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.     

Fluorine etching on the Si(111)-7×7 surfaces using fluorinated fullerene

Fluorine etching on the Si(1 1 1)-7×7 surfaces using fluorinated fullerene molecules as a fluorine source has been investigated. At room temperature, adsorbed fluorinated fullerene molecules reacted with the Si(1 1 1)-7×7 surface to create a localized distribution of fluorine on the surface. Nanoscale etch pits were created by annealing at 300 °C, due to the adsorption of the fluorine localized around the C₆₀F_x molecules. Annealing at 400 °C resulted in the delocalized fluorine distribution on the surface and healing of the etch pits, due to the enhancement of the diffusion of both the fluorine and silicon atoms. Subsequent annealing at 500 °C led to desorption of SiF₂ reactants formed on the surface. The fluorine diffusion process was found to be an elemental process in the etching because the diffusion of adsorbed fluorines is a key for the formation of the SiF₂ species and their subsequent 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.     

Further investigation on the formation mechanisms of (NH4)2SiF6 synthesized by dry etching technique

The validity of two formation mechanisms of ammonium silicofluoride (ASF), which are proposed to take place when a silicon surface is exposed to the vapor of HNO₃/HF acid mixture is investigated. Of the two proposed mechanisms regarding the synthesis of ASF on silicon surface, validity of the first predicting the release of hydrofluosilicic acid (H₂SiF₆) at the intermediate stage is examined by FTIR spectroscopy and the second mechanism suggesting O₂ release is investigated using the Winkler technique. IR absorbance bands of SiF₆²⁺ are observed on the fresh samples prepared at low (1/100) HNO₃/HF volume fractions. No significant amount of oxygen is detected during the synthesis of ASF films on silicon surface by dry etching technique. These two observations together provide firmer support for the validity of the second mechanism.     

Growth of SiO2 on InP substrate by liquid phase deposition

We have grown silicon dioxide (SiO₂) on indium phosphorous (InP) substrate by liquid phase deposition (LPD) method. With inserting InP wafer in the treatment solution composed of SiO₂ saturated hydrofluorosilicic acid (H₂SiF₆), 0.1 M boric acid (H₃BO₃) and 1.74 M diluted hydrochloric acid (HCl), the maximum deposition rate and refractive index for the as-grown LPD-SiO₂ film were about 187.5 Å/h and 1.495 under the constant growth temperature of 40 °C. The secondary ion mass spectroscope (SIMS) and energy dispersive X-ray (EDX) confirmed that the elements of silicon, oxygen, and chloride were found in the as-grown LPD-SiO₂ film. On the other hand, the effects of treatment solution incorporated with the hydrogen peroxide (H₂O₂) that can regulate the concentration of OH⁻ ion were also shown in this article. The experimental results represented that the deposition rate decreases with increasing the concentration of hydrogen peroxide due to the reduced concentration of SiO₂ saturated H₂SiF₆ in treatment solution.     

Millimeter and submillimeter-wave spectroscopy of silicon difluoride

The rotational spectra of ²⁸SiF₂, ²⁹SiF₂, and ³⁰SiF₂ in their ground vibrational states, as well as those of ²⁸SiF₂ in the v₁ = 1, v₂ = 1, v₃ = 1, and v₂ = 2 excited states have been studied in selected frequency regions between 80 and 700 GHz. Transitions involving a large range of quantum numbers have been observed, so that precise rotational and quartic centrifugal distortion constants could be determined for each of the spectra investigated. In addition, the complete set of sextic distortion constants was also obtained for the most abundant isotopomer in its ground vibrational state. The quadratic and cubic force constants of silicon difluoride have been refined by a least-squares procedure using a larger and more precise set of data.     

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%.     

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}   

Roles of SiH4 and SiF4 in growth and structural changes of poly-Si films

The structural properties of polycrystalline silicon films, prepared by plasma enhanced chemical vapor deposition system, with different flow rates of SiH₄/SiF₄ mixtures at 300 °C were investigated. This study indicates that the low hydrogen coverage on the growing surface, under optimum fluorine radicals, will be leaded to an improvement of crystallized area as compared with case of high hydrogen coverage surface. Moreover, the studies of the role of SiH₄ and SiF₄ radicals show that the SiH₄ radicals are important in the nucleation and growth of grains. However, SiF₄ radicals are effective in the structural change of grain boundaries regions and by this way, in the present system, establish the growth of grains under the dominant 〈1 1 0〉 direction. The stress investigation indicates that addition of high flow rate of SiF₄ in amorphous film, results in the nearly stress free films. Finally, we found that the changes in g-value reflect the changes in the intrinsic compressive and tensile stress in the both polycrystalline and amorphous silicon films.     

