Charged-particle activation analysis studies on carbon,nitrogen and oxygen mainly in semiconductor silicon

High utility value of charged-particle activation analysis is exemplified by the study on carbon, nitrogen and oxygen in semiconductor silicon. A summary of the present authors' works is shown, and the equilibrium of carbon and oxygen in a silicon melt with ambient carbon monoxide is discussed. Also, a note is given about the chemical separation of¹⁸F for the³He activation analysis of various matrices.     

Charged particle activation analysis for carbon,nitrogen and oxygen in semiconductor silicon

Convenient processes are described for the charged particle activation analysis for carbon, nitrogen, and oxygen in semiconductor silicon. Suitable activation reactions and incident particle energies were selected, and the interferences examined; the activation curves for the Si+³He→¹¹C and Si+³He→¹⁸F reactions, which may seriously interfere with³He activation analysis, were measured, and the interference caused by the fission of the matrix itself is discussed. A simple technique for the separation of¹¹C present in silicon is proposed. Reliable determination of as low as several parts per billion of the three elements has thus become possible. Semiconductor silicons of various origin were analyzed for C, N and O, and the behaviour of these elements during zone-melting is reported.     

The determination of trace oxygen in lead by helium-3 and helium-4 activation analysis

The determination of oxygen in lead by³He and⁴He activation analysis was studied. Both methods were applied to the same material containing 0.9 μg·g^?1 of oxygen. The¹⁸F formed from oxygen was separated from matrix activities by extraction of Po with N-benzoyl-N-fenylhydroxylamine, followed by distillation of fluorosilicic acid and precipitation of lead fluorochloride (⁴He activation) or by distillation followed by precipitation (³He activation). The yield of the separation, which amounted on the average to 68%, was determined via the¹⁹F(n,⁴He)¹⁶N reaction. The coefficients of variation were 21 and 45% for⁴He and³He activation analysis, respectively, thus indicating a less homogeneous distribution of the oxygen. Nuclear interferences of sodium and fluorine were shown to be negligible.     

On the determination of carbon and oxygen impurities in silicon by3He activation analysis

Carbon and oxygen impurities in silicon have been determined by 7.00 MeV³He activation analysis. The detection limits obtained for interference-free conditions are 0.1 ppb (wt) for carbon and 1.0 ppb (wt) for oxygen in silicon.     

Charged particle activation analysis for surface oxygen under various ambient pressures

Charged particle activation analysis has proved to be useful for the determination of surface oxygen under any atmospheric conditions. The¹⁶O(³He, p)¹⁸F reaction was used for activation. The sample in a form of two plates was contacted intimately with each other and bombarded with³He particles of such an energy as to give the maximum cross section at the inside surfaces of the plates. The¹⁸F thus formed in the forward plate was then measured. Oxygen in the gap between the two plates can be shown to cause no noticeable interference. This method was applied to silicon, aluminium and lead in four different ambient pressures.     

Oxygen depth profiling by activation with the16O(3He,p,)18F reaction

A technique has been developed for oxygen depth profiling in a thickness range of 5 to about 100 mg cm⁻² by activation with the¹⁶O(³He, p)¹⁸F reaction. An apparatus was set up for the activation of oxygen with a uniform probability along the depth, and a method has been devised for step-wise etching of the activated sample. This technique has been applied to the study of oxygen behaviour in heat treatment of silicon under various conditions.     

Microanalysis of “biometallic” compounds using nuclear and atomic activation

A novel method for the characterization of metal containing biological compounds has been developed which utilizes both nuclear activation [e.g.,¹²C(³He, α)¹¹C] and atomic activations (X-ray emission) induced by 8 MeV³He bombardment. Detection limits for carbon (≈1 μg), oxygen (≈1μg), and metals (1 to 10 ng for elements between P and Zn) were obtained under routine experimental conditions. The metal stoichiometry of six different compounds (alkaline phosphatase, amylase, carbonic anhydrase, diamine oxidase, my oglobin, vitamin B₁₂) were determined with typical relative precisions of ±25% for a 40 μg sample. A comparison of these ratios with carbon and metal measurements obtained by other methods showed a relative accuracy of 1 to 20%.     

