New Developments in Activation Analysis for Material and Environmental Sciences

Activation analysis in general and mainly reactor neutron activation analysis (NAA) has been used extensively for measuring trace elements in high purity materials, particularly semiconductor materials. The advantages of NAA in determination of trace elements differ from one semiconductor material to another. For all of them the inherent properties of activation analysis especially those of non contamination with the reagents, low blanks and high sensitivity are the reasons for the choice of NAA as the main analytical procedure. These inherent properties are essential for analysis of high-purity materials where concentrations of ppb's and sub ppb's have to be measured. NAA is specially suitable for the determination of trace elements in silicon due to the very short lived very low activity induced by neutron reaction in silicon. This enables easy instrumental (i.e. without chemical separations) determination of trace elements in silicon. In the HFR reactor at Peten, Netherlands, a special facility was constructed for irradiation of silicon samples of Philips, in which silicon wafers of up to 15 cm diameter can be irradiated with 4 × 10¹³n. cm^?2. sec^?1 and the irradiation is done for 72–96 hours. using large Ge(Li) detectors (100 to 150cc) and long counting time (8–16 hours) they measured 22 elements in concentrations below ppb and 10 others between ppb and 300 ppm. Trace elements in germanium have been determined both instrumentally after very long decay time (100 days) or after short decay time removing the activities from the matrix by chemical separation. Trace elements in GaAs are determined only after chemical separtion. Several other semiconductor material such as Sc, Te, GaP and CuInS₂ were also determined by NAA. Some trace elements cannot be determined by neutron activation. Carbon, nitrogen and oxygen are determined by activation with protons, alphas or ³He particles. Boron and hydrogen are determined by prompt emission induced by charged particle activation, which gives not only the total concentration but also the depth profile. Carbon, nitrogen, oxygen and phosphorus were also determined by prompt proton activation analysis. The environmental samples studied by activation analysis can be divided into three categories: atmospheric aerosols, water samples and solid wastes. NAA of atmospheric aerosols have been used for their posible toxicological hazards, their source identification and for studies of atmospheric transport processes.     

Determination of oxygen in metals and semiconductors by means of the16O(T,n)18F reaction

Tritons accelerated up to 3.5 MeV by a Van de Graaff, were used to study the¹⁶O(T, n)¹⁸F reaction, which was then applied to the analysis of oxygen in metals and semiconductors. The calculated sensitivity for the determination of oxygen is 0.5 ppb at 3.5 MeV. Si, Ti and Mo were analyzed non-destructively at 3.5 MeV and the results agreed with results obtained by other methods. Pure Ge and AsGa were analyzed non-destructively at 3 MeV and the detection limits were respectively 25 and 6 ppb.     

Contribution of activation analysis with low energy charged particles to studies on GaAs

It is shown that the instrumental analysis of carbon and oxygen in GaAs, at trace level, can be achieved by irradiation with low energy deuterons and tritons (3 MeV). The experimental sensitivities are 6 ppb/weight for the¹⁶O( ₁ ³ H,n)¹⁸F reaction and 25 ppb/weight for the¹²C( ₁ ² H,n)¹³N reaction. Applications related to the metallurgy of GaAs are described.     

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.     

Synthesis, characterization and thermal properties of novel epoxy containing silicon and phosphorus nanocomposites by sol-gel method

