Time-resolved Optical Emission Spectroscopy Research Articles

A comparative study on the spectral characteristics of nanosecond pulsed discharges in atmospheric He and a He+2.3%H2O mixture

Nanosecond pulsed discharges at atmospheric pressure in a pin-to-pin electrode configuration are well reproducible in time and space, which is beneficial to the fundamentals and applications of low-temperature plasmas. In this experiment, the discharges in helium (He) and He with 2.3% water vapor (H2O) are driven by a series of 10 ns overvoltage pulses (~13 kV). Special attention is paid to the spectral characteristics obtained in the center of discharges by time-resolved optical emission spectroscopy. It is found that in helium, the emission of atomic and molecular helium during the afterglow is more intense than that in the active discharge, while in the He+2.3%H2O mixture, helium emission is only observed during the discharge pulse and the molecular helium emission disappears. In addition, the emissions of OH(A-X) and Hα present similar behavior that increases sharply during the falling edge of the voltage pulse as the electrons cool down rapidly. The gas temperature is set to remain low at 540 K by fitting the OH(A-X) band. A comparative study on the emission of radiative species (He, He2, OH and H) is performed between these two discharge cases to derive their main production mechanisms. In both cases, the dominant primary ion is He+ at the onset of discharges, but their He+ charge transfer processes are quite different. Based on these experimental data and a qualitative discussion on the discharge kinetics, with regard to the present discharge conditions, it is shown that the electron-assisted three-body recombination processes appear to be the significant sources of radiative OH and H species in high-density plasmas.

Influence of the RF voltage amplitude on the space- and time-resolved properties of RF–LF dielectric barrier discharges in α–γ mode

This work reports the results of an experimental and modeling study on dual-frequency Ar–NH3 dielectric barrier discharges (DBDs) exhibiting the α–γ transition. A combination of space- and time-resolved optical absorption and emission spectroscopy is used to record spatio-temporal mappings of the Ar metastable number density, Ar 750.4 nm line emission intensity, and electron–Ar bremsstrahlung continuum emission intensity. With the increase of the radio frequency (RF) voltage amplitude in a 50 kHz–5 MHz DBD, maximum populations of Ar excited species (1s and 2p states, linked to the population of high-energy electrons) observed in the γ mode decrease and appear earlier in the low-frequency cycle. On the other hand, the density of the bulk electrons, monitored from the continuum emission intensity, increases, with a more prominent rise in the RF-α mode than in the γ regime. Such behaviors are consistent with the predictions of 1D fluid model and results from a decrease of the gas voltage required for self-maintenance of the cathode sheath in the γ breakdown.

Dual-frequency sheath oscillations and consequences on the ion and electron transport in dielectric barrier discharges at atmospheric pressure

Current–voltage characteristics, space- and time-resolved optical emission spectroscopy, and 1D fluid modeling are used to examine the effect of dual-frequency sheath oscillations on the ion and electron transport in dielectric barrier discharges sustained by a combination of low frequency (LF, 50 kHz, 650 V) and radiofrequency (RF, 5.3 MHz, 195 V) voltages, exhibiting the α-to-γ mode transition. On one hand, when polarities of the LF and RF voltages are opposite, an electric field near the LF cathode (due to LF cathode sheath) drives the secondary electrons to the plasma bulk and an opposite electric field between the sheath edge and the LF anode attracts the electrons toward the LF cathode (to maintain quasi-neutrality in the plasma bulk). At the sheath edge, electrons become trapped and ions drift toward the cathode and the anode simultaneously according to their position in the gap. On the other hand, when the RF voltage has the same polarity as the LF voltage, the total applied voltage increases and this yields to enhanced production of electrons and ions in the sheath. To maintain quasi-neutrality in the bulk, the electric field along the gap exhibits the same polarity as the one in the sheath, allowing electrons created in the sheath to be evacuated toward the LF anode. The behavior of the LF cathode is, therefore, controlled by the LF sheath, and, thus, by the LF voltage amplitude, while the behavior in the bulk and at the anode alternates on the time scale of the RF voltage.

Layer-by-layer structured nanocomposite deposits from plasma-synthesized organosilicon nanoparticles and organosilicon nanoparticles decorated with Ag nanoparticles by taking advantage of cyclic nanoparticle formation in Ar/HMDSO reactive plasmas