Investigation of the depth distribution of impurities by charged-particle activation

A method is described for the quantitative determination of the distribution of impurities, utilizing charged particles. Experimental data obtained by activation with 7.5 MeV³He ions are reported on the distribution of oxygen in Ge and Nb samples.     

3He NMR: from free gas to its encapsulation in fullerene

The ³He nuclear magnetic shieldings were calculated for single helium atom, its dimer, simple models of fullerene cages (He@C_n), and single wall carbon nanotubes. The performances of several levels of theory (HF, MP2, DFT‐VSXC, CCSD, CCSD(T), and CCSDT) were tested. Two sets of polarization‐consistent basis sets were used (pcS‐n and aug‐pcS‐n), and an estimate of ³He nuclear magnetic shieldings in the complete basis set limit using a two‐parameter fit was established. Theoretical ³He results reproduced accurately previously reported theoretical values for helium gas, dimer, and helium probe inside several fullerene cages. Excellent agreement with experimental values was achieved. ³He nuclear magnetic shieldings of single helium atom approaching various points of benzene ring were tested, and an impact of ³He confinement within fullerene cages of different size on the ³He chemical shift was determined. Copyright © 2013 John Wiley & Sons, Ltd.     

Helium-3 activation analysis of oxygen in silicon nitride films on silicon wafers

Oxygen in silicon nitride films on silicon wafers was analyzed by activation with the¹⁶O(³He, p)¹⁸F reaction. By³He bombardment of samples propertly arranged under consideration of the¹⁸F recoil effect, total oxygen was reliably determined and its predominant part was estimated to be located whether on film surface, in film interior, or on film-substrate interface. Sample films with 0.1 to 2 μm thicknesses were found to contain 0.2 to 2 μg/cm² of oxygen in locations varying with preparation conditions. This method has been compared with ESCA and other methods for surface analysis.     

o-Cresol,thiourea and formaldehyde terpolymer – A cation exchange resin

o-Cresol–thiourea–formaldehyde terpolymer resin was synthesized through the condensation of o-cresol and thiourea with formaldehyde in the mole ratio 1:3:5 in the presence of 2 M hydrochloric acid as a catalyst. The resulting copolymer was characterized with IR and ¹H NMR spectral data. The average molecular weight of the resin was determined by Gel permeation chromatography. Thermal study of the resin was carried out to calculate the activation energy (Ea), enthalpy of activation (H³), entropy of activation (S³), free energy of activation (G³), and pre-exponential factor (A) of various steps of thermal decomposition of the terpolymer. The Dharwadkar and Kharkhanavala method has been used to calculate thermal activation energy and thermal stability. The chelation ion-exchange properties were also studied with the batch equilibrium method. The chelation ion-exchange properties of the copolymer was studied for Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Pb²⁺ and Cd²⁺ ions. The resin was proved to be selective chelating ion-exchange copolymer for certain metals. The study was carried out over a wide pH range and in media of various ionic strengths.     

Role of Iron Carbonyls in the Inhibition of Oxygen Activation for the Oxidation of CO Catalyzed by Iron Oxide‐Supported Gold

Iron oxide‐supported gold samples were prepared by co‐precipitation from HAuCl₄ and Fe(NO₃)₃. The activities of the samples as CO oxidation catalysts were tested without thermal treatment and following treatments in flows of He and O₂ at various temperatures. It was found that the untreated samples and those treated in a flow of He at 150 °C were more active than samples that had been treated at 400 °C in either a flow of O₂ or of He. Infrared spectra recorded during CO oxidation catalysis indicate the presence of bonded CO molecules to cationic gold on all samples, whereas spectra of the least active catalysts indicate a predominant presence of Fe²⁺ carbonyls, which were highly stable under the conditions of our experiments. Our results indicate that in the least active samples the Fe²⁺‐bound CO blocks sites that would otherwise be available for oxygen activation.     