Organic-inorganic hybrids were prepared using diglycidyl ether of bisphenol A (DGEBA) type epoxy and tetraethoxysilane via the sol-gel process. The DGEBA type epoxy was modified by a coupling agent to improve the compatibility of the organic and inorganic phases. The sol-gel technique was used successfully to incorporate silicon and phosphorus into the network of hybrids increasing flame retardance.Fourier transform infrared spectroscopy and ²⁹Si nuclear magnetic resonance spectroscopy were used to characterize the structure of the hybrids. In condensed siloxane species for TEOS, silicon atoms through mono-, di-, tri-, and tetra-substituted siloxane bonds are designated as Q¹, Q², Q³, Q⁴, respectively. For 3-isocyanatopropyltriethoxysilane and diethylphosphatoethyltriethoxysilane, mono-, di-, tri-, tetra-substituted siloxane bonds are designated as T¹, T², T³. Results revealed that Q⁴, Q³, T³ are the major environments forming a network structure. The morphology of the ceramer was examined by scanning electron microscopy and Si mapping. Particle sizes were below 100 nm. The hybrids were nanocomposites. The char yield of pure epoxy resin was 14.8 wt.% and that of modified epoxy nanocomposite was 31 wt.% at 800 °C. A higher char yield enhances the flame retardance. Values of limiting oxygen index of pure epoxy and modified epoxy nanocomposites are 24 and 32, respectively, indicating that modified epoxy nanocomposites possess better flame retardance than the pure epoxy resin.     

Voltammetric behavior and trace determination of Pb at a mercury-free screen-printed silver electrode

Screen-printed silver electrodes (AgSPEs), without chemical modification, has been investigated as disposable sensors for the measurement of trace levels of Pb²⁺. Potential segment analysis indicates that the formation of underpotential and bulk depositions of Pb is not strongly coupled on the AgSPE. The possibility of determining Pb²⁺ at trace levels using the reversible underpotential deposition peak was examined by square-wave anodic stripping voltammetry without removal of oxygen. Under the optimized analytical conditions, the obtained sensitivity, linearity, and detection limit are 0.355 μA/ppb, 5-80 ppb (r=0.9992), and 0.46 ppb (S/N=3), respectively. The electrode is quite stable for repetitive measurements. The interference effect was thoroughly studied with various metals and no significant change in current was found in the determination of 5 ppb Pb²⁺. The practical applications were demonstrated to measure trace Pb²⁺ in natural waters.     

Determination of oxygen with reactor neutrons

Oxygen in silicon was determined by the secondary nuclear reactions of⁶Li(n, α)T and¹⁶O(t, n)¹⁸F. Lithium fluoride was deposited in vacuum on fused quartz, covered with the sample and irradiated in a nuclear reactor. The depth profiles of¹⁸F in fused quartz and in silicon were observed, and enough depth to eliminate surface oxygen was estimated. On the basis of these results, oxygen was determined by the average cross-section method. Oxygen concentration in CZ silicon with various growing condition was 5–26 ppm and was consistent with those determined by the infrared absorption method. The detection limit of oxygen in silicon is 5 ppm.     

Impact sensitivity of energy systems based on nanoporous silicon and oxidant: influence of the hydrogen content and specific surface

The impact sensitivity of the energy systems based on nanoporous silicon, obtained by electrochemical etching of monocrystalline silicon wafers in an HF-containing electrolyte, and calcium perchlorate was studied using a modified Weller—Ventselberg technique (estimation of the impact sensitivity of initiating explosives). The impact sensitivity of these systems is shown to be determined by both the presence of hydrogen, which is stored on the porous silicon surface during the preparation of the latter, and also the influence of other factors, including the specific surface of porous silicon. The composition, amount of the generated gas, and gas evolution rate during nonisothermal and isothermal calcination of porous silicon in a temperature range of 60—120 °С were determined using methods of thermal gravimetry (TG), measurement of the gas volume, and mass spectrometry. The generated gas almost completely consists of hydrogen, and its content in the studied samples of porous silicon achieved ~3.8 wt.%. The calculated activation energy of the hydrogen evolution process in vacuo was 103.7±3.3 kJ mol^–1. The dependences of the impact sensitivity of the energy composition based on porous silicon and heat of combustion of porous silicon on oxygen on the hydrogen content were established. The impact sensitivity of the energy system decreases with a decrease in the hydrogen content in porous silicon and its specific surface.     