Rational engineering of thin nanocomposite layers, deposited in reactive plasmas, requires knowledge on the plasma behavior in order to produce multifunctional deposits with tailored properties (structural, optical, electrical, etc.) This work presents an experimental study of nanoparticles synthesized in the plasma gas-phase and their subsequent use as building-blocks to form layer-by-layer nanostructures. The experiment is performed in a plasma process that successfully combines plasma polymerization of an organosilicon molecular precursor (hexamethyldisiloxane, HMDSO) and sputtering of a metallic (silver) target. Pulsed injection of the precursor is found to promote cyclic nanoparticle formation in Ar/HMDSO reactive plasmas. The plasma electron temperature is found to vary in the range 1.6—2.2 eV as derived from time-resolved optical emission spectroscopy of the plasma energetic conditions. This diagnostic method is also shown to provide a reliable tool for online monitoring of the nanoparticle synthesis process. Two types of layer-by-layer structured nanocomposites can be obtained depending on the type of nanoparticles synthesized: (i) organosilicon nanoparticles of size less than 100 nm in all studied plasma conditions for a large quantity of injected HMDSO and (ii) raspberry-like nanoparticles of size less than 150 nm when the quantity of injected HMDSO is reduced. The organosilicon nanoparticle growth follows a polydimethylsiloxane (PDMS)-like oligomerization scheme in which the R2-Si(-O)2 silicon bond tends towards the formation of polymeric structure in a R3-Si(-O)1 silicon chemical environment, containing Si-(CH2)-Si type bridges that are involved in cross-linking. The elemental composition of the raspberry-like nanoparticles is similar to that of the organosilicon nanoparticles, supplemented by the Ag component. The decorating silver nanoparticles are ∼15 nm of size, round in shape and polycrystalline. There is no evidence for silver oxides in the nanostructures. The Si-O-Ag bridges, revealed by infrared spectroscopy, suggest the presence of junction sites between the metallic and the organosilicon parts of the raspberry-like nanoparticles. The silver nanoparticles are found to decorate the organosilicon nanoparticles to form the raspberry-like nanoparticles in the plasma gas-phase, before being deposited. This reveals a very interesting phenomenon of simultaneous growth of the silver- and organosilicon-parts in the plasma without mixing during the nucleation phase.

Application of emission spectroscopy in plasma-assisted NH3/air combustion using nanosecond pulsed discharge

This work investigates the effects of atmospheric-pressure nanosecond (ns) pulsed plasma discharges on NH3/air flames using optical emission spectroscopy (OES). Firstly, spatially-resolved OES in the 200–800 nm range of NH3/air flames with and without discharges are presented to identify the plasma-induced excited species (such as N2* and H*). Then, time-resolved OES with ns timescale resolution are achieved to illustrate the discharge dynamics using a statistical imaging strategy, which is specifically designed to overcome the timing jitter of the discharge. From the time-resolved spectra of excited N2, the first and second emission events in NH3/air flames with a time interval of 80 ns are revealed, and each exhibits a profile with two exponential decays. Furthermore, spatial- and time-resolved rotational and vibrational temperatures are derived from the spectral fitting of N2(C→B) to quantify the thermal effects of ns plasmas, thus revealing the ultrafast and slow gas heating processes. In addition, the electron number density along the flame is obtained from the intense Hα line, which locally reaches up to 1 × 1017 cm−3. Besides, the spatial-resolved Hα line intensity suggests that the flame chemistry does not directly affect, but the discharge dominates the production of the atomic hydrogen. It provides insight into the kinetic effects of ns pulsed discharge on NH3 combustion enhancement.

Spectroscopic investigation of early light emission from anode-initiated surface flashover in vacuum

Time-resolved optical emission spectroscopy is used to explore the early development of anode-initiated flashover in vacuum. An experimental apparatus for collecting flashover self-luminosity is introduced, which enables spatially resolved light collection from regions adjacent to the anode and cathode triple junctions. The emitted light is spectrally and temporally resolved utilizing an imaging spectrograph and a fast electronic shutter camera. The first light detectable from flashovers across both Rexolite and polytetrafluoroethylene (PTFE) insulators begins less than 10 ns prior to the flashover gap's impedance collapse and consists of faint broadband feature in primarily visible wavelengths. This suggests luminosity due to excitation in the solid, possibly occurring as a result of field emitted electrons. In the few nanoseconds leading up to and including the impedance collapse, the broadband spectrum grows in intensity and extends into the UV, eventually accompanied by a few emission lines of the insulator material. This is strong evidence that the early stages of anode-initiated flashover include surface layer breakdown of the insulator, as a contrast from cathode-initiated flashover, which is predominately an above-surface process. Spectra accumulated over longer exposures of PTFE flashovers indicate that, in the first few hundred nanoseconds after the impedance collapse, ions from the insulator material constitute the majority of the emission lines. Later, neutral and ionic metal species from the electrode contribute with similar prominence as well as molecular bands from diatomic carbon. Finally, a comparison is provided of the results of these studies to other spectroscopic investigations of vacuum flashover from the literature.

Overview of TOMAS plasma diagnostics

This paper presents an overview of the TOMAS plasma diagnostics. The Langmuir probe method is employed to measure electron temperature, density and floating potential distributions.Two triple probes (horizontal and vertical distributions) and a single probe (horizontal distribution) are used. The measured plasma parameters by the triple and single probes are compared. The ion and neutral atom flux and