Dielectric barrier discharge (DBD)-based analytical applications have experienced rapid development in recent years. DBD designs and parameters and the application they are used for can vary considerably. This leads to a diverse field with many apparently unique systems that are all based on the same physical principle. The most significant changes among DBDs used for chemical analysis are in how the discharge electrodes are separated from the ignited discharge gas. While the official definition of a DBD states that at least one electrode has to be covered by a dielectric to be considered a DBD, configurations with both electrodes covered by dielectric layers can also be realized. The electrode surface plays a major role in several plasma-related technical fields, surface treatment or sputtering processes, for example, and has hence been studied in great detail. Analytical DBDs are often operated at low power and atmospheric pressure, making a direct transfer of insight and know-how gained from the aforementioned well-studied fields complicated. This work focuses on comparing two DBD configurations: the low temperature plasma probe (LTP) and the dielectric barrier discharge for soft ionization (DBDI). The LTP is representative of a DBD with one covered electrode and the DBDI of a design in which both electrodes are covered. These two configurations are well suited for a systematic comparison due to their similar geometric designs based on a dielectric capillary.

A capillary He dielectric barrier discharge was investigated with respect to its performance as a soft or dissociative ionization source. Spatiotemporal measurements of the plasma emission showed that in one voltage duty cycle the plasma evolved from a soft to dissociative ionization source. At the earliest time, the soft plasma was generated between the electrodes as well as outside the capillary forming the plasma jet. It was characterized by significant radiation arising only from He and N2(+), which are known to be important in the process of the soft ionization of the analyte. Later in time, the plasma capable of dissociating molecules develops. It is characterized by appreciable radiation from analyte dissociation products and is restricted to the interelectrode region in the capillary. Thus, for the soft ionization purposes, it is feasible to introduce the analyte exclusively in the plasma jet. For elemental analysis, the interelectrode plasma is appropriate.

While the influence of trace impurities in noble gas discharges is well established in theoretical work, experimental approaches are difficult. Particularly the effects of trace concentrations of N2 on He discharges are complicated to investigate due to the fact that for He 5.0 the purity of He is only 99.999%. This corresponds to a residual concentration of 10 ppm, thereof 3 ppm of N2, in He. Matters are made difficult by the fact that He DBD plasmajets are normally operated under an ambient atmosphere, which has a high abundance of N2. This work tackles these problems from two sides. The first approach is to operate a DBD plasmajet under a quasi-controlled He atmosphere, therefore diminishing the effect of atmospheric N2 and making a defined contamination with N2 possible. The second approach is using Ar as the operating gas and introducing propane (C3H8) as a suitable substitute impurity like N2 in He. As will be shown both discharges in either He or Ar, with their respective impurity show the same qualitative behaviour.

Helium capillary dielectric barrier discharge driven by the square wave-shaped high voltage was investigated spatially and temporally by means of optical emission spectroscopy. The finding of the previous investigation conducted with the sinusoidal-like high voltage was confirmed, i.e., the plasma in the jet and the plasma in the capillary constitute two temporally separated events. The plasma in the jet occurs prior to the discharge in the capillary and exists only during the positive half period of the applied high voltage. The time delay of the capillary discharge with respect to the discharge in the jet depended on the high voltage, and it was between 2.4 and 8.4 μs for the voltage amplitude change in the range from 1.96 to 2.31 kV, respectively. It was found that, compared to sinusoidal-like voltage, application of the square wave high voltage results with stronger (~6 times) He line emission in the jet, which makes the latter more favorable for efficient soft ionization. The use of the square wave high voltage enabled comparison of the currents (~1 mA) flowing in the capillary during the positive and negative high voltage periods, which yielded the estimation for the charge dissipated in the atmosphere ((4 ± 20 %) × 10−11 C) through the plasma jet.

A helium capillary dielectric barrier discharge was investigated by means of time-resolved optical emission spectroscopy with the aim of elucidating the process of the formation of the plasma jet. The helium emission line at 706 nm was utilized to monitor spatial and temporal propagation of the excitation of helium atoms. The discharge was sustained with quasi-sinusoidal high voltage, and the temporal evolution of the helium atomic emission was measured simultaneously with the discharge current. The spatial development of the plasma was investigated along the discharge axis in the whole region, which covers the positions in the capillary between the electrodes as well as the plasma jet outside the capillary. The high voltage electrode was placed 2 mm from the capillary orifice, and the distance between the ground and high voltage electrode was 10 mm. The complete spatiotemporal grid of the development of the helium excitation has shown that during the positive half-period of the applied voltage, two independent plasmas, separated in time, are formed. First, the early plasma that constitutes the plasma jet is formed, while the discharge in the capillary follows subsequently. In the early plasma, the helium atom excitation propagation starts in the vicinity of the high voltage electrode and departs from the capillary towards the ground electrode as well as several millimeters outside of the capillary in the form of the plasma jet. After relatively slow propagation of the early plasma in the capillary and the jet, the second plasma starts between the electrodes. During the negative voltage period, only the plasma in the capillary between the electrodes occurs.

