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.     

A New Method of the Microwave Diagnostics for Determining the Electron Density

A improved method of the microwave diagnostics for the determination of the electron density in the column plasma of dc glow discharges is presented. This method overcomes significant limitations involved in the conventional method. The latter is mainly based on the measurement of the resonance frequency shift of the resonator cavity caused by the presence of the dc column plasma and is strictly valid only in the so-called high field frequency limit of the resonator operation. Of significant importance with respect to the improved method is the additional inclusion of the measurable phase delay between the electric hf field, superimposed on the dc plasma by the microwave field of the resonator, and the induced hf electron current. This new method has been critically evaluated with respect to its extended applicability and has been successfully applied to the experimental determination of the electron density in dc plasmas of neon and molecular nitrogen.     

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.     

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.     

On the Nonlocal Electron Kinetics in s and p Striations of DC Glow Discharge Plasmas: II. Electron Properties in Periodic States

The spatial relaxation behavior of the electron gas acted upon by stronglymodulated striation-like electric fields, typically occurring in s and pstriations of dc neon plasmas, has been investigated on a kinetic basis inpart I of this paper. These studies have clearly shown that the electronrelaxation in the striationlike field leads to the establishment of anunambiguous spatially periodic state, which is characterized by largemodulation depths and phase delays of the microscopic and macroscopicquantities with respect to the striationlike field. The present part givesa detailed analysis of these quantities in the established striationlikestates. These investigations clearly reveal the distinctly nonlocal electronproperties, which are especially pronounced in the s-type of striations. Inaddition, the kinetic studies are completed by analyzing the impact of thefield modulation degree and the sensitive destruction of the resonancebehavior of the electron gas when imposing slightly nonresonant electric fields.     

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.     

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.     

Some fundamental measurements of the atmospheric-pressure,microwave-induced discharge

Measurements of several fundamental parameters in a microwave-induced atmospheric-pressure flowing plasma are presented. Optical and electrical measurements were performed on argon and argon/nitrogen plasmas in the region 1–7 cm outside the cavity, as the applied microwave power, and plasma composition were varied.The stability of the plasma, atomic emission from the argon support gas, and emission from the analyte species, are proportional to the electron density. The observed electron density was varied when the power was changed,-when an electrophilic species was added, and as the observation zone was moved relative to the microwave field. In all cases, the change in the emission signal followed the change in electron density.The electron temperature, as measured by the double-probe method, is related to the kinetic energy of the fastest-moving electrons in the plasma. It is unchanged by variations in power, plasma gas composition, flow rate, and is independent of the location of the probes relative to the cavity. The spectroscopic and electrical data are consistent with excitation by ion—electron radiative recombination.     

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.     

Spatial Electron Relaxation: Comparison of Monte Carlo and Boltzmann Equation Results

In former investigations on the spatial relaxation of the electron component of weakly ionized plasmas a considerable spectrum of distinct spatial structures has been found in the velocity distribution function as well as in various macroscopic quantities of the electrons. These results have been mainly obtained by solving the spatially inhomogeneous electron Boltzmann equation considering the action of uniform electric fields and the impact of elastic and inelastic collisions of the electrons with the gas atoms. To verify these partly unexpected results on the complex structure formation, analogous Monte Carlo simulations were performed now for a helium plasma at various reduced electric field strengths. Detailed comparisons were made between the results of the two independent kinetic approaches with respect to the spatial evolution of the velocity distribution function as well as of associated macroscopic quantities. Good agreement was generally found, thus confirming the earlier results on the complex spatial relaxation structures.     

Spatial relaxation of electrons in nonisothermal plasmas

The spatial relaxation of electrons to homogeneous states under the action of space-independent electric fields is investigated in helium, krypton, and N₂ plasmas for various electric field strengths. These investigations are based on a new method recently developed for solving the one-dimensional inhomogeneous electron Boltzmann equation in weakly ionized, collision-dominated plasmas. Elastic as well as conservative inelastic collisions of electrons with gas atoms have been included in the kinetic treatment. The spatial relaxation is caused by an imposed direct disturbance in the velocity distribution of the electrons on a spatial boundary. A pronounced dependence of the relaxation structure and the resultant relaxation length on the atomic data of the electron collision processes in different gases has been found. Furthermore the relaxation process sensitively depends on the electric field strength in the region of medium field values.     

Neutral and ion chemistry in low pressure dc plasmas of H2/N2 mixtures: routes for the efficient production of NH3 and NH4(+)

The chemistry in low pressure (0.8-8 Pa) plasmas of H(2) + 10% N(2) mixtures has been experimentally investigated in a hollow cathode dc reactor using electrical probes for the estimation of electron temperatures and densities, and mass spectrometry to determine the concentration of ions and stable neutral species. The analysis of the measurements by means of a kinetic model has allowed the identification of the main physicochemical mechanisms responsible for the observed distributions of neutrals and ions and for their evolution with discharge pressure. The chemistry of neutral species is dominated by the formation of appreciable amounts of NH(3) at the metallic walls of the reactor through the successive hydrogenation of atomic nitrogen and nitrogen containing radicals. Both Eley-Rideal and Langmuir-Hinshelwood mechanisms are needed in the chain of hydrogenation steps in order to account satisfactorily for the observed ammonia concentrations, which, in the steady state, are found to reach values ~30-70% of those of N(2). The ionic composition of the plasma, which is entirely due to gas-phase processes, is the result of a competition between direct electron impact dissociation, more relevant for high electron temperatures (lower pressures), and ion-molecule chemistry that prevails for the lower electron temperatures (higher pressures). At the lowest pressure, products from the protonation of the precursor molecules (H(3)(+), N(2)H(+) and NH(4)(+)) and others from direct ionization (H(2)(+) and NH(3)(+)) are found in comparable amounts. At the higher pressures, the ionic distribution is largely dominated by ammonium. It is found that collisions of H(3)(+), NH(3)(+) and N(2)H(+) with the minor neutral component NH(3) are to a great extent responsible for the final prevalence of NH(4)(+).     

