Electrical characteristics of a millisecond pulsed glow discharge

A μs and ms pulsed argon glow discharge was investigated with respect to the breakdown condition (Paschen curve). Moreover, current–voltage profiles were acquired for different discharge frequencies, pulse durations, cathode–anode spacing and discharge pressures. The breakdown voltage was dependent on the cathode material (Cu, steel, Ti and Al). No severe change in the breakdown voltage was observed for a 1 ms pulse at different frequencies. However, the theoretical breakdown curve, calculated based on the Paschen equation did not fit the experimental data. The current plots for different cathode–anode spacing showed a maximum at intermediate distance (8–10 mm). These data were consistent with mass spectrometric data acquired using the same instrument in a GC-GD-TOFMS chemical speciation study.     

Spectral,spatial and temporal characterization of a millisecond pulsed glow discharge: copper analyte emission and ionization

Two-dimensional maps of the spatial distributions of excited and ionized sputtered copper atoms are presented for a millisecond pulsed argon glow discharge. These maps demonstrate the temporal as well as spatial dependence of different excitation and ionization processes over the pulse cycle. Transitions from the low energy electronic states for the atom, characterized by emission such as that at 324.75 nm (3.82→0.00 eV), dominate the plateau time regime at a distance of 2.5 mm from the cathode surface. These processes originate from the electron excitation of ground state copper atoms. Transitions from high-energy electronic states, such as that characterized by emission at 368.74 nm (7.16→3.82 eV), predominate during the afterpeak time regime at a distance of 5.0–6.0 mm from the cathode surface. This observation is consistent with the relaxation of highly excited copper atoms produced by electron recombination with copper ions during the afterpeak time regime. Analyses of afterpeak and plateau intensities for a series of copper emission lines indicate an electron excitation temperature equivalent to 5.78 eV at 0.8 torr and 1.5 W. Temporal profiles exhibit copper ion emission only during the plateau time regime.     

Spectral, spatial and temporal characteristics of a millisecond pulsed glow discharge: metastable argon atom production

Time resolved atomic emission, atomic absorbance, and laser-induced atomic fluorescence measurements of a millisecond pulsed glow discharge, made perpendicular to the insertion probe, provide temporal profiles of 1s₅ (³P₂) and 1s₃ (³P₀) metastable argon atom populations. Acquisition of these profiles at different spatial positions in the plasma provides data from which two-dimensional spatial plots of relative populations are constructed. Each map, the result of 368 individual pulse profiles, provides insight into the production of metastable argon atoms as a function of time and position within the plasma. During power application, intensities plateau after 3 ms as the plasma reaches a steady state condition. Metastable argon atoms are most abundant 1–2 mm above the cathode surface during this time. Excitation mechanisms such as electron excitation and fast atom/ion impact appear to dominate in this temporal regime. In contrast, argon ion–electron recombination dominates metastable formation after pulse termination. The relative population maximum for metastable argon atoms in the afterpeak shifts to 5–9 mm above the cathode surface. This shift should impact signals for analyte species generated by Penning processes in the plasma. Absorption and fluorescence measurements of the ³P₂ (11.55 eV) and the ³P₀ (11.72 eV) metastable argon atom states indicate possible differences in the populations of these two states between the plateau and afterpeak time regimes.     

Incorporation of sodium into silicon dioxide film fabricated in glow discharge plasma

Results of experiments on the plasma-assisted fabrication of a silicon dioxide film with incorporated sodium are reported. The film was obtained via the decomposition of vaporized tetraethoxysilane and sodium compounds in a glow-discharge plasma and the deposition of the degradation products on a substrate. It is shown that this procedure makes it possible to incorporate up to 7 wt % sodium in the film composition.     

Elimination of water interference in pulsed glow discharge time-of-flight mass spectrometry

The presence of water in the discharge cell is a serious problem in glow discharge mass spectrometry. Even very small quantities of water can make considerable changes in the composition and electrical parameters of the plasma, which lead to a decrease in the signal intensity and the appearance of various cluster components. This results in a very complicated mass spectrum and significantly deteriorates the analytical performance of the method. Different approaches to solving the this problem are discussed in the paper. A multiple position interface that allows analyzing 6–10 samples without decapsulation of the discharge cell is presented in this work. It is also shown that the use of a tantalum auxiliary cathode ensures a several-order depression of the interfering components (OH⁺, OH ₂ ⁺ , OH ₃ ⁺ , ¹²C¹H ₂ ⁺ , ¹⁶O⁺, ¹²C¹H ₃ ⁺ ) because of its getter behavior. The simultaneous application of all proposed approaches ensures solving the problem of interferences in the combined hollow cathode with pulsed glow discharge to the great extent.     