Effect of the content of hydrogen fluoride in an etchant on the formation of nanopores in silicon during electrolytic etching

The effect of the HF content on the formation of nanopores in silicon during electrochemical etching was studied. Nanoporous silicon layers were established to be formed only when hydrogen fluoride content in etchants (initial HF content: 49 wt %) was higher than 10–12 vol %. The mass and charge balance of the electrolytic etching of silicon was calculated, and the change in charge number of reaction (effective silicon valence) was determined depending on the HF content. The obtained data were used to propose a silicon etching model with the formation of SiF₄ and nanoporous silicon (where nanopores were formed due to the action of predominantly (HF₂)^? ions).     

Die Bestimmung des Sauerstoffgehaltes in Silizium nach Ionenimplantation durch eine SiO2-Deckschicht mit Hilfe der Reaktion18O(p, α)15N

The recoil implantation yield of oxygen atoms recoiled from¹⁸O-enriched SiO₂ layers into silicon substrates has been studied using the¹⁸O(p, α)¹⁵N nuclear reaction. The method to determine the number of oxygen atoms in silicon is described in detail and the results are compared to the theoretical predictions.     

Monitor for measuring the total concentration of reactive hydrocarbons in ambient air based on their chemiluminescence reaction with oxygen atoms

The monitor functions by measuring the intensity of the chemiluminescence radiation at 309 nm which is emitted during the reaction of hydrocarbons with O(³p) atoms. The system comprises a specially-developed stable source of atomic oxygen, a detection unit for measuring the intensity of the chemiluminescence radiation and a device for preconcentration of the hydrocarbons to be determined. The sensitivity of the monitor depends on the concentration and reactivity of the hydrocarbons, and is greatest for unsaturated compounds. For butadiene, the detection limit is 3 ppb, and response is linear over the range 0–2500 ppb. The monitor can also serve as a detector for unsaturated hydrocarbons in gas chromatography.     

多次透射反射红外光谱法灵敏和准确地测量单晶硅中间隙氧和代位碳的含量

建立了室温下使用多次透射反射红外光谱法(MTR-IR)测量单晶硅中间隙氧和代位碳含量的新红外光谱吸收方法,在理论和实验上证明了MTR-IR优于常规使用的单次垂直透射红外(IR)吸收测量方法。与IR法相比较,MTR-IR法的优点为:(1)间隙氧在1107 cm^-1处和代位碳在605 cm^-1处的吸收峰与MTR-IR法中红外光透过硅片的的次数N(6~12)成线性增加的正比例关系,因此单晶硅中间隙氧和代位碳含量的检测限至少比IR法低一个数量级;(2)MTR-IR法测量薄硅片如0.2 mm的厚度时产生的干涉条纹强度是单次垂直透射红外吸收法(IR)的1/23、是单次Brewster角透射红外吸收法的1/11;(3)单次垂直透射红外吸收法(IR)1次只测量样品上的1个点,MTR-IR法则在更长的样品上1次测量多个样品点,每次测量更具有代表性。理论计算和实验结果都证实了MTR-IR吸收法测量晶体硅中间隙氧和代位碳杂质含量的高灵敏度、可靠性和重复性。     

Inkjet Printed Multi‐walled Carbon Nanotube Sensor for the Detection of Lead in Drinking Water

