Experimental check of the high-frequency behavior of the electrons in molecular and atomic gas plasmas

The high-frequency behavior of the electron component in collision-dominated nitrogen plasmas of dc glow discharges, acted upon by an additional microwave field, has been studied on an adequate kinetic basis for field frequencies exceeding the characteristic frequency for energy dissipation in electron collisions with nitrogen molecules. In particular, the phase delay of the electron current density with respect to the driving microwave field has been calculated. To check the validity of the results obtained by the electron kinetic approach, the phase delay has been experimentally determined adapting an appropriate microwave resonator method to the dc plasma. The comparison of the theoretically and experimentally determined phase delay of the ac electron current in the nitrogen plasma leads to a good agreement in the entire range of high-field frequencies and confirms the conclusions on the high-frequency behavior of the electrons deduced from the electron kinetic approach. Using previous results for a neon plasma, the remarkable impact of the atomic data of the collision processes in different gases on the high-frequency behavior of the electron component in these gas plasmas is additionally evaluated.     

Microwave Diagnostics in Diffusive and Constricted Medium-Pressure Discharges

The high-frequency (HF) electron current induced in a dc discharge plasma bysuperimposing a HF electric field presents a useful tool for the diagnosticsof the time-dependent electron behavior of the plasma. This response to theHF field has been recently studied in diffusive discharge plasmas at lowergas pressures and discharge currents. These studies are extended tomedium-pressure plasmas operating in the diffusive as well as in theconstricted mode. In particular, the impact of the electron–electroninteraction on the phase delay between the HF field and electron current inconstricted column plasmas has been experimentally and theoreticallyanalyzed. Furthermore, the problem has been studied if, under the conditionsof pronounced electron–electron interaction, the determination of theelectron density will further on be possible by using the phase delay. Themeasurements of the delay have been performed by means of the microwaveresonator method in a medium-pressure krypton glow discharge operating inthe diffusive as well as the strongly constricted mode. In addition, thedelay has been theoretically determined by treating the appropriatetime-dependent electron kinetic equation at high frequencies of thesuperimposed microwave field.     

Microwave and RF surface wave sustained discharges as plasma sources for plasma chemistry and plasma processing

The surface wave produced plasma belongs to a class of RF and microwave induced plasmas. It results from the propagation of an electromagnetic wave which uses the plasma column it sustains and the plasma tube as its sole propagating media. This type of plasma offers several advantages compared to the positive column plasma of dc discharges or to other RF and microwave produced plasmas. Surface wave plasmas require no internal electrodes, and they can be applied over an extremely broad range of wave frequencies (27 MHz to 10 GHz demonstrated) and gas pressures (about 10^–4 Torr to a few times the atmospheric pressures). Using the surface wave plasma technique, a large variety of plasma column diameters have been created (0.5–150 mm demonstrated) and no limitation on plasma column length (column up to 6 m long demonstrated) has been found. The surface wave produced plasma is used in elemental analysis and to sustain emission in lasing media. This article is intended as a guide for potential users of surface wave plasmas in the field of plasma processing and plasma chemistry.     

Measurement of electron densities by a microwave cavity method in 13.56-MHz RF plasmas of Ar,CF4, C2F6, and CHF3

Electron densit ies have been determined /or RF plasmas that were generated within a microwave resonant cavity by measuring the difference of the resonance frequencies with and without plasma. Since that method only yields a value of the electron density weighted ouer the microwave electric field distribution, to obtain real values an assumption on the spatial distribution of the electron density had to he made. Spatial profiles were taken of the emission of a 4s–5p Ar line at 419.8 not (with a small Ar admixture). The electron densities have been determined as a function of pressure and RF power in Ar, CF₄, C₂ F₆ and CHF, plasmas. The results indicate that the electron density for the last three gases decreases as a function of pressure above 50 m Torr. Typical values for the electron density for the investigated parameter range are 1–6 · 10³ cm^–3. Furthermore, the electron density is the lowest in gases with a high attachment cross .section.     

Infrared radiation from an arc plasma and its application to plasma diagnostics

In this paper, a feasibility stud v has been conducted to determine if infrared radiation from an arc plasma can be used for diagnostic purposes. The properties of IR radiation of an atmospheric-pressure arc plasma are described from the viewpoint of continuous radiation theory, and the effects of electron density and temperature on the spectral radiance of an arc plasma column of finite size have been evaluated using a plasma slab model. As a result, it is shown that the spectral radiance of the atmospheric arc plasma column is very sensitive to the electron density in the near infrared frequency range, and the temperature dependence of the spectral radiance is negligibly small in this frequency range. Finally, it is concluded that IR radiation in the wavelength range of 3-15 m can be used to measure the electron density of the arc plasma, and a simple formula for the measurement is proposed.     

