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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.
RESUMO
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.
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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.
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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.
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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.
RESUMO
Recent theoretical studies with alkali atoms A* excited to high Rydberg states predicted the existence of ultra-long-range molecular bound states. Such excited dimers have large electric dipole moments which, in combination with their long radiative lifetimes, make them excellent candidates for manipulation in applications. This Letter reports on experimental investigations of the self-broadening of Rb principal series lines, which revealed multiple satellites in the line wings. The positions of the satellites agree quantitatively with theoretically predicted minima in the excited long-range Rydberg states of Rb2.
