si etching by CHF3 plasma source

A model of CF₃ etching Si (2 × 4) surface has been developed based on density functional theory. We find that the reconstruction Si surface tends to be fully F-terminated. Meanwhile, C-C chain forms spontaneously on the top of the surface to resist further F-Si interacting. Over-saturated Si bonds could still be stable as well due to the strong F-Si bonding, however, it needs to overcome an energy barrier of 1.85 eV to achieve this doubly saturated bonding. Two reaction paths are found to investigate chemical reaction of CF₃ with the full F-terminated Si surface. The first path displays that all fully saturated F-Si bonds could be over-saturated and thus produce F-Si-F bonds with an energy barrier of ∼1.85 eV. For this path, there is no product of SiF₄; the second path indicates a formation of SiF₄ with a much lower surface energy than the first path. The formation of SiF₄ shows the possible etching mechanism.     

E.S.R. spectra of SiF3 radicals produced in a single crystal of SiF4

E.S.R. spectra of a γ-irradiated single crystal of SiF₄ were investigated. The spectra observed were attributed to SiF₃ radicals having ²⁸Si (I=0) and ²⁹Si (I=1/2) atoms. From the angular dependence of the spectral lines on rotation of the single crystal, hyperfine tensors were determined for three fluorine atoms and the ²⁹Si atom of the SiF₃ radical. The three fluorine atoms in the radical are equivalent, whereas the directions of their hyperfine tensors are different from one another owing to the pyramidal structure of the radical. In addition to the hyperfine analysis, the analysis of the superhyperfine structure due to neighbouring fluorine atoms gave information on the orientation of the radicals in the crystal and the mechanism of radical formation. The structure of the radical is discussed in comparison with that of the CF₃ radical.     

Diffusion of sodium ions in borosilicate glasses by molecular dynamics method

Molecular dynamics simulations of borosilicate glasses with different sodium oxide content has been carried out. The generated structure indicates that the major number of oxygen atoms introduced as Na₂O consumes in the borate network to convert the BO₃ triangles to BO₄ tetrahedra. The formation of nonbridging oxygen ions in the silica site occurs during the formation of BO₄ tetrahedra with low rate. At higher concentrations of Na₂O, the NBO's increases abruptly. The self diffusion of sodium ions depends essentially on the temperature, composition (number of Na⁺ ions) and the rate of cooling. The phase separation mechanism in borosilicate glasses can be detected by MD simulation since the environment of the B–O, Si–O and B–O–Si can be easily reached.     

Oxidizing agent concentration effect on metal-assisted electroless etching mechanism in HF-oxidizing agent-H2O solutions

The mechanism of metal-assisted electroless etching of silicon in HF-oxidizing agent-H₂O etching system as a function of oxidizing agent concentration was studied. Three types of oxidizing agent were experimented namely Na₂S₂O₈, K₂Cr₂O₇ and KMnO₄. Their concentrations were varied from 0.05 M to 0.3 M. The layers formed on silicon were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive X-ray (EDX). It is shown that an insoluble solid-phase film (K₂SiF₆) form on silicon surface when concentration of K₂Cr₂O₇ or KMnO₄ increases in chemical solutions. On other hand, when Na₂S₂O₈ concentration increases, the surface roughness decreases without any chemical complex formation.     

Thin-film formation of Si clathrates on Si wafers

In this study, we prepared Si clathrate films (Na₈Si₄₆ and Na_xSi₁₃₆) using a single-crystalline Si substrate. Highly oriented film growth of Zintl-phase sodium silicide, which is a precursor of Si clathrate, was achieved by exposing Na vapour to Si substrates under an Ar atmosphere. Subsequent heat treatment of the NaSi film at 400 °C (3 h) under vacuum (<10⁻² Pa) resulted in a film of Si clathrates having a thickness of several micrometres. Furthermore, this technique enabled the selective growth of Na₈Si₄₆ and Na_xSi₁₃₆ using the appropriate crystalline orientation of Si substrates.     

Novel clays: Solid-state synthesis,characterization and cation exchange selectivity

Several novel swelling mica-type clays have been synthesized by solid-state processes. Synthetic clays of ideal compositions such as Na₂Si₆Al₂Mg₆O₂₀F₄ · xH₂O (Na-2-mica), Na₃Si₅Al₃Mg₆O₂₀F₄ · xH₂O (Na-3-mica) and Na₄Si₄Al₄Mg₆O₂₀F₄ · xH₂O (Na-4-mica) have been prepared and characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and ²⁷Al and ²⁹Si solid-state magic angle spinning nuclear magnetic resonance (MASNMR) spectroscopy. Powder XRD showed that all syntheses yielded water swollen micas with c-axis spacing of ∼1.2 nm except in the case of Na-2-mica which also showed a small peak of anhydrous mica phase with a c-axis spacing of 0.96 nm. Solid-state ²⁷Al MASNMR spectroscopy revealed that almost all the Al is present in the tetrahedral environment of the different micas. Solid-state ²⁹Si MASNMR spectroscopy revealed different Si (Al) nearest neighbor environments depending upon the composition of the various micas. Selective cation exchange studies were performed on the various micas using 0.5 N NaCl solution containing 12.9 ppm Sr²⁺ or 8.12 ppm of La³⁺. The results showed, for the first time, that Na-3-mica has a high selectivity for the trivalent cation tested. The previously reported high selectivity of these synthetic micas for the divalent cations has been confirmed. These selective cation exchange studies are of relevance in cation separations from drinking and waste waters.     