Spatially Dependent Kinetics of Electrons and Excited Atoms in the Column Plasma of a He–Xe dc Discharge

The radially varying kinetics of electrons and excited atoms in the cylindrical axially homogeneous positive column of a dc glow discharge in a gas mixture of helium and 2% xenon was studied. The experimental investigations comprise the radially resolved measurements of the isotropic part of the electron velocity distribution function (EVDF) using a single-probe technique and of the densities of atoms in the lower excited states by using a laser diode absorption method. The theoretical investigations are based on the solution of the space-dependent kinetic equation for the EVDF and the balance equations of excited gas atoms. Besides a strict solution, various simplified treatments of the electron kinetics as the conventional homogeneous approach and the nonlocal approach have been applied. The electron kinetic behavior in the helium–xenon column plasma changes remarkably with increasing helium gas pressure from a distinctly nonlocal behavior at a low pressure of 100 Pa to a nearly local behavior at a medium pressure of 600 Pa.     

An Investigation of the Positive Column of a Cd–Ne Glow Discharge. I: Steady State

An investigation of cadmium-neon plasma in cylindrical axially homogeneouspositive column of a dc glow discharge at low and intermediate pressure ispresented. Electron impact excitation cross sections, heavy-particlecollision rate coefficients, and radiative decay rates for Cd–Nemixture have been assembled from the literature and summarized. Aself-consistent collisional-radiative model based on numerical solution ofthe electron Boltzmann equation coupled with a system of particle balanceequations for the electrons, excited atoms and ions, as well as the electronenergy balance equation, is developed. By this model, the electron energydistribution function, mean energy, electron density, electron mobility, anddiffusion coefficient, populations of Cd and Ne excited states and theapplied dc electric field are calculated. The populations of the excitedCd(5p³P_0,1,2) atoms are measured using opticalabsorption spectroscopy. From these measurements the effective lifetime ofthe resonance state Cd(5p³P₁) and the diffusioncoefficients of both metastable states Cd(5p³P₀) andCd(5p³P₂) are determined. The electron density isderived by probes measurements. The influence of the Cd vapor pressure anddischarge current on the main plasma characteristics is studied. Modelpredictions compare favorably with measured electron density and populationsof excited states in a wide range of discharge conditions.     

Attachment and ionization in a self-consistent treatment of the electron kinetics of a collision-dominated rf plasma

This paper deals with the self-consistent determination of the rf field amplitude for sustaining the steady-state collision-dominated weakley ionized plasmas in the bulk of the rf discharge and of the time-resolved behavior of the isotropic part of the distribution function as well as of relevant macroscopic quantities in plasmas whose particle loss is dominantly determined by electron attachment. The strict timeresolved treatment is based on the nonstationary Boltzmann equation of the electrons and its numerical solution including, apart from electron number conservative collision processes, the electron attachment and ionization. The investigations are related to an rf plasma in a model gas and in SF₆ and are performed for reduced rf field frequencies around 10 MHz Torr^–1 which are of particular interest from the point of application of rf discharges for plasma processing. The numerical results show that a large field amplitude of around 160 V cm^–1 Torr^–1 is necessary to maintain the discharge and that the isotropic distribution, the relevant collision frequencies for attachment and ionization, and the electron density undergo a large modulation during a period of the rf field.     

Characterization of an argon-hydrogen microwave discharge used as an atomic hydrogen source. Effect of hydrogen dilution on the atomic hydrogen production

This work is devoted to the study of an argon-hydrogen microwave plasma used as an atomic hydrogen source. Our attention has focused on the effect of the hydrogen dilution in argon on atomic hydrogen production. Diagnostics are performed either in the discharge or in the post-discharge using emission spectroscopy (actinometry) and mass spectrometry. The agreement between actinometry and mass spectrometry diagnostics proves that actinometry on the Ha(656.3 nm) and Hβ(486.1 nm) hydrogen Balmer lines can be used to measure the relative atomic hydrogen density within the microwave discharge. Results show that the atomic hydrogen density is maximum for a gas mixture corresponding to the partial pressure ratioP _{H 2}/P _Ar range between 1.5 and 2. The variation of atomic hydrogen density can be explained by a change of the dominant reactive mechanisms. At a low hydrogen partial pressure the dominant processes are the charge transfers with recombinations between Ar⁺ and H₂ which lead to ArH⁺ and H ₂ ⁺ ion formation. Both ions are dissociated in dissociative electron attachment processes. At a low argon partial pressure the electron temperature and the electron density decrease with increasing partial pressure ratio. The dominant mechanisms become direct reactions between charged particles (e, H⁺, H ₂ ⁺ , and H ₃ ⁺ ) or excited species H(n=2) with H₂ producing H atoms.     