Ion formation processes in the afterpeak time regime of pulsed glow discharge plasmas

The formation of ions following the termination of power in a pulsed glow discharge ion source is investigated. The populations of ionized species containing sputtered atoms M⁺, M ₂ ¹ :, and MAr⁺ are observed to maximize after the termination of discharge power. Collisions involving sputtered atoms and metastable argon atoms, Penning and associative ionization, are considered to be responsible for the formation of ions in the discharge afterpeak time regime. The domination of these ion formation processes during the afterpeak time regime is supported by the results from investigations of discharge operating parameters, metastable argon atom quenching, and ion kinetic energy distributions.     

Spectroscopic investigations of a cathode fall region of the Grimm-type glow discharge

This paper presents the results of the spectroscopic study of the cathode fall region of a plane cathode Grimm-type glow discharge in pure hydrogen and in argon with small admixtures of hydrogen. In contrast with the discharge in an argon-hydrogen mixture, the volt-ampere characteristics of the pure hydrogen discharge show a maximum typical for an abnormal glow-to-arc transition. This maximum in the V-A curve is explained here as being due to the increasing role of self-sputtering of the cathode material in sustaining the discharge at higher currents.For the measurements of the electric fields in the cathode fall region, Stark spectroscopy of the hydrogen Balmer lines is employed. Consistent results were obtained from H_β and H_γ recordings in a pure hydrogen discharge. Some of the difficulties in applying Stark spectroscopy for the diagnostics of a spatially inhomogeneous electric field inherent to Grimm glow discharges are discussed in detail. The experimental results are used to test the theoretical predictions of the electric field distribution in the cathode fall region. Reasonable agreement between theories and experiment is reported.Doppler spectroscopy of the same Balmer lines is used to determine the energies of the excited hydrogen atoms in the discharge. In the cathode fall region of a pure hydrogen discharge, two groups of excited atoms are detected: “slow”, in the range 3.4–8.2 eV, and “fast”, in the range 80–190 eV. The relative concentrations of “slow” and “fast” excited hydrogen atoms in the cathode fall region are determined. In addition, the relative concentration of hydrogen atoms with temperatures around 0.1 eV, excited in the plasma of the negative glow region, is also determined. The origin of these “slow” and “fast” hydrogen atoms is related to the presence of H⁺ and H₃⁺ ions, respectively. In the cathode fall region of an argon-hydrogen mixture discharge, only excited hydrogen neutrals with energies of 32–43 eV are detected. Their origin is related to the dominant role of H₃⁺ ions in this discharge. For both gases, in the negative glow region, an increase in the temperature of excited hydrogen atoms is detected, and is explained by the additional excitation of energetic neutrals in collisions with electrons.The axial intensity distributions of the hydrogen Balmer lines, in comparison with other atomic and ionic lines, show different shapes with maxima in the vicinity of the cathode surface. These shapes are explained by the excitation of reflected high-energy neutral atoms in collisions with the matrix gas.     

Selective excitation of singly-ionized silver emission lines by Grimm glow discharge plasmas using several different plasma gases

The relative intensities of silver emission lines from Grimm glow discharge plasmas were investigated in the wavelength range from 160 to 600 nm when using different plasma gases. It was characteristic of the plasma excitation that the spectral patterns were strongly dependent on the nature of the plasma gas employed. Intense emission lines of silver ion were observed when argonhelium mixed gases were employed as the plasma gas. Selective excitation of the ionic lines could be principally attributed to the charge transfer collisions between silver atoms and helium ions.     

About some pecularities of ionization in radio-frequency glow discharge (rfGD)

Two modes of rfGD formation were observed: intense and mild. In the mild mode mainly molecular peaks and large molecular fragments were observed and they were more abundant than with electron impact ionization. In the intense mode more molecular destruction was observed.     

About some pecularities of ionization in radio-frequency glow discharge (rfGD)

Two modes of rfGD formation were observed: intense and mild. In the mild mode mainly molecular peaks and large molecular fragments were observed and they were more abundant than with electron impact ionization. In the intense mode more molecular destruction was observed.     

Model of microsecond pulsed glow discharge in hollow cathode for mass spectrometry

A new model for microsecond pulsed glow discharge in a hollow cathode and its afterglow is described. The model is based on the Monte-Carlo method together with a new method for electrical field calculation, which is based on some phenomenological laws of plasma behavior. The afterglow model uses continuity and Poisson equations. A qualitative agreement between the model results and results published in experimental and theoretical works is demonstrated. Some processes in the microsecond pulsed discharge in the hollow cathode, such as sputtering, ionization and transfer of sample, are investigated. The model is successfully used for the optimization of the operational parameters of the time-of-flight mass spectrometer with ionization by microsecond pulsed glow discharge in a hollow cathode.     

