Some trends in the development of microplasmas for spectrochemical analysis

The development of microplasmas for spectrochemical analysis by optical methods is discussed. Recent achievements in miniaturization are highlighted, especially for three types of plasmas, namely high-frequency plasmas, dc-discharges and microwave plasmas. The potentials of each of these groups of plasmas as sources for atomic emission spectrometry are discussed. Literature citations and experiments indicate that the plasmas are also very useful as atom reservoirs for atomic absorption spectrometry. Methods of sampling, including feeding with gas chromatography effluents, the use of electrothermal vaporization, and the evolution of gaseous species (as shown for the case of Hg vapor), are discussed as prominent interfaces to make use of these sources for elemental analysis.     

Impact of electron-electron interaction on the electron energy distribution function in molecular plasmas under rf field action

Calculations of the electron energy distribution and of relevant macroscopic quantities of collision-dominated, weakly ionized plasmas under rf field action have been performed with increasing degrees of ionization, and the impact of the electron-electron interaction on these quantities was determined. The investigations were performed for the gas plasmas in CO and H₂ as representatives of molecular plasmas The energy distribution and macroscopic quantities are obtained by solving the nonstationary Bolizmann equation for a given rf field and degree of ionization taking into accoung and additional Fokker-Planck term besides the collision integrals for the elastic and the main inelastic collision processes. In these molecular plasmas a remarkable impact of the electron-electron interaction connected with increasing Maxwellization is observed for degrees of ionization greater than 10.     

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.     

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.     

Calorimetric and dimensional studies on inductively coupled plasmas

The validity of the use of metallic loads to obtain formulae for the power dissipated in plasmas is confirmed by direct calorimetry on plasmas. As a rule of thumb, when high powers are used, about 40% of the power supplied to the generator reaches the plasma. The power in the plasma, as a function of plate kVA seems to be independent of plasma gas flow coolant. Measurements of plasma volumes show that those obtained with a nitrogen coolant are smaller than with an argon coolant; because of this, and in spite of higher losses to the coolant, nitrogen-cooled plasmas have higher power densities.     

Photodestruction of Diatomic Molecular Ions: Laboratory and Astrophysical Application

In this work, the processes of photodissociation of some diatomic molecular ions are investigated. The partial photodissociation cross-sections for the individual rovibrational states of the diatomic molecular ions, which involves alkali metals, as well as corresponding data on molecular species and molecular state characterizations, are calculated. Also, the average cross-section and the corresponding spectral absorption rate coefficients for those small molecules are presented in tabulated form as a function of wavelengths and temperatures. The presented results can be of interest for laboratory plasmas as well as for the research of chemistry of different stellar objects with various astrophysical plasmas.     

Critical analysis of viscosity data of thermal argon plasmas at atmospheric pressure

Reliable values of the viscosity in thermal argon plasmas are most important for our understanding of the momentum transfer and for realistic modeling of various plasma applications. Despite numerous attempts to determine reliable viscosity values over the last three decades, discrepancies still exist among the data reported by different authors. In this paper, a critical analysis is undertaken of calculated and experimental data of the argon viscosity based on recent publications. Our recalculation of viscosities in thermal argon plasmas are performed by using Lennard-Jones, Morse, Aziz, and exponential repulsive potentials for Ar-Ar atom interactions in different temperature ranges from 300 to 20,000 K. The contributions of elastic collisions of e-Ar, e-Ar⁺, and Ar⁺-Ar, as well as charge exchange of Ar⁺-Ar, to the viscosity become important with increasing temperature and degree of ionization in argon plasmas. Based on a critical analysis and recalculations, improved values of the argon viscosity are recommended, covering temperatures from 300 to 20,000 K. Polynomial expressions have been developed for calculating argon viscosities, which will be useful for numerical work and other applications of thermal argon plasmas at atmospheric pressure.     

Effects of argon dilution on the translational and rotational temperatures of SiH in silane and disilane plasmas

The effects of argon dilution on the translational and rotational temperatures of SiH in both silane and disilane plasmas have been investigated using the imaging of radicals interacting with surfaces (IRIS) technique. The average rotational temperature of SiH determined from the SiH excitation spectra is approximately 500 K in both SiH(4)/Ar and Si(2)H(6)/Ar plasmas, with no obvious dependence on the fraction of argon dilution. Modeling of kinetic data yields average SiH translational temperatures of approximately 1000 K, with no dependence on the fraction of argon in the SiH(4)/Ar plasmas within the studied range. In the Si(2)H(6)/Ar plasmas, however, the translational temperature decreases from approximately 1000 to approximately 550 K as the Ar fraction in the plasma increases. Thus, at the highest Ar fractions, the translational and rotational temperatures are nearly identical, indicating that the SiH radicals are thermally equilibrated. The underlying chemistry and mechanisms of SiH energy equilibration in Ar-diluted plasmas are discussed.     