The spatially and temporally resolved optical emission from the helium capillary dielectric barrier discharge driven by a square wave high voltage was measured simultaneously with the discharge currents during the positive and negative voltage periods. The He and N2+ emission intensities were monitored at 501nm and 391nm, respectively. The plasma jet was found to be formed only during the positive voltage period, and it preceded the discharge ignition in the capillary. Thus, the measurements of the difference between the capillary discharge currents during the positive and negative voltage periods enabled quantification of the charge, which was transported through the plasma jet. The analysis of the spatiotemporal behavior of the He emission intensities in the plasma jet yielded the velocity of the helium excitation propagation and the effective plasma jet length. The combination of these measurements enabled determination of the absolute values of the plasma jet currents. The linear relationship between the He emission intensities in the plasma jet and the plasma jet currents was found to exist over the emission intensity range of two orders of magnitude. The N2+ emission intensity was also found to be linearly dependent on the plasma jet current. The fast electrons, producing the excited He atoms, were found to be located mostly within the estimated effective plasma jet length. In this region a cascade of processes involving excited He atoms, N2+ and H2O molecules lead to establishment of the conditions necessary for the plasma jet to be used as soft ionization source. The production of reactive species can be related to the plasma jet current, which can serve as a measure of the soft ionization efficiency.

Permanent need for simple to apply and efficient methods for molecular mass spectrometry resulted in the development of a variety of methods now commonly termed ambient desorption/ionization mass spectrometry (ADI-MS), which experienced a very rapid development during the last 10years. The most widely used techniques are direct analysis in real time (DART), plasma assisted desorption/ionization (PADI), flowing afterglow-atmospheric pressure glow discharge ionization (FA-APGDI), low-temperature plasma probe (LTP) and dielectric barrier discharge ionization (DBDI). They all share the advantage of direct, ambient analysis of samples with little or no pretreatment, and employ some kind of electrical discharge to desorb and ionize the analyte species. However, the investigations focused on the characterization, examination and understanding of underlying ionization mechanisms of these discharges are relatively small in number. More efforts are clearly needed in this segment, since the understanding of the fundamentals of these discharges is a prerequisite for optimization of working parameters of ADI-MS sources with the aim of increasing ionization efficiency. Here, ADI-MS techniques will be overviewed, with the emphasis put on the review and the analysis of the recent progress in dielectric barrier discharges utilized for soft ionization.

The populations of the lowest excited helium states 2s 3S1, 2s 1S, 2p 3P0 J, and 2p 1P0 created in an atmospheric helium capillary dielectric barrier discharge were determined by means of optical emission spectroscopy. The emitted intensities of 388, 501, 587, and 667 nm lines were measured side-on and end-on with respect to the discharge axis. The comparison of optically thin side-on spectra with end-on spectra, which exhibited the absorption effects in the line kernels, enabled the determination of the average values of the number densities n1 in the considered He states along the plasma length L. The field of the theoretical profiles for a series of the n1L parameters pertinent to the experimental conditions was calculated for each line. By introducing the experimental data into the field of calculated curves, n1L corresponding to the particular state could be obtained. The measurements of the emission profiles were done as a function of the discharge voltage in the range covering homogeneous as well as filamentary DBD operation mode. Due to nonuniformity of the excited atom density distribution along the plasma, the values of n1 could be obtained only in the homogeneous operation mode where the nonuniformity was small. The following maximum values were found for the number densities in the investigated states: n1 av (2s 3S1) = (2.9 ± 1.1) × 1013 cm−3, n1 av (2s 1S) = (1.4 ± 0.5) × 1013 cm−3, n1 av (2p 3P0 J) = (1.1 ± 0.4) × 1013 cm−3, n1 av (2p 1P0) = (4.2 ± 1.6) × 1012 cm−3, and they represent the average populations along the plasma column in the capillary.

Among different applications of dielectric barrier discharge (DBD) plasma, the soft ionization ability is certainly one of the most interesting. In this paper the helium plasma jet, produced by a capillary DBD, penetrating in the ambient atmosphere, has been spectroscopically investigated in dependence on applied voltage and helium flow. It was found that the change of the applied voltage leads to different discharge modes. Based on the measurements of the emission spectra of atomic He and N2+ and N2 molecules in the capillary and in the plasma jet with high spatial resolution, it can be assessed in which mode, i.e. under which conditions the plasma jet is expected to be most effective for soft ionization of molecules.