Electroanalytical methods can be used for the reliable detection of the toxic heavy metal lead in drinking water samples. Inkjet printed electrodes have potential for the rapid and affordable assessment of drinking water. Researchers have shown the electrochemical sensing applicability of inkjet printed electrodes. In this work, Pb²⁺ was detected using an inkjet printed multi‐walled carbon nanotube (IJP‐MW‐CNT) electrode with silver tracks printed underneath. The silver tracks provide the sensor with the conductivity needed for sensitive measurements. MW‐CNT were dispersed in water using bile salts as a surfactant to prepare the ink. The IJP‐MW‐CNT electrode was used as the working electrode with a platinum wire and Ag/AgCl as auxiliary and reference electrode, respectively. The electrodes performance was optimized in 0.1 M acetate buffer (pH=4.3) and had two linear ranges of 5 to 20 ppb (R²=0.99) with a sensitivity of 38 nA/ppb and 20 to 50 ppb (R²=0.98) with a sensitivity of 15 nA/ppb and a limit of detection (LOD) of 1.0 ppb for Pb²⁺. The analytical applicability of electrode was determined by constructing a calibration curve in an unaltered drinking water sample (i. e.) Cincinnati tap water with two linear ranges of 15 to 40 ppb (R²=0.99) with a sensitivity of 1.5 nA/ppb and 40 to 70 ppb (R²=0.99) with a sensitivity of 3.5 nA/ppb and a LOD of 1.0 ppb for Pb²⁺. Effects of copper and cadmium as potential interferents are reported.     

多次透射反射红外光谱法灵敏和准确地测量单晶硅中间隙氧和代位碳的含量

建立了室温下使用多次透射反射红外光谱法(MTR-IR)测量单晶硅中间隙氧和代位碳含量的新红外光谱吸收方法,在理论和实验上证明了MTR-IR优于常规使用的单次垂直透射红外(IR)吸收测量方法。与IR法相比较,MTR-IR法的优点为:(1)间隙氧在1 107 cm^-1处和代位碳在605 cm^-1处的吸收峰与MTR-IR法中红外光透过硅片的的次数N(6~12)成线性增加的正比例关系,因此单晶硅中间隙氧和代位碳含量的检测限至少比IR法低一个数量级;(2)MTR-IR法测量薄硅片如0.2 mm的厚度时产生的干涉条纹强度是单次垂直透射红外吸收法(IR)的1/23、是单次Brewster角透射红外吸收法的1/11;(3)单次垂直透射红外吸收法(IR)1次只测量样品上的1个点,MTR-IR法则在更长的样品上1次测量多个样品点,每次测量更具有代表性。理论计算和实验结果都证实了MTR-IR吸收法测量晶体硅中间隙氧和代位碳杂质含量的高灵敏度、可靠性和重复性。     

Differential Response of Pentanal and Hexanal Exhalation to Supplemental Oxygen and Mechanical Ventilation in Rats

High inspired oxygen during mechanical ventilation may influence the exhalation of the previously proposed breath biomarkers pentanal and hexanal, and additionally induce systemic inflammation. We therefore investigated the effect of various concentrations of inspired oxygen on pentanal and hexanal exhalation and serum interleukin concentrations in 30 Sprague Dawley rats mechanically ventilated with 30, 60, or 93% inspired oxygen for 12 h. Pentanal exhalation did not differ as a function of inspired oxygen but increased by an average of 0.4 (95%CI: 0.3; 0.5) ppb per hour, with concentrations doubling from 3.8 (IQR: 2.8; 5.1) ppb at baseline to 7.3 (IQR: 5.0; 10.8) ppb after 12 h. Hexanal exhalation was slightly higher at 93% of inspired oxygen with an average difference of 0.09 (95%CI: 0.002; 0.172) ppb compared to 30%. Serum IL-6 did not differ by inspired oxygen, whereas IL-10 at 60% and 93% of inspired oxygen was greater than with 30%. Both interleukins increased over 12 h of mechanical ventilation at all oxygen concentrations. Mechanical ventilation at high inspired oxygen promotes pulmonary lipid peroxidation and systemic inflammation. However, the response of pentanal and hexanal exhalation varies, with pentanal increasing by mechanical ventilation, whereas hexanal increases by high inspired oxygen concentrations.     

