Separation et dosage de traces de bore dans le silicium : Nouvelle méthode de séparation et de dosage de traces de bore. application au dosage du bore dans le silicium

A new method is described for the separation and determination of traces of boron by extraction of methylene blue fluoroborate by dichlorethane The method has been applied to the determination of traces of boron in silicon and silica     

Spectrophotometric determination of traces of boron in silicon by means of solvent extraction

A spectrophotometric method for the determination of boron in silicon based on the extraction of the methylene blue-fluoroborate complex has been improved. Some important points, such as the dissolution of silicon with hydrofluoric acid and hydrogen peroxide, the effect of various anions on the blank absorbance and the best working conditions for forming and extracting the complex, have been studied. The method is applied to the determination of boron in silicon containing at least 1 p.p.m. of boron, with a relative standard deviation of ±5%.     

Spectrographic determination of ultramicro amounts of boron in high-purity silicon tetrachloride and trichlorosilane

A new sensitive method is proposed for the determination of boron in highpurity silicon tetra chloride and trichlorosilane. The method consists of complexing boron with triphenylchloromethane, removal of excess silicon tetrachloride, hydrolysis of the complex, and improved spectrographic excitation of liberated boric acid.The best sensitivity attainable is 0.03μg B, which corresponds to 0.06 p.p.b. B for a 500-g sample.     

PVC膜修饰电极上零电流示波电位滴定法测定硼的研究

以氯化十六烷基吡啶（ＣＰＣ）和氟硼酸钠形成的离子缔合物为活性物质，制成ＰＶＣ膜涂层石墨电极，提出了一个快速测定硼的零电流示波电位滴定法。以ＣＰＣ为滴定剂，用ＰＶＣ膜电极为指示电极，甘汞电极为参比电极，利用阴极射线示波器荧光屏上荧光点的突然位移来指示ＣＰＣ滴定硼的终点，具有灵敏、准确、快速等特点，用该法测定玻璃中的硼，结果良好。     

SIMS-characterization of ultra shallow boron-profiles after BF2+-and B+-low-energy-implantation in silicon

It has been shown using SIMS profiling that, by means of low energy ion implantation into crystalline and amorphous silicon, doping profiles with depths around 30 nm can be reproducibly produced. The deposition of a cap layer onto the silicon surface considerably improves the depth resolution of the SIMS apparatus in the case of extremely shallow doping layers. Fifty nanometre thick Au/Ge cap layers were applied successfully for the accurate measurement of the trailing course of the boron distribution. For future measurements of the course of reaction, a silicon cap layer is necessary to avoid or minimize the change of the sputter rate and the secondary ion yield in the interface region to the boron implanted silicon. A comparison with the measured boron distributions showed good agreement with simulations in the case of implantation into amorphous material.     

SIMS-characterization of ultra shallow boron-profiles after BF 2 + -and B+-low-energy-implantation in silicon

It has been shown using SIMS profiling that, by means of low energy ion implantation into crystalline and amorphous silicon, doping profiles with depths around 30 nm can be reproducibly produced. The deposition of a cap layer onto the silicon surface considerably improves the depth resolution of the SIMS apparatus in the case of extremely shallow doping layers. Fifty nanometre thick Au/Ge cap layers were applied successfully for the accurate measurement of the trailing course of the boron distribution. For future measurements of the course of reaction, a silicon cap layer is necessary to avoid or minimize the change of the sputter rate and the secondary ion yield in the interface region to the boron implanted silicon. A comparison with the measured boron distributions showed good agreement with simulations in the case of implantation into amorphous material.     