样品温度对CF3+ 与Si表面相互作用影响的分子动力学模拟

利用分子动力学模拟方法研究了不同温度下CF_x层对CF⁺₃刻蚀Si表面过程的影响.由模拟数据可知,温度对C和F的沉积有显著的影响,通过提高样品的温度,物理刻蚀得到了加强,而化学刻蚀被减弱.同时,随着温度的升高,Si的刻蚀率相应增加.刻蚀产物中的SiF,SiF₂的量随温度的增加而增加,SiF₃的量与基体温度没有直接的关系.Si刻蚀率的增加主要是通过提高SiF,SiF_{2相似文献}   

Structure of Na2O·MO·SiO2·CaF2 (M=Mg,Ca) oxyfluoride glasses

(9−x)CaO·xMgO·15Na₂O·60SiO₂·16CaF₂(x=0, 2, 4, 6, and 9) oxyfluoride glasses were prepared. Utilizing the Raman scattering technique together with ²⁹Si and ¹⁹F MAS NMR, the effect of alkaline metal oxides on the Q species of glass was characterized. Raman results show that as magnesia is added at the expense of calcium oxide, the disproportional reaction Q³→Q⁴+Q² (Qⁿ is a SiO₄ tetrahedron with n bridging oxygens) prompted due to the high ionic field strength of magnesia, magnesium oxide entered into the silicate network as tetrahedral MgO₄, and removed other modifying ions for charge compensation. This reaction was confirmed by ²⁹Si MAS NMR. ¹⁹F MAS NMR results show that fluorine exists in the form of mixed calcium sodium fluoride species in all glasses and no Si–F bonds were formed. As CaO is gradually replaced by MgO (x=6, 9), a proportion of the magnesium ions combines with fluorine to form the MgF⁺ species. Meanwhile, some part of Na⁺ ions complex F⁻ in the form of F–Na(6).     

Effect of ultrasound on the synthesis of low-modulus zeolites from a metakaolin

It was studied the effect of ultrasonic processing (22 kHz) of the aqueous suspension of metakaolin, sodium hydroxide and alumina with a molar ratio 2Al₂Si₂O₇:12NaOH:2Al₂O₃ on the low-modulus zeolite synthesis processes. To investigate the XRD, SEM, IR, EDS had been used. It was shown that after ultrasonic processing, sodium aluminates are formed, what leads to a change in process of further synthesis. It was found that without ultrasonic processing on the stage of thermal treatment at 650 °C, SOD zeolite (|Na₆|[Al₆Si₆O₂₄]) and sodium aluminosilicate (Na₆Al₄Si₄O₁₇) are synthesized. In the sample after ultrasound during thermal treatment, only sodium aluminosilicates of cubic syngony (Na₆Al₄Si₄O₁₇ and Na₈Al₄Si₄O₁₈) are formed. It was demonstrated that sodium aluminosilicates are precursors for the formation of LTA zeolite (|Na₁₂|[Al₁₂Si₁₂O₄₈]). As a result zeolitization of sodium aluminosilicates after the hydrothermal crystallization in alkaline solution, the sonicated sample contained 97 wt% LTA. Without ultrasonic processing, the product of synthesis contained 50 wt% SOD and 40 wt% LTA.     

Application of synchrotron radiation to investigation of the mechanism of increase in the yield of alkali metal ions in electron-stimulated desorption

Core-level photoelectron spectroscopy with synchrotron radiation (hv = 140 eV) has been applied to study the variation in the Si⁺ charge state in silicon films deposited on the W(100) surface after thermal annealing of the substrate. The purpose of this study is to check the mechanism responsible for the sharp increase in the yield of Na⁺ ions in electron-stimulated desorption from a sodium layer adsorbed on the Si/W(100) surface after high-temperature annealing. The evolution of the W 4f _7/2 and Si 2p photoelectron spectra and the valence band photoemission spectra is investigated for two silicon coverages (1 and 3 ML) on the W(100) surface in the temperature range 300<T<2200 K. It is shown that annealing of 1 ML Si on the W(100) surface results in the formation of a W-Si covalent bond, which can weaken the Si-Na bond and lead to an increase in the equilibrium distance X ₀ and, hence, to an increase in the yield of Na⁺ ions in electron-stimulated desorption. The variation in the photoelectron spectra under annealing of 3 ML Si differs from that observed after annealing of 1 ML Si in the direction of charge transfer, thus correlating with the opposite effect of annealing of 3 ML Si/W on the Na⁺ yield in electron-stimulated desorption.     