Effect of excitation states of nitrogen on the surface nitridation of iron and steel in d.c. glow discharge plasma

The plasma nitriding phenomena that occur on the surfaces of iron and steel were investigated. In particular, the correlation between the kinds of nitrogen radicals and the surface nitriding reaction was investigated using a glow‐discharge apparatus. To control the excitation of nitrogen radicals, noble gas mixtures were used for the plasma gas. The highly populated metastables of noble gases selectively produce excited nitrogen molecules (N₂*) or nitrogen molecule ions (N₂⁺). The optical emission spectra suggested that the formation of N₂*‐rich or N₂⁺‐rich plasma was successfully controlled by introducing different kinds of noble gases. Auger electron spectroscopy and XPS were used to characterize the depth profile of the elements and chemical species on the nitrided surface. The nitride layer formed by a N₂⁺‐rich plasma had a much higher nitrogen concentration than that by a N₂*‐rich plasma, likely due to the larger chemical activity of the N₂⁺ species as well as the N₂⁺ sputtering bombardment to the cathode surface. The strong reactivity of the N₂⁺ species was also confirmed from the chemical shift of N 1s spectra for iron nitrides. An iron nitride formed by the N₂⁺‐rich plasma has higher stoichiometric quantity of nitrogen than that formed by the N₂*‐rich plasma. Besides the effect of nitrogen radicals on surface nitridation, the contribution of the chromium in steel to the nitriding reaction was also examined. This chromium can promote a nitriding reaction at the surface, which results in an increase in the nitrogen concentration and the formation of nitride with high nitrogen coordination. Copyright © 2010 John Wiley & Sons, Ltd.     

Thermoluminescence of thin polymeric films obtained in a glow discharge plasma

The thermoluminescence and radiothermoluminescence were studied of thin polymeric films produced in a glow discharge plasma. It was shown that during the formation of polymeric films in the plasma, not only radical states but also ionic states are stabilized in them. Four luminescence maxima were detected on the radiothermoluminescence curves of the films. The possible assignment of the position of these maxima on a temperature scale to the relaxational transitions in the films is discussed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 6, pp. 743–747, November–December, 1988.     

Electronic excitation and ionization temperature measurements in a high frequency inductively coupled argon plasma source and the influence of water vapour on plasma parameters

Excitation temperatures measured from Fe I lines with a wide range of upper energy levels have shown that the environment of the central channel of an argon ICP is not in a state of local thermal equilibrium, as predicted from Griem's criterion. Deviations from a Boltzmann distribution have been observed in the population of the excited states of Fe I. The significance of water in providing extra electrons by ionization in the ICP is demonstrated and discussed.     

Temperatures,electron densities and degrees of ionization in a boosted glow discharge emission lamp

The intensities of FeI and FeII spectral lines emitted by a boosted glow discharge lamp were measured over a range of typical lamp operating conditions. Several spectral lines were chosen for determinations of FeI and FeII excitation temperatures.It was found that when sufficient booster current was applied, the FeI and FeII temperatures were comparable (ca. 4000 K) and reasonably independent of discharge parameters. Determinations of electron density (5 × 10¹³ cm^?3) and degrees of ionization for calcium (81.3%), chromium (19.5%), magnesium (5.5%) and manganese (5.2%) were made in similar stable excitation conditions.An equation which allows the calculation of the degree of ionization for any element in typical discharge conditions was formulated and the expected degree of ionization was calculated for fifteen elements.     

Improving pulsed radiofrequency glow discharge for time-of-flight mass spectrometry simultaneous elemental and molecular analysis

The performance of radiofrequency (rf) millisecond pulsed glow discharge (PGD) coupled to a fast orthogonal time-of-flight mass spectrometer (TOFMS) for chemical characterization and quantification of organic volatile compounds was investigated by using two different GD chamber designs. The designs investigated had substantial differences in the way that the volatile organic compound is introduced into the GD and the distance between the cathode and the sampling cone of the mass spectrometer. Bromochloromethane was selected as the model analyte because of the practical interest of determining trihalomethanes at low concentrations, and also because of both its low boiling point (to avoid problems associated with condensations in the interface) and the fact that it has two different heteroatoms, making the fragmentation patterns easier to follow. Pulse shapes of element, fragment, and molecular parent ions obtained by using the two GD chambers under investigation were critically compared. Results revealed the critical effect of the GD chamber geometry in obtaining the three types of chemical information, temporally discriminated. The spectra of the gaseous samples and of a polymer containing TBBPA (solid sample) were also compared. Detection limits for bromochloromethane in the order of low ng L^?1, and the required high tolerance of the plasmas to the introduction of organic vapours, were achieved using one of the proposed GD designs. The capability of the designed system for the analysis of other volatile compounds, for example dimethyl disulfide and dimethyl selenide, was also successfully evaluated, making use of the analytical potential of the information obtained from the different pulse time regions. Figure