3He Impurities in Nearly Frictionless Transport of Solid 4He at Low Temperatures

Glassy matter, when subjected to high shear rates exhibit shear thinning, that is, the viscosity diminishes with increasing shear rate. One possible outcome for the almost vanishing viscosity is nearly frictionless transport, which is possible in solid ⁴He due to the presence of minute concentrations of ³He. The glassy state of solid ⁴He is also relevant to the possible onset of superuidity in solid ⁴He. By treating the solid ⁴He locally as an amorphous matter and using the transition‐rate dependent model together with the specific activation energy, we observe a series of sudden changes of the shearing stresses (which directly relates to the resistance) at corresponding onset temperatures of supersolid ⁴He (ranging from 175 to 1200 mK) for different activation volumes of ³He. Even at higher concentrations of ³He than previous reported (around 1700 ppm), the supersolidity of ⁴He still occurs.     

Contribution a l'etude de la determination de Be,B, C,N, O et F par activation au moyen de p,d,3He et α

The activation of these elements, homogeneously contained in a medium thicker than the path length, of slowing-down capacity close to that of aluminium, was determined as a function of energy by irradiating standards with p, d,³He and α particles of energies between: 5 and 15 MeV for protons, 5 and 20 MeV for deuterons and³He particles, 25 and 42 MeV for α particles. The detection sensitivities intrinsically possible in these energy ranges are deduced from the curves obtained. The results apply to all materials through a simple relationship taking into account the path lengths. They may be used in particular to foresee the possibilities offered by activation with these charged particles, from the viewpoint of sensitivity, when the samples to be analysed are irradiated with a beam of given intensity and energy lying between the above limits.     

Investigation on the reaction of iron powder mixture as a portable heat source for thermoelectric power generators

This paper reports our investigation on the thermal behavior and ignition characteristics of iron powder and mixtures of iron with other materials such as activated carbon and sodium chloride in which iron is the main ingredient used as fuel. Thermal analysis techniques such as differential scanning calorimetry (DSC) and thermogravimetric analysis were used to characterize the materials and for further understanding of reaction kinetics of the pyrophoric iron mixtures. The experimental results demonstrated that iron micron particles react exothermically to the oxygen in atmosphere and produced iron oxide with ignition temperature of 427.87 °C and heat generation of 4,844 J g^?1. However, in this study, the pyrophoric iron mixture acts as a heat source for the thermoelectric power generators, the final mixture composition is determined to compose of iron powder, activated carbon, and sodium chloride with the mass ratio of approximately 5/1/1. The mixture generated two exothermic peaks DSC curves that showed ignition temperature of 431.53 and 554.85 °C and with a higher heat generation of 9,366 J g^?1 at higher temperature. The effects of test pan materials and heating rate on the ignition were also examined by DSC method. Kinetic data such as the activation energy (E _a), the entropy of activation (ΔS ^# ), enthalpy of activation (ΔH ^# ), and Gibbs energy of activation (ΔG ^# ) on the ignition processes was also derived from the DSC analysis. From the ignition temperature, heat generation, and kinetics test data, the mass ratio of 5/1/1 proved to generate the most amount of heat with high temperatures for the standalone thermoelectric power generators.     