Structures of vibrational absorption bands of the SiF4 molecule in a low-temperature nitrogen matrix

We have studied the IR absorption spectra of diluted mixtures SiF₄/M = 1/6000–1/10 000 in an N₂ matrix at 11 K (for comparison, the spectra of SiF₄ in Ar and Xe matrices have also been studied). It has been shown that, in solid nitrogen, the appearance of doublets is observed both in the range of the ν₃ band of the SiF₄ (²⁸SiF, ²⁹SiF₄, and ³⁰SiF₄) isotopologues of the SiF₄ molecule and in the range of the ν₁ + ν₄, ν₂ + ν₃, and ν₁ + ν₃ bands of ²⁸SiF₄, whereas, in the range of the 2ν₃ band of ²⁸SiF, a triplet appears. In order to analyze the influence of the matrix on the spectrum of free SiF₄ molecules, we have used a model that makes it possible to successively calculate (i) the spectrum of SiF₄ in terms of the model of local modes, (ii) the structure of a matrix composed by 864 N₂ molecules + a rigid SiF₄ molecule using the Monte Carlo method, and (iii) the interaction of matrix particles with local dipole moments in the approximation of dipole-induced dipole and dipole-quadrupole interactions. The model describes satisfactorily the low-frequency shift of bands in the nitrogen matrix. All obtained experimental and theoretical results are consistent with the assumption that two kinds of stable trapping centers of SiF₄ molecules obeying the T _d symmetry are realized in the nitrogen matrix.     

Structural characterization of pure Na-nephelines synthesized by zeolite conversion route

Using the zeolite thermally induced transformation route and starting from Na-LTA, Na-FAU and Na-GIS zeolites as precursors, we synthesized pure sodium nephelines (ps-Ne) with Si/Al ratios between 1.0 and 1.5 (ps-Ne_LTA, ps-Ne_FAU, ps-Ne_GIS). By X-ray diffraction analysis of intermediaries, we found that ps-Ne_LTA and ps-Ne_FAU were obtained as polymorphous transformation products from carnegieite phases and ps-Ne_GIS was synthesized directly from amorphous zeolite precursor. Stoichiometric ps-Ne_LTA {Na₈[Al₈Si₈]₁₆O₃₂} and non-stoichiometric ps-Ne_FAU {(Na_7.20□_0.80)₈[Al_7.20Si_8.80]₁₆O₃₂} and ps-Ne_GIS {(Na_6.41□_1.59)₈[Al_6.41Si_9.59]₁₆O₃₂} were obtained at temperatures 900-1200 °C. The crystal structures of these ps-Ne-s were refined in the P6₃ space group, from X-ray powder data using the Rietveld method. Mean T-O bond lengths decreases almost linearly with increasing the Si/Al ratio. These changes are induced by short-range order-disorder of Si, Al cations through the T_G and T_S sites. The increase of short-range disorder over T-sites, is followed and confirmed by ²⁹Si MAS NMR and IR spectroscopy. Comparison of the Si/Al ordering of synthesized ps-Ne structures with the published data shows inverse segregation of framework cations (Si; T1=T4 and Al; T2=T3). That is probably a consequence of applied synthesis route.     

Molecular dynamics study of particle emission by reactive cluster ion impact

Molecular dynamics (MD) simulations of sputtering process with fluorine cluster impact onto silicon targets were performed. By iterating collisional simulations on a same target, accumulation of incident atoms and evolution of surface morphology were examined as well as emission process of precursors. When (F₂)₃₀₀ clusters were sequentially irradiated on Si(1 0 0) target at 6 keV of total incident energy, column-like surface structure covered with F atoms was formed. As the number of incident clusters increased, sputtering yield of Si atoms also increased because the target surface was well fluoridised to provide SiF_x precursors. Size distribution of emitted particles showed that SiF₂ was the major sputtered particle, but various types of silicon-fluoride compounds such like Si₂F_x, Si₃F_x and very large molecules consists of 100 atoms were also observed. This size distribution and kinetic energy distribution of desorbed materials were studied, which showed that the sputtering mechanism with reactive cluster ions is similar to that under thermal equilibrium condition at high-temperature.     

SiF$lt;sub$gt;2$lt;/sub$gt;基态分子的结构与势能函数

运用Gaussian03软件包,采用密度泛函理论中的B3P86 方法,结合6-311++G^**（3df,3pd） 基组对基态SiF₂分子的平衡电子结构和谐振频率进行了优化计算,得到了其稳定结构为C_2v构型.SiF₂基态电子态为X¹A₁,平衡核间距R_Si—F=0.1061　nm,键角α_F—Si—F=100.6762°,离解能D_e=13.8　eV.应用多体项展式理论推导了基态SiF₂分子的解析势能函数,其等值势能图准确地再现了SiF₂分子的平衡构型特征和能量变化. 关键词： 2')" href="#">SiF₂ Murrell-Sorbie函数 多体项展式理论