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Elemental ratio determinations and compound-independent calibration using microsecond pulsed glow discharge time-of-flight mass spectrometry

A new prototype based on a microsecond pulsed glow discharge ion source coupled to a time-of-flight mass spectrometer was recently designed, constructed and analytically evaluated in our laboratory for simultaneous collection of elemental and molecular information, and as a gas-chromatographic detector of compounds of environmental concern. To investigate further the analytical capabilities of such a new setup, its capability for the determination of element ratios in volatile organic halogenated compounds has been explored. Moreover, compound-independent calibration has been carried out with the prototype as well. The results demonstrated that the intensity ratios (analyte to internal standard) were linear with the corresponding ratio of concentrations. Both for chlorine and bromine (measured in the prepeak) and for BrC (measured in the plateau) the slope was 1 and the intercept was 0. Moreover, detection limits were improved by more than 1 order of magnitude as compared with using external calibration. The applicability of the proposed approach has been demonstrated for the straightforward determination of chloroform in drinking and river waters.     

Factors influencing the analytical performance of an atmospheric sampling glow discharge ionization source as revealed via ionization dynamics modeling

A kinetic model is developed for the dynamic events occurring within an atmospheric sampling glow discharge that affect its performance as an ion source for analytical mass spectrometry. The differential equations incorporate secondary electron generation and thermalization, reagent and analyte ion formation via electron capture and ion-molecule reactions, ion loss via recombination processes, diffusion, and ion-molecule reactions with matrix components, and the sampling and pumping parameters of the source. Because the ion source has a flow-through configuration, the number densities of selected species can be estimated by applying the steady-state assumption. However, understanding of its operation is aided by knowledge of the dynamic behavior, so numerical methods are applied to examine the time dependence of those species as well. As in other plasma ionization sources, the ionization efficiency is essentially determined by the ratio of the relevant ion formation and recombination rates. Although thermal electron and positive reagent ion number densities are comparable, the electron capture/ion-molecule reaction rate coefficient ratio is normally quite large and the ion-electron recombination rate coefficient is about an order of magnitude greater than that for ion-ion recombination. Consequently, the efficiency for negative analyte ion formation via electron capture is generally superior to that for positive analyte ion generation via ion-molecule reaction. However, the efficiency for positive analyte ion formation should be equal to or better than that for negative analyte ions when both ionization processes occur via ion-molecule reaction processes (with comparable rate coefficients), since the negative reagent ion density is considerably less than that for positive reagent ions. Furthermore, the particularly high number densities of thermal electrons and reagent ions leads to a large dynamic range of linear response for the source. Simulation results also suggest that analyte ion number densities might be enhanced by modification of the standard physical and operating parameters of the source.     

On plasma composition of a pulsed discharge in electrolyte

The equilibrium plasma composition for a system containing H, O, N, Na, and Cu is determined for the temperature range between 5000–20,000 K. This corresponds to the pulsed discharge plasma in electrolyte with energy dissipation which is near threshold. For computing the plasma composition of the system based on the minimization of free energy, the method of steepest descent was used. The plasma composition was calculated for different electrolyte contents, conductivity, and various external pressures.     

Analytical performance of high-voltage neon plasma in glow discharge optical emission spectrometry

In a high-voltage Ne glow discharge plasma (Ne-GDP), calibration factors as well as the limit of determination were compared between atomic resonance lines and singly-ionized lines of copper and aluminium in optical emission spectrometry. These elements have intense ionic lines which are excited by resonance charge-transfer collisions of Ne ions. The ionic lines gave better detection sensitivity in the Ne-GDP, whereas the atomic resonance lines were commonly employed as analytical lines in the other plasma sources such as Ar-GDP and ICP. The limit of determination was 1.3 × 10^–3 mass % for the Cu II 248.58 nm line and 1.0 × 10^–3 mass % Al for the Al II 358.66 nm line at a discharge parameter of 1.60 kV/36 mA.