Alpha-activation analysis of nitrogen in boron-doped silicon single crystal

The rapid dissolution of silicon and the substoichiometric separation of¹⁸F were studied in order to determine nitrogen in a boron-doped silicon single crystal by activation analysis via¹⁵N(,n)¹⁸F. The silicon dissolution method was developed by using a nitric acid-based solution containing a known amount of ammonium fluoride, instead of hydrofluoric acid, as the¹⁸F carrier. The silicon could be dissolved to a depth of 100 m with a 10 mm Ø in 9 minutes. The conditions for¹⁸F steam distillation and substoichiometric precipitation as lanthanum fluoride were improved. 50% of the fluorine could be separated substoichiometrically even though the carrier amount was increased from 6–12 mmol to more than 16 mmol in order to add it to the dissolving solution. This dissolution method and improved substoichiometric separation were used to determine nitrogen in a boron-doped silicon single crystal. The nitrogen concentration was found to be less than the detection limit (50 ppb).     

Gas sensing properties of MWCNTs decorated with gold or tin oxide nanoparticles

Gas sensors based on oxygen plasma functionalised MWCNTs and plasma-treated nanotubes decorated either with gold nanoclusters or tin oxide nanoparticles were evaluated for the detection of NO₂, CO and ethylene. The sensor active layers were deposited by airbrushing onto micro-machined silicon transducers. Sensitivity, linearity, selectivity, response and recovery times and humidity effect were studied. XPS and TEM were employed to analyse the gas sensitive films. Among the different sensors tested, those based on tin oxide decorated MWCNTs showed the highest sensitivity to NO₂ (at ppb level) and the lowest humidity cross-sensitivity when operated at room temperature.     

Structural Fusion Yields Guest Acceptors that Enable Ternary Organic Solar Cells with 18.77 % Efficiency

The design and selection of a suitable guest acceptor are particularly important for improving the photovoltaic performance of ternary organic solar cells (OSCs). Herein, we designed and successfully synthesized two asymmetric silicon–oxygen bridged guest acceptors, which featured distinct blue-shifted absorption, upshifted lowest unoccupied molecular orbital energy levels, and larger dipole moments than symmetric silicon–oxygen-bridged acceptor. Ternary devices with the incorporation of 14.2 wt % these two asymmetric guest acceptors exhibited excellent performance with power conversion efficiencies (PCEs) of 18.22 % and 18.77 %, respectively. Our success in precise control of material properties via structural fusion of five-membered carbon linkages and six-membered silicon–oxygen connection at the central electron-donating core unit of fused-ring electron acceptors can attract considerable attention and bring new vigor and vitality for developing new materials toward more efficient OSCs.     

Synthesis of N-(trifluorosilylmethyl)glutarimide. Alternate intramolecular coordination of the silicon atom to two oxygen atoms

A new representative of draconoids, N-(trifluorosilylmethyl)glutarimide, was synthesized by reaction of N-(trimethyoxysilylmethyl)glutarimide with boron trifluoride-ether complex. According to the IR and ¹H, ¹³C, ¹⁵N, ¹⁹F, and ²⁹Si NMR data, this compound molecule is characterized by intramolecular coordination between the silicon and carbonyl oxygen atoms (alternate coordination of the silicon atom to each oxygen atom).     

A radioreagent method for determination of traces of phosphorus in high-purity silicon

The present study explores the feasibility of the determination of phosphorus at the extreme trace levels in high-purity silicon by radioreagent method. After silicon dissolution with hydrofluoric and nitric acids and matrix volatilization, 12-molybdophosphoric acid (12-MPA) is formed by the addition of the radioreagent,⁹⁹MoO ₄ ^2– , in nitric acid medium and then extracted into isobutyl acetate. By plotting the phosphorus content against the radioactivity of⁹⁹Mo in the organic phase, a linear relationship persisting down to 5 ng is obtained. Special effort has been made to the elimination of the unreacted⁹⁹MoO ₄ ^2– reagent and the optimal control of phosphorus blank introduced through the multistage analytical procedure in order to ensure reliable determination of phosphorus at the ppb level.