The capillary helium dielectric barrier discharge (DBD) operating at atmospheric pressure was investigated by means of optical emission spectroscopy with the aim to determine the dominant broadening mechanism of the helium spectral lines, gas temperature and electron number density. The dependence of emission profiles of helium 388 nm, 501 nm, 587 nm, 667 nm, 706 nm and 728 nm lines on discharge voltage, helium pressure and position along the DBD capillary was investigated. Also, the pressure and voltage dependence of the profiles of hydrogen H-alpha and H-beta lines was examined. The Lorentzian widths of the normalized helium line profiles were found to be constant with respect to the applied voltage and the position along the capillary. The dominant broadening mechanism for all investigated lines was identified to be due to collisions with ground-state helium atoms, with the Stark broadening being negligible. It was determined that the temperature of the gas was constant along the capillary and independent of the voltage applied on the DBD electrodes and that its value coincided with the room temperature. The measurements of the dependence of the Lorentzian width of hydrogen H-alpha and H-beta lines on helium pressure, combined with gas temperature determined in the experiment, yielded the following values for the broadening parameters due to broadening by neutral helium: γνHe(Hα) = 1.56 × 10−9 cm3 s−1 and γνHe(Hβ) = 3.16 × 10−9 cm3 s−1. From the analysis of the measured H-alpha and H-beta line profiles the upper limit of the electron number density in the investigated plasma was obtained as ne ≤ 1.4× 1012 cm−3.

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry and as ionization source for ion mobility spectrometry. It turned out that dielectric barrier discharge ionization could be regarded as a soft ionization technique characterized by only minor fragmentation similar to atmospheric pressure chemical ionization (APCI). Mainly protonated molecules were detected. In order to characterize the soft ionization mechanism spatially resolved optical emission spectrometry (OES) measurements were performed on plasma jets burning either in He or in Ar. Besides to spatial intensity distributions of noble gas spectral lines, in both cases a special attention was paid to lines of N2+ and N2. The obtained mapping of the plasma jet shows very different number density distributions of relevant excited species. In the case of helium plasma jet, strong N2+ lines were observed. In contrast to that, the intensities of N2 lines in Ar were below the present detection limit. The positions of N2+ and N2 distribution maxima in helium indicate the regions where the highest efficiency of the water ionization and the protonation process is expected.

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry and as ionization source for Ion mobility spectrometry. It turned out that dielectric barrier discharge ionization could be regarded as a soft ionization technique characterized by only minor fragmentation similar to APCI. Mainly protonated molecules were detected. In order to characterize the soft ionization mechanism spatially resolved OES measurements of the He, N2 and N2 spectral line intensities were performed. The obtained mapping of the plasma jet shows clearly different number density distributions of relevant excited species and indicates the positions where the highest efficiency of the water ionization and the protonation process is expected. A modeling of the spatially dependent excitation energy transfer processes involving He, N2 N2 and H2O is presented and compared with the experimental findings.

The present work is a systematic experimental study of the plasma formation in cesium vapor induced by a continuous laser tuned to the resonance transition 6S1/2–6P3/2. Taking into account the measured absolute population densities of Cs ground and excited state atoms as well as the electron densities derived from Stark broadening of the Cs lines, complete local thermodynamic equilibrium in the laser-produced plasma was found for laser power densities ≈10Wcm−2 at cesium ground state number densities of about 1017cm−3. Direct conversion of the excitation energy or parts of the excitation energy in exothermic collisions of laser-excited atoms is concluded to be the major process for atomic vapor heating and subsequent formation of LTE plasmas.

Recent absorption measurements of the self-broadening of Rb principal series lines C. H. Greene, E. L. Hamilton, H. Crowell, C. Vadla, and K. Niemax, Phys. Rev. Lett. 97, 233002 2006 verified the existence of minima in highly excited long-range potentials of Rb2 which were predicted theoretically as bound Rydberg molecule C. H. Greene, A. S. Dickinson, and H. R. Sadeghpour, Phys. Rev. Lett. 85, 2458 2000 . The present paper reports on the extension of these experimental studies to principal series lines of K broadened by K as well as Cs broadened by Cs. In addition, the broadening of some lower members of the K, Rb, and Cs principal line series due to heteroatomic interactions was investigated. The analysis of the measured satellite structures in the quasistatic line wings and their comparison to the previously published analogous data for Rb +Rb system lead to the conclusion that one can expect existence of potential minima in homoand heteroatomic alkali-metal A +B systems in a wide range of principal quantum numbers, starting with K, Rb, and Cs excited to the third resonance states. The positions and strengths of the satellite structures indicate that the potential minima are due to scattering of the valence electron by ground-state perturbers.