Characterization of laser induced plasmas by optical emission spectroscopy: A review of experiments and methods

Advances in characterization of laser induced plasmas by optical emission spectroscopy are reviewed in this article. The review is focused on the progress achieved in the determination of the physical parameters characteristic of the plasma, such as electron density, temperature and densities of atoms and ions. The experimental issues important for characterization by optical emission spectroscopy, as well as the different measurement methods are discussed. The main assumptions of the methods, namely the optical thin emission of spectral lines and the existence of local thermodynamic equilibrium in the plasma are evaluated. For dense and inhomogeneous sources of radiation such as laser induced plasmas, the characterization methods are classified in terms of the optical depth and the spatial resolution of the emission used for the measurements. The review deals firstly with optically thin spatially integrated measurements. Next, local measurements and characterization in not optically thin conditions are discussed. Two tables are included that provide reference to the works reporting measurements of electron density and temperature of laser induced plasmas generated with diverse samples.     

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.     

Polymer degradation in reactive-gas plasmas

This paper presents an account of the main features of the degradation of polymers in plasmas used in the manufacture of integrated circuits. The first such use was in photoresist stripping by an oxygen plasma. The recent extensive use of plasmas for dry etching of semiconductor materials and for dry development of resists means that much more detailed knowledge of the behaviour of polymers in such plasmas is now essential. This account outlines the main processes where resists are exposed to plasmas, and deals with studies of individual homopolymers and some copolymers, concentrating on understanding of the reaction mechanisms gained thereby.     

Emission characteristics of mixed gas plasmas in low-pressure glow discharges

Glow discharge optical emission spectrometry (GD-OES) with mixed plasma gases is reviewed. The major topic is the effect of type and content of gases added to an argon plasma on the emission characteristics as well as the excitation processes. Emphasis is placed on argon–helium, argon–oxygen, and argon–nitrogen mixed gas plasmas. Results for non-argon-matrix plasmas, such as neon–helium and nitrogen–helium mixtures, are also presented. Apart from the GD-OES, glow discharge mass spectrometry and furnace atomization plasma emission spectrometry with mixed plasma gases are also discussed.     

Analysis of the effect of malaria on lipid composition of rhesus plasma

The phospholipid distribution and the ratio of cholesterol-to-cholesterol ester have been determined for plasmas isolated from normal, fasted and P. knowlesi-infected rhesus monkeys. Compared to normal plasmas, the infected plasmas show phospholipid patterns with slight increases in phosphatidylcholine and larger decreases in lysophosphatidylcholine. The cholesterol-to-cholesterol ester ratio is always less than one in normal plasmas and greater than one for infected plasmas. There are no differences between samples isolated from fasting and non-fasting animals for any of the constituents examined.     

Fundamental reference data for understanding analytical plasmas—what's missing

Several areas where fundamental reference data are still needed for the utilization of quantitative atomic and molecular spectroscopy in studying anlytical plasmas are outlined. Possible remedies are proposed for provision of these quantities so that chemists might better design new analytical applications of plasmas. In addition, a general recommendation is made that better funded collaboration amongst analytical and physical chemists would yield large dividends in understanding analytical plasmas, thus, enhancing the facility with which these devices are employed.     

Characterization of laser induced breakdown plasmas used for measurements of arsenic,antimony and selenium hydrides

Studies have been performed to characterize laser induced breakdown spectroscopy (LIBS) plasmas formed in Ar/H₂ gas mixtures that are used for hydride generation (HG) LIBS measurements of arsenic (As), antimony (Sb) and selenium (Se) hydrides. The plasma electron density and plasma excitation temperature have been determined through hydrogen, argon and arsenic emission measurements. The electron density ranges from 4.5 × 10¹⁷ to 8.3 × 10¹⁵ cm^?3 over time delays of 0.2 to 15 μs. The plasma temperatures range from 8800 to 7700 K for Ar and from 8800 to 6500 K for As in the HG LIBS plasmas. Evaluation of the plasma properties leads to the conclusion that partial local thermodynamic equilibrium conditions are present in the HG LIBS plasmas. Comparison measurements in LIBS plasmas formed in Ar gas only indicate that the temperatures are similar in both plasmas. However it is also observed that the electron density is higher in the Ar only plasmas and that the emission intensities of Ar are higher and decay more slowly in the Ar only plasmas. These differences are attributed to the presence of H₂ which has a higher thermal conductivity and provides additional dissociation, excitation and ionization processes in the HG LIBS plasma environment. Based on the observed results, it is anticipated that changes to the HG conditions that change the amount of H₂ in the plasma will have a significant effect on analyte emission in the HG LIBS plasmas that is independent of changes in the HG efficiency. The HG LIBS plasmas have been evaluated for measurements of elements hydrides using a constant set of HG LIBS plasma conditions. Linear responses are observed and limits of detection of 0.7, 0.2 and 0.6 mg/L are reported for As, Sb and Se, respectively.     

Mass spectrometer-wall probe diagnostic of Ar discharges containing SF6 and/or O2: Reactive ions in etching plasmas

Positive and negative ions of Ar/SF₆ and Ar/SF₆/O₂ plasmas (etching plasmas) and of Ar/O₂ plasmas (cleaning plasmas) in Pyrex tubes have been investigated using a mass spectrometer-wall probe diagnostic technique. The measurement of negative ions proved to be a very sensitive method for the detection of wall material. In etching plasmas with small admixtures of SF₆, oxygen was found as the only representative of wall material. At larger amounts of SF₆, silicon could be detected. In cleaning plasmas with small admixtures of O₂ applied to a previously etched Pyrex surface, fluorine was found, indicating the reversal of fluoridation by oxygenation.     

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.