Measurements of the neutron spectra from the 7Li(p,n) accelerator based neutron source: Position and angular dependences

Thick target ⁷Li(p,n) neutron spectra were measured using a ³He ion chamber in the proton energy range of 1.95 to 2.30 MeV. The fast neutron spectra were collected for various distances from the lithium target as well as for various neutron emission angles. By unfolding the ³He raw data with the iterative van Cittert algorithm, the neutron fluence spectra were obtained. The ³He measured neutron spectra were compared with both analytically computed and Monte Carlo simulated spectra to account for neutron scatterings in the lithium target assembly and in the experimental area. To verify the accuracy of the neutron dose computation, the fast neutron kerma was obtained for each neutron spectrum using the fluence to kerma conversion coefficients and was compared with the measured neutron dose using tissue-equivalent proportional counters. In the position dependence investigation at the 0° emission angle, the analytically computed neutron kerma overestimates the experimental kerma by a factor of two mainly due to neutron moderation. The corresponding neutron kerma from the ³He measured spectra were in agreement with the neutron doses measured using tissue-equivalent proportional counters within 20% for lower proton energies, but the discrepancy increased to ～50% for higher proton energies. In the angular distribution investigation, a notable discrepancy between measured and computed neutron spectra were observed due to the neutron scattering effects in the target assembly and experimental room.     

Neutron energy spectra of 252Cf, Am-Be source and of the D(d,n)3He reaction

The neutron energy spectrum of the following sources were measured using a fast neutron spectrometer with the NE-213 liquid scintillator: ²⁵²Cf, Am-Be and D(d,n)³He reaction from a 3 MeV Pelletron accelerator in Tokyo Institute of Technology. The measured proton recoil pulse height data of ²⁵²Cf, Am-Be and D(d,n)³He were unfolded using the mathematical program to obtain the neutron energy spectrum. The ²⁵²Cf and Am-Be neutron energy spectra were measured and the results obtained showed a good agreement with the spectra usually published in the literature. The neutron energy spectrum from D(d,n)³He was measured and the results obtained also showed a good agreement with the calculation by time of flight (TOF) methods.     

The thermodynamic properties of weakly bound oxygen and electron transport in Sr3Fe2O6+δ under oxidizing conditions

The content of oxygen, electrical conductivity, and thermal electromotive force were measured for ferrite Sr₃Fe₂O_6+δ over the oxygen partial pressure range 10^?4–0.5 atm at 650–950°C. The partial molar thermodynamic functions of weakly bound oxygen in the oxide structure were determined. Labile oxygen ions were characterized as an ensemble of weakly interacting particles. The predominant charge carriers under experimental conditions were electron holes. An analysis of conductivity was performed using the data on the oxygen content. The concentration, activation energy, and mobility of charge carriers were determined. The results can be satisfactorily interpreted using the polaron transfer model of conductivity taking into account the charge disproportionation reaction for iron ions, 2Fe⁴⁺ = Fe³⁺ + Fe⁵⁺.     

Trace determination of oxygen in gold-copper alloys and in high purity gold using3He and4He activation analysis

Trace amounts of oxygen in gold-copper alloys and high purity gold have been determined by³He and⁴He activation analysis. Interferences from the matrix have been identified and the factors which can have an effect upon the precision and the accuracy of the method have been investigated. Thus a destructive technique has been choosen. The¹⁸F produced was chemically separated by steam distillation and precipitated as PbClF. The values of the oxygen concentration were found to range between 0.2 and 2 μg·g⁻¹ depending on the copper concentration and the thermal treatment applied to the samples. A possible mechanism of internal oxidation is presented.     

Vibration—vibration energy exchange between carbon monoxide and carbon dioxide

Measurements have been made on the vibration—vibration (V—V) energy exchange rate between carbon monoxide and carbon dioxide in the temperature range 180 to 345 K. A steady-state vibrational fluorecence quenching technique was used in conjunction with an open flow gas system. Vibrational excitation of the carbon monoxide was accomplished by absorption of infrared radiation from prospane—oxygen flames. The measured rate constant for the process CO* (υ = 1) + CO₂ → CO + CO^*₂(001) increased linearly with temperature, and after correction for the V—V exchange rate fo the back reaction, the rate constant has a value of (2.2 ± 0.3) × 10³ torr^?1 s^?1 at 296 K. The data are compared to results at highest temperatures and to available theoretical calculations.