芳香族重氮盐氧化还原引发体系的研究——Ⅲ.芳香族重氮盐与亚铁盐氧化还原引发丙烯腈聚合过程中微量铜离子的影响

以苯重氮硼氟酸盐与亚铁盐在微量铜离子存在时能引发丙烯腈聚合,聚合速率服从:R∝[φN_2~+]~(1/2)[Fe~(++)]~(1/4)[Cu~(++)]~(1/4),氧化还原引发历程为: Fe~(++)+Cu~(++) Fe~(+++)+Cu~+ φN_2~++Cu~+→φ·+N_2+Cu~(++) φ·+M→φM·→φMM·…该历程符合上述动力学关系。但使用对硝基苯重氮硼氟酸盐时,微量铜离子对聚合反应速率影响不大,与亚铁盐浓度在一定范围呈R∝[Fe~(++)]~(1/2)的关系,因此例的引发历程为: φN_2~++Fe~(++)→φ·+N_2+Fe~(+++) φ·+M→φM·→φMM·…苯环上推电子取代基降低了重氮基的氧化势,如对位取代甲氧基、甲基或没有取代基都不能用纯亚铁盐引发丙烯腈聚合,需有微量铜盐存在才能聚合。而拉电子取代基如对位取代硝基、羧基可用纯亚铁盐引发聚合。     

Oxonium ions as initiators for vinyl polymerizations. A reappraisal

Triethyl oxonium fluoroborate either preformed or preparedin situ by the reaction of boron trifluoride etherate with epichlorohydrin does not initiate the homo or copolymerization of vinyl monomers. Small conversions to copolymers by use of these initiators with low methyl methacrylate incorporation is ascribed to conventional vinyl copolymerizations, initiated by free boron trifluoride and/or protonic impurities in the system.     

Development of an on-line isotope dilution laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method for determination of boron in silicon wafers

A method has been developed based on an on-line isotope dilution technique couple with laser ablation/inductively coupled plasma mass spectrometry (LA-ICP-MS), for the determination of boron in p-type silicon wafers. The laser-ablated sample aerosol was mixed on-line with an enriched boron aerosol supplied continuously using a conventional nebulization system. Upon mixing the two aerosol streams, the isotope ratio of boron changed rapidly and was then recorded by the ICP-MS system for subsequent quantification based on the isotope dilution principle. As an on-line solid analysis method, this system accurately quantifies boron concentrations in silicon wafers without the need for an internal or external solid reference standard material. Using this on-line isotope dilution technique, the limit of detection for boron in silicon wafers is 2.8 × 10¹⁵ atoms cm⁻³. The analytical results obtained using this on-line methodology agree well with those obtained using wet chemical digestion methods for the analysis of p-type silicon wafers containing boron concentrations ranging from 1.0 × 10¹⁶ to 9.6 × 10¹⁸ atoms cm⁻³.     

Summary of ISO/TC 201 Standard: X ISO 17560:2002—Surface chemical analysis—Secondary ion mass spectrometry—Method for depth profiling of boron in silicon

This International Standard specifies a secondary ion mass spectrometric method using magnetic‐sector or quadrupole mass spectrometers for depth profiling of boron in silicon, and using stylus profilometry or optical interferometry for depth calibration. This method is applicable to single‐crystal, polycrystal or amorphous silicon specimens with boron atomic concentrations between 1 × 10¹⁶ and 1 × 10²⁰ atoms cm^?3, and to the crater depth of 50 nm or deeper. Optical interferometry is generally applicable to crater depths in the range 0.5–5 µm. Copyright © 2004 John Wiley & Sons, Ltd.     

Mass spectrometry of some triphenylcyclopropenium salts. Competition between dimerisation and adduct formation

The triphenylcyclopropenium chloride, bromide and iodide evaporate in the mass spectrometer mainly as the covalent cation-halide adduct, the fluoroborate as the corresponding fluoride adduct and boron trifluoride. In addition di-3,3′-triphenylcyclopropene is formed, presumably via triphenylcyclopropenyl radicals.     

Colorimetric fluoride ion sensing by boron-containing pi-electron systems.

The boron-containing pi-conjugated systems, including tri(9-anthryl)borane (1) and tris[(10-dimesitylboryl)-9-anthryl]borane (2), have been investigated as a new type of fluoride chemosensor. Upon complexation of 1 with a fluoride ion, a significant color change from orange to colorless was observed and, in the UV-visible absorption spectra, the characteristic band of 1 at 470 nm disappeared and new bands around 360-400 nm assignable to pi-pi transitions of the anthryl moieties were observed. This change can be rationalized as a result of the interruption of the pi-conjugation extended through the vacant p-orbital of the boron atom by the formation of the corresponding fluoroborate. The binding constant of compound 1 with the fluoride ion was quite high [(2.8 +/- 0.3) x 10(5) M(-1)], whereas 1 only showed small binding constants with AcO- and OH- of around 10(3) M(-1) and no sensitivity to other halide ions such as Cl-, Br-, and I-, thus demonstrating its selective sensing ability to the fluoride ion. In contrast to the monoboron system 1, compound 2 having four boron atoms showed multistage changes in the absorption spectra by the stepwise complexation with fluoride ions.     