Enantioselective analysis of bambuterol in human plasma using microwave‐assisted chiral derivatization coupled with ultra high performance liquid chromatography and tandem mass spectrometry

In this study, an enantioselective analytical method based on microwave‐assisted chiral derivatization coupled with ultra high performance liquid chromatography and tandem mass spectrometry was developed for the determination of bambuterol enantiomers in human plasma. The chiral derivatization reaction was greatly accelerated by microwave irradiation. Under the optimized conditions, both the derivatization time and separation time on column was only 3 min, and the lower limit of quantification was 2.5 pg/mL. The recoveries were in the range of 90.1–93.0% without significant matrix effect. Compared with the conventional heating chiral derivatization, microwave‐assisted chiral derivatization obtained higher chiral derivatization yields with much shorter time due to the effect of microwave irradiation. Furthermore, the racemization during the derivatization reaction was systematically investigated. The results showed the concentration of acetic acid and the reaction time had significant effects on the racemization, which could be well controlled during microwave‐assisted chiral derivatization for the short reaction time. Finally, this novel approach was demonstrated by determining bambuterol in human plasma of a clinical pharmacokinetic study in eight healthy volunteers. On the basis of the results, microwave‐assisted chiral derivatization coupled with ultra high performance liquid chromatography and tandem mass spectrometry as a simple and effective enantioselective analysis technique for the determination of chiral drugs in complex biological samples showed great promise.     

Electron Kinetics in Nonisothermal Plasmas with Spatially Two-Dimensional Structures

A method for the study of the steady-state nonlocal electron kinetics in radially and axially inhomogeneous cylindrical plasmas is presented. The method is based on the solution of the relevant space-dependent kinetic equation for the electron velocity distribution using the two-term expansion. A three-dimensional initial boundary value problem for the isotropic distribution component with the total energy as the evolution variable of the kinetic problem has to be treated. The technique is applied to analyze the electron kinetics in a cylindrical DC column plasma under impact of a space-independent axial field and a radially increasing radial field. Particularly, the spatial relaxation of the electron gas in axial direction in response to a disturbance of the axial homogeneity is investigated. A detailed analysis of the spatially resolved energy balance is given. Considerable modification of the results with respect to those obtained by earlier studies of axially homogeneous DC column plasmas, as well as of relaxation processes in one spatial dimension, has been found.     

Low frequency epr surface probe based on dielectric resonator

A new surface probe for low frequency in vivo EPR studies was designed and constructed based on a dielectric resonator. Dielectric resonators previously have been used in X-band EPR for small samples to take advantage of its well separated microwave magnetic and electric field distributions and high Q. In this work we have built a dielectric resonator for use as a surface probe for in vivo EPR at low frequency (1.2 GHz). The core of the probe was a commercially available dielectric ceramic resonator supported by a PTFE ring. The resonator was coupled to a 50 Ω line by an inductive loop which was interfaced by a quarter wave length transformer. The quarter wave length transformer improved the matching and stabilized the resonant frequency. The resonator was surrounded by a silver coated brass shielding. The shielding blocked the penetration of the field modulation and therefore there was no contribution from any intrinsic EPR signal from the dielectric material. The Q factor before loading samples was 3,600 which was much higher than the Q factors of ～ 1000 obtained by other types of surface probes. The use of animals or biological samples decreases the Q factor to about 330 but this is at least two times higher than occurs with other types of surface probes. The sensitivity of the dielectric surface probe in air decreased more slowly than with other types of surface probes. This would be especially useful for in vivo studies in which the animal has an irregular surface at the site(s) of measurement and/or there is a significant air gap between the probe and the animal. This dielectric resonator can be inexpensively constructed and is robust, and sensitive for in vivo EPR spectroscopy and imaging.     

Electron Capture Gas Chromatography of Nitrazepam in Human Plasma as Methyl Derivative

Abstract

A method for quantitative determination of nitrazepam in human plasma in the range 5 - 100 ng/ml is presented.

Nitrazepam is extracted with benzene from plasma samples of 0.5 ml, methylated with methyl iodide and determined gas chromatographically with an electron capture detector of ⁶³Ni-type.