微波等离子体光谱技术的发展(二)

微波等离子体光源是一类重要的有较强激发能力的原子发射光谱光源,主要包括微波感生等离子体光源,电容耦合微波等离子体光源及微波等离子体炬光源。本文是微波等离子体光谱技术发展的第二部分,主要介绍了电容耦合微波等离子体光源及微波等离子体炬光源的结构原理和性能。并对它们的技术特点和进展进行评述。     

Atomic spectroscopy with surface wave plasmas

The use of microwave induced plasmas, particularly of surface wave plasmas, as detectors in atomic emission spectrometry for elemental analysis is reviewed. Surface wave plasmas have been produced at low HF power and used as gas chromatographic detectors. The analytical performances for the detection of non-metals with a Fourier transform spectrometer and a two-channel filter unit are reported. The excitation behavior of non-metals in helium-based mixed gas-plasmas has also be studied. In particular, the effect of power and of nitrogen concentration on the bromine emission has been systematically investigated. A nine-fold improvement of the detection limits for bromine can be obtained in a high power (900 W) helium-nitrogen (0.1-0.2%) plasma.     

Impact of Electron–Electron Collisions on the Spatial Electron Relaxation in Non-Isothermal Plasmas

The impact of electron–electron collisions on the spatial relaxation of electrons in the column-anode plasma of a glow discharge, acted upon by a space-independent electric field and initiated by a constant influx at the cathode side of the plasma, is investigated in inert gas plasmas. The investigations are based on a new method for numerically solving the one-dimensional inhomogeneous Boltzmann equation of the electrons including electron–electron interaction in weakly ionized, collision-dominated plasmas. A detailed analysis of the spatial behaviour of the velocity distribution function and relevant macroscopic properties of the electrons is given for various degrees of ionization and electric field strengths. A significant impact of the electron–electron collisions on the relaxation structure and the resultant relaxation length already at relatively low ionization degrees has been found for low to medium electric fields.     

Atomic spectroscopy with surface wave plasmas

The use of microwave induced plasmas, particularly of surface wave plasmas, as detectors in atomic emission spectrometry for elemental analysis is reviewed. Surface wave plasmas have been produced at low HF power and used as gas chromatographic detectors. The analytical performances for the detection of non-metals with a Fourier transform spectrometer and a two-channel filter unit are reported. The excitation behavior of non-metals in helium-based mixed gas-plasmas has also be studied. In particular, the effect of power and of nitrogen concentration on the bromine emission has been systematically investigated. A nine-fold improvement of the detection limits for bromine can be obtained in a high power (900 W) helium-nitrogen (0.1–0.2%) plasma.     

The development of microplasmas for spectrochemical analysis

Miniaturized microwave, high-frequency, and dc-powered microplasmas are discussed, with emphasis on the state-of-the-art and development trends. Specific atomic emission sources discussed include the microstrip microwave plasma operated in argon and helium at ca 10-30 W and below 1 L min(-1) gas at atmospheric pressure, the capacitively coupled microplasma, operated at 13.56 MHz, 5-25 W, and 17-150 mL min(-1) helium, the miniaturized inductively coupled plasma operated at several watts and reduced pressure, and dc glow-discharge plasmas on a chip, including a barrier-layer discharge as atom reservoir for atomic absorption spectrometry. Diagnostics for these sources are discussed and some of their figures of merit are compared with those of conventional sources. Current possibilities for introduction of gaseous samples are reported and scope for further development and outlook are both discussed.     

Effects of Vibrational Nonequilibrium on the Chemistry of Two-Temperature Nitrogen Plasmas

A new two-temperature chemical kinetics model for nitrogen plasmas is presented. The model is used together with the vibrationally-specific collisional-radiative model to study the effects of vibrational nonequilibrium distributions on the chemical composition of two-temperature atmospheric pressure nitrogen plasmas. It is found that over a wide range of conditions the vibrational levels follow Boltzmann distributions and that the vibrational temperature T_v is well approximated by gas temperature T_g at low electron number densities and by electron temperature T_e at high electron number densities. This result suggests that simple kinetic models with two-temperature rate coefficients can be used to reliably model nonthermal plasmas. The calculation also yields a surprising result that, for a given constant gas temperature, the steady-state electron number density exhibits an S-shaped dependence on the electron temperature. This S-shaped behavior is caused by competing ionization, charge transfer reactions, two-body dissociative recombination, and three-body electron recombination reactions, and therefore is characteristic of molecular plasmas.     

The influence of flow rate and pressure on the excitation conditions in low-pressure microwave induced plasmas

Using a double probe technique, electron temperatures and electron concentrations together with spectral line intensities have been measured in low-pressure microwave induced plasmas at various pressures and flow rates of monoatomic and polyatomic support gases. For two distinct pressures viz. 0.2 and 1.0 torr (0.267–1.333 mbar) the flow rate has been independently varied.

Measurements of spectral-line intensities in the absence and presence of the probes demonstrate that the probes exert little or no influence upon the plasma conditions. The results show that when low-pressure microwave induced plasmas in flow systems are applied for quantitative analytical purposes exact specification of both flow rate and pressure of the carrier gas is required.