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     

Roles of SiH4 and SiF4 in growth and structural changes of poly-Si films

The structural properties of polycrystalline silicon films, prepared by plasma enhanced chemical vapor deposition system, with different flow rates of SiH₄/SiF₄ mixtures at 300 °C were investigated. This study indicates that the low hydrogen coverage on the growing surface, under optimum fluorine radicals, will be leaded to an improvement of crystallized area as compared with case of high hydrogen coverage surface. Moreover, the studies of the role of SiH₄ and SiF₄ radicals show that the SiH₄ radicals are important in the nucleation and growth of grains. However, SiF₄ radicals are effective in the structural change of grain boundaries regions and by this way, in the present system, establish the growth of grains under the dominant 〈1 1 0〉 direction. The stress investigation indicates that addition of high flow rate of SiF₄ in amorphous film, results in the nearly stress free films. Finally, we found that the changes in g-value reflect the changes in the intrinsic compressive and tensile stress in the both polycrystalline and amorphous silicon films.     

Synthesis and luminescence in some fluoro-silicates for the possible applications in OSL dosimetry

Various fluoro-silicates, viz. M₂SiF₆ (M=Li, Na, K) were synthesized by reacting the mixture of corresponding salt and silicic acid with Hydrofluoric acid. The thermal analysis of these materials was performed. These materials were doped with ions Ce³⁺, Cu⁺, Ag⁺ and photoluminescence, TL, OSL properties were studied. Intense TL and OSL was observed from these materials. Due to decomposition during heating, these materials may not be suitable as TL Phosphors, but will be good phosphors for radiation dosimetry using OSL.     

High resolution F1s absorption spectra of solid fluorides of 3d elements

The near-edge fine structure of the 1s absorption spectrum of fluorine atoms from solid-state fluorides of some elements belonging to the first-row transition series was studied for the first time with a high-energy resolution. The spectra were measured with the method of total electron yield by using the Russian-German beamline of monochromatized synchrotron radiation at the electron storage ring BESSY II. The fine structure in the spectra of these most ionic compounds of the 3d atoms is analyzed from comparison of their spectra with the absorption spectrum of fluorine in TiF ₆ ^2? molecular anions from the K₂TiF₆ crystal. The latter absorption spectrum is preliminarily identified by its simultaneous consideration with the 2p absorption spectrum of titanium in TiF ₆ ^2? and the spectrum of fluorine in PF ₆ ^? anions from the KPF₆ crystal and in free SF₆ molecules. The lowest free electronic states are shown to form due to covalent mixing of the 3d states of a metal atom with the 2p states of the nearest fluorine atoms.     

Kinetic Carbon Isotope Effects in the Decarbonylation of Lactic Acid of Natural Isotopic Composition and of [1-14C] Lactic Acid

Studies of carbon-13 and carbon-14 kinetic isotope effects (K. I. E.) in the decarbonylation of lactic acid (L. A.) in sulphuric acid and in phosphoric acids media have been summarized and compared with earlier studies of ¹⁴C and ¹³C K. I. E. in the decarbonylation of formic and oxalic acids in concentrated sulphuric acid. Supplementary data concerning the decarbonylation of L. A. in sulphuric acid diluted with water and in pyrophosphoric acid are presented and discussed. The observed temperature dependences of ¹³C and ¹⁴C K. I. E. in concentrated H₂SO₄ and in concentrated phosphoric acids media have been rationalized by invoking a change of the mechanism of decarbonylation of L. A. in concentrated sulphuric and phosphoric acids with temperature. Preliminary calculational results concerning ¹³C and ^1??C K. I. E. in decarbonylation processes are also presented. In H₂SO₄ diluted with water and in H₃PO₄ diluted with water the temperature dependence of ¹³C and ¹⁴C K. I. E. is normal and well reproduced by one frequency approximation. In concentrated sulphuric acid and in concentrated phosphoric acids besides the C—OH bond rupture the rupture of a C—C bond had to be considered also to reproduce the observed ¹³C K. I. E. in selected temperature regions.     

Synthesis of nano-β-CD@Fe3O4 magnetic material and its application in ultrasonic treatment of oily sludge

The extraction process of Tarim oil field in Xinjiang is accompanied by a large amount of oily sludge generation, which seriously restricts the progress of oil and gas development and causes serious pollution to the environment due to its large production, complex composition, and difficult treatment. Nanomaterials combined with ultrasound have been demonstrated to be a promising method for the disposal of hazardous oily sludge. In this paper, a magnetic material Nano-β-CD@Fe₃O₄ was prepared by hydrothermal method and surface modification method. Nano-β-CD@Fe₃O₄ can be intelligently enriched at the oil–water interface and oil-solid interface, and it can be stably dispersed to form nanofluid under the action of ultrasound. Nano-β-CD@Fe₃O₄ can cause changes in oil composition when it is exposed to ultrasound, resulting in the decrease of viscosity and increase of fluidity. The experimental results of treating oily sludge in Xinjiang Tarim showed that the best treatment effect was achieved when the concentration of Nano-β-CD@Fe₃O₄ was 0.5 %, the ultrasonic frequency was 60 Hz and the temperature was 60℃. This solution can reach 90.17 % oil removal efficiency within 45 min, and the secondary oil removal efficiency of Nano-β-CD@Fe₃O₄ recovered by magnetic separation could still reach 85.65 %. This efficient oily sludge treatment method proposed in our study provides valuable information for the development of oily sludge treatment technology.     