Acid dissociation constants of nitrazepam are determined and the partition properties studied with benzene, methylene chloride and diethyl ether as organic phases.

The selectivity of the method with respect to the metabolites has been thoroughly studied.     

Determination of mineral and trace element concentrations in pine needles by ICP-OES: evaluation of different sample pre-treatment methods

In the present study, the determination of mineral and trace elements (Al, B, Ca, Cu, Fe, K, Mg, Mn, Na, P and Zn) from pine needles using three sample pre-treatment methods followed by inductively coupled plasma optical emission spectrometry, was examined. Sample pre-treatment methods tested were microwave digestion, ultrasound-assisted digestion and dry ashing. The new ultrasound-assisted digestion method was optimised by the analysis of the standard reference material (SRM) 1575a (pine needles) sample. The speed of dry ashing method was significantly increased by ultrasound dissolution after ashing. All the ICP-OES measurements were performed in robust plasma conditions which were tested by measuring the Mg II 280.270 nm/Mg I 285.213 nm line intensity ratios. The microwave digestion resulted generally in slightly higher element concentrations than ultrasound-assisted digestion. B, Cu and Na resulted in such low concentrations that they could not be accurately determined by using the microwave digestion method. The t-tests found no significant differences between the certified and the determined element concentrations of the SRM 1575a using the dry ashing method followed with ultrasound dissolution.     

Magic angle spinning NMR with metallized rotors as cylindrical microwave resonators

We introduce a novel design for millimeter wave electromagnetic structures within magic angle spinning (MAS) rotors. In this demonstration, a copper coating is vacuum deposited onto the outside surface of a sapphire rotor at a thickness of 50 nm. This thickness is sufficient to reflect 197‐GHz microwaves, yet not too thick as to interfere with radiofrequency fields at 300 MHz or prevent sample spinning due to eddy currents. Electromagnetic simulations of an idealized rotor geometry show a microwave quality factor of 148. MAS experiments with sample rotation frequencies of ω_r/2π = 5.4 kHz demonstrate that the drag force due to eddy currents within the copper does not prevent sample spinning. Spectra of sodium acetate show resolved ¹³C J‐couplings of 60 Hz and no appreciable broadening between coated and uncoated sapphire rotors, demonstrating that the copper coating does not prevent shimming and high‐resolution nuclear magnetic resonance spectroscopy. Additionally, ¹³C Rabi nutation curves of ω₁/2π = 103 kHz for both coated and uncoated rotors indicate no detrimental impact of the copper coating on radio frequency coupling of the nuclear spins to the sample coil. We present this metal coated rotor as a first step towards an MAS resonator. MAS resonators are expected to have a significant impact on developments in electron decoupling, pulsed dynamic nuclear polarization (DNP), room temperature DNP, DNP with low‐power microwave sources, and electron paramagnetic resonance detection.     

On the Kinetic Study of the Electron Velocity Distribution Function in the Cathode Region of a Glow Discharge

The recently developed multi-term approach for solving the space-dependent electron Boltzmann equation is adopted to study, under the extreme field conditions occurring in the cathode region of the dc glow discharge, the energy distribution and all important macroscopic quantities of the electrons. It is shown that even under the difficult conditions in the cathode region an efficient determination of significant components of the electron velocity distribution by the multi-term treatment of the kinetic equation is possible. These significant components can be calculated with remarkable accuracy and with relatively less computational expenditure by a multi-term approach with the inclusion of about ten coefficients of the Legendre polynomial expansion of the velocity distribution. Based on the results for a typical example, main features of the electrons in the cathode region are presented and discussed.     

Multilayer graphene/amorphous carbon hybrid films prepared by microwave surface‐wave plasma CVD: synthesis and characterization

Hybrid films of multilayer graphene (MG) containing amorphous carbon (a‐C) were synthesized on Al substrates by microwave surface‐wave plasma chemical vapor deposition. Raman scattering and surface transmission electron microscopy showed that the carbon films contained a large quantity of MG when a radio frequency (RF) substrate bias was not applied. Amorphization of graphene in the carbon film was promoted by applying an RF bias, which generated Ar⁺ in the plasma. The bandgaps of the films were found to increase as the Raman intensity ratios between the 2D‐band (at 2700 cm^?1) and D‐band (at 1350 cm^?1) decreased, indicating the formation of a‐C. The MG/a‐C all‐sp² phase of carbon hybrid films exhibited an increase in current density under 5 mW/cm² of AM1.5G solar simulated irradiation as the RF bias increased because of Ar⁺‐induced amorphization of the graphene. Copyright © 2016 John Wiley & Sons, Ltd.