Elemental fractionation in femtosecond laser ablation is studied by ICP-MS by applying successive single laser shots to binary metallic and semiconductor samples as well as to multi-component glasses. Fractionation can be observed in the first laser shots in particular if the laser fluence is near the ablation threshold of the sample. However, the element ratio in the laser-sampled masses changes from shot to shot until it reaches an asymptotic fluence-independent value representing stoichiometric sampling. The asymptotic stoichiometric ratios can be obtained with fewer shots if higher laser fluences are applied. It is shown by electron probe X-ray analysis that different elemental ablation probabilities modify the element compositions in the surface layers of the laser craters until equilibrium conditions are obtained. These conditions can be reached by applying many shots of low laser fluence or with one high-fluence laser shot only. The experimental data reveal that in most cases the elemental ablation probability can be correlated with the respective ionization energies of the elements, i.e., the elements with lower first ionization energy have higher ablation probability. No or only very weak fractionation was observed when elements with nearly the same ionization energies were sampled.

The collisional broadening and shift rate coefficients of the "forbidden" 6p(2) P-3(o) -> 6p(2) P-3(1) transition in lead were determined by diode laser absorption measurements performed simultaneously in two resistively heated hot-pipes. One hot-pipe contained Pb vapor and noble gas (Ar or He) at low pressure, while the other was filled with Ph and noble gas at variable pressure. The measurements were performed at temperatures of 1220 K and 1290 K, i.e., lead number densities of 4.8 x 1015 cm(-3) and 1.2x 1016 cm(-3). The broadening rates were obtained by fitting the experimental collisionally broadened absorption line shapes to theoretical Voigt profiles. The shift rates were determined by measuring the difference between the peak absorption positions in the spectra measured simultaneously in the heat pipe filled with noble gas at reference pressure and the one with noble gas at variable pressure. The following data for the broadening and shift rate coefficients due to collisions with Ar and He were obtained: gamma(Ar)(B)=(3.4 +/- 0.1)x10(-10) cm(3) s(-1), gamma(He)(B) = (3.8 +/- 0.1)x10(-10) cm(3) s(-1), gamma(Ar)(S) = (-7.3 +/- 0.8) x 10(-11) cm(3) s(,)(-1) gamma(He)(B) = (-6.5 +/- 0.7)x10(-10) cm(3) s(-1) . (c) 2008 Elsevier B.V. All rights reserved.

A simple and accurate way of determining atom number densities in dense rubidium vapors is presented. The method relies on the experimental finding that the reduced absorption coefficients of the Rb triplet satellite bands between 740 nm and 750 nm and the triplet diffuse band between 600 nm and 610 nm are not temperature dependent in the range between 600 K and 800 K. Therefore, the absolute values of the reduced absorption coefficients of these molecular bands can provide accurate information about atomic number density of the vapor. The rubidium absorption spectrum was measured by spatially resolved white-light absorption in overheated rubidium vapor generated in a heat pipe oven. The absolute values for the reduced absorption coefficients of the triplet bands were determined at lower vapor densities, by using an accurate expression for the reduced absorption coefficient in the quasistatic wing of the Rb D1 line, and measured triplet satellite bands to the resonance wing optical depth ratio. These triplet satellite band datawere used to calibrate in absolute scale the reduced absorption coefficients of the triplet diffuse band at higher temperatures. The obtained values for the reduced absorption coefficient of these Rb molecular features can be used for accurate determination of rubidium atomic number densities in the range from about 5 x 10(16) cm(-3) to 1 x 10(19) cm(-3). (C) 2007 Elsevier B.V. All rights reserved.

Experimental studies of the absorption spectrum of the Rb-2 dimer are performed in the 600-1100 nm wavelength range for temperatures between 615 and 745 K. The reduced absorption coefficient is measured by spatially resolved white light absorption in overheated rubidium vapor with a radial temperature gradient, which enables simultaneous measurements at different temperatures. Semiclassical and quantum spectral simulations are obtained by taking into account all possible transitions involving the potential curves stemming from the 5 S-2+5 S-2 and 5 S-2+5 P-2 asymptotes. The most accurate experimental potential curves are used where available, and newly calculated potential curves and transition dipole moments otherwise. The overall consistency of the theoretical model with the experimental interpretation is obtained only if the radial dependence of both the calculated transition dipole moments and the spin-orbit coupling is taken into account. This highlights the low-resolution absorption spectroscopy as a valuable tool for checking the accuracy of molecular electronic structure calculations.