Chemical sputtering,a discussion of mechanisms

Sputtering can be defined as the process whereby particles leave the surface as a direct consequence of the presence of incident radiation. When particles leave the surface as a result of receiving momentum from the collision cascade induced by the incident radiation, the process is called “physical sputtering”. If the incoming radiation (ions, electrons, or photons) induces a chemical reaction which leads to the subsequent desorp-tion of particles, the process could be classified as “chemical sputtering”. There are a number of molecules such as CH₄, CF₄, CF₃H, CF₃CI, etc., whose binding energy to a large variety of surfaces is believed to be only a few kcal/mole. Therefore, these molecules will not remain absorbed at room temperature. Consequently, if they are generated from surface atoms by radiation-induced processes, they will almost immediately desorb into the gas phase. This process is one type of chemical sputtering. Recent data obtained in plasma environments suggest that this type of reaction is a widely occurring phenomena: however, few systematic quantitative investigations of the subject have been completed. In this paper we will review the evidence for chemical sputtering and discuss mechanisms based on experimental information obtained for the chemical sputtering of silicon and SiO₂ under argon ion bombardment in the presence of a molecular beam of XeF2. Under these conditions, 25 or more silicon atoms can leave the surface per incident argon ion. About 75% of the silicon is emitted as SiF₄ (gas) and the rest leaves as silicon atoms or SiFx radicals. The total yield (silicon plus fluorine) is greater than 100 atoms/ion. The measured yields are a strong function of XeF₂ flux and a much weaker function of ion energy in the range 500-5000 eV. The chemical-sputtering yield for SiO₂ is smaller than that of silicon by about an order of magnitude, but it is still larger than the physical-sputtering yield. Moreover, SiO₂ is also sputtered by electrons. These results indicate that the incident radiation induces a chemical reaction between silicon and adsorbed fluorine which produces SiF₄, and the SiF4 is subsequently desorbed into the gas phase. We define this process as chemical sputtering. The large yields are probably a consequence of weak binding between the surface and the SiF₄ molecule.     

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).     

First principles investigation of19F* nuclear quadrupole interaction in fourth group tetrafluorides

Using the Hartree-Fock-Roothaan procedure the nuclear quadrupole interactions of the¹⁹F (spin 5/2) nucleus in CF₄, SiF₄ and GeF₄ are studied. The theoretical results explain within 10% the observed experimental measurements by the time-differential perturbed angular distribution technique, including the important feature of sharp decrease of the¹⁹F^* nuclear quadrupole coupling constant in going from CF₄ to SiF₄, followed by an increase in going to GeF₄, while a simple consideration of the ionic characters of the C-F, Si-F and Ge-F bonds together with Townes and Dailey theory would lead to a continuous decrease from CF₄ to GeF₄. The dependence of the results on the choice of basis sets and the role of many-body effects is discussed.     

18O/16O and 13C/12C Fractionation During the Reaction of Carbonates with Phosphoric Acid: Effects of Cationic Substitution and Reaction Temperature

Abstract

The factors for ¹⁸O/¹⁶O fractionation between carbonates and CO₂ gas produced by the dissolution of the carbonates in phosphoric acid (sealed vessel method) have been investigated as a function of reaction temperature (20–90°C) and cationic substitution in the solid. Synthetic CaCO₃, Ca_0.75 Mn_0.25 CO₃, MnCO₃, BaCO₃ and SrCO₃ powders, and a natural kutnahorite sample were used as solids. The δ¹⁸O values of the gaseous CO₂ liberated by the reaction with phosphoric acid decrease with increasing temperature and seem to be a linear function of T(°K)^?2. The slopes are specific for different carbonates. No temperature-depended ¹³C/¹²C fractionation seems to exist.     

Enhancement of Anammox performances in an ABR at normal temperature by the low-intensity ultrasonic irradiation

A lab-scale ultrasound enhancing Anammox reactor (ABR_U) was established and irradiated once a week by ultrasound with the optimal parameter (frequency of 25.0 kHz, intensity of 1.00 W cm⁻² and exposure time of 36.0 s) obtained by response surface methodology (RSM). ABR_U and the controlled Anammox reactor (ABR_C) without ultrasonic treatment were operated in parallel. The start-up time of Anammox process in ABR_U (59 d) was shorter than that in ABR_C (69 d). At the end of the nitrogen load-enhancing period, NLR (0.500 kg N m⁻³ d⁻¹) and NRR (0.430 kg N m⁻³ d⁻¹) in ABR_U were both higher than NLR (0.400 kg N m⁻³ d⁻¹) and NRR (0.333 kg N m⁻³ d⁻¹) in ABR_C. The results of RTQ-PCR demonstrated that the specific low-intensity ultrasound irradiation improved the enrichment levels of AnAOB in mature sludge. SEM images and the observation of the macroscopic morphology of mature sludge showed that the ultrasound irradiation strengthened the formation of Anammox granular sludge, thereby improved the interception capacity and impact load resistance of the reactor, and enhanced the nitrogen removal performance in ABR_U. The ultrasonic enhanced Anammox reactor based on an ABR with the optimal parameters can promote the rapid start-up and efficient and stable operation of the Anammox process at normal temperature (around 25.0 °C).