Determination of boron in silicon by SIMS with the matrix ion species ratio method

Summary In quantitative SIMS, the oxygen content of the sample surface proves to be a very important analytical parameter. The matrix ion species ratio method (MISR) was used to investigate the influence of the presence of oxygen on the determination of boron in silicon. By analysing standard samples at conditions of different oxygen coverage, the relation between the sensitivity of boron and the oxygen content of the sample surface, as indexed by the SiO⁺/Si³⁺ matrix ion species ratio, was established. The influence of the primary ion current density on this relation was investigated. The MISR procedure proves to be a suitable method to perform quantitative determinations (relative error < 10%) in conditions of changing oxygen content on the sample surface.

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Bestimmung von Bor in Silicium durch SIMS mit der Matrix Ion Species Ratio Method

     

Quantitative analysis of boron profiles in silicon using ion microprobe mass spectrometry

Single crystal silicon samples of various boron concentrations are studied using an ion microprobe. Argon and oxygen ion beams are used for the scanning and the determination of the boron profiles. Erosion rates are discussed.     

Potentiometric determination of the stability constants of the fluoroborate-dye complexes used in colorimetric analysis for boron

An extensive bibliography on the determination of boron by means of tetrafluoroborate-dye complexes is given. The stability constants of the fluoroborate—dye complexes are calculated from potentiometric measurements with an Orion fluoroborate ion-selective electrode, for the following nineteen dyes: methylene blue, methylene green, new methylene blue N, thionine, toluidine blue O, malachite green, brilliant green, crystal violet, fuchsine, methyl green, methyl violet, Victoria blue B, brilliant cresyl blue, Nile blue A, rhodamine B, rhodamine 6G, pyronine Y, safranine T and Janus green B. The solubilities of these dyes have been determined by spectrophotometry.     

Consolidation by Spark Plasma Sintering of a Ceramic Material Based on Silicon Carbide with Good Physicomechanical Properties,Mechanochemically Activated with Boron

Industrial silicon carbide powder was consolidated with boron by the spark-plasma-sintering (SPS) method. It was shown that a preliminary mechanical activation is a promising method for introduction of high concentrations of boron into silicon carbide. The influence exerted by the boron concentration on the sintering and properties of the material based on silicon carbide was examined. A ceramic based on silicon carbide with 10 wt % amorphous boron was obtained with density of 3.12 g cm^–3, hardness of 31.9 GPa, and crack-resistance coefficient of 5.7 MPa m^1/2. The ceramic is promising as a construction ceramic for nuclear reactors and gas-turbine engines.     

Boron implantation in Si: Channeling effects studied by SIMS and simulation

The axial channeling behaviour of boron implants in <100>, <110> and <111> silicon wafers is investigated by SIMS. Large differences of channeling characteristics such as channeled projected range (the projected range of channeled ions or channeling peak) and the fraction of channeled to implanted ions are observed among the three major crystal orientations. Within the critical angle, the channeling behaviour is very sensitive to the incidence beam angle with respect to crystal orientations. SIMS measurements are performed at different positions along several critical directions over a whole wafer. Well channeled profiles with an incidence beam angle to crystal orientations of 0 ° are obtained for each ion implantation energy and orientation. The results are used to test various models of ion implantation by simulation. A 3-parameter model for electronic stopping power of boron in silicon was proposed.     

Synthetic applications of dimethyl(methylthio)sulfonium fluoroborate: Sulfenyletherification and sulfenyllactonization

A new method for the formation of cyclic ethers and lactones is described. Dimethyl(methylthio)sulfonium fluoroborate (DMTSF) initiates formation of an episulfonium ion, which is followed by internal nucleophilic displacement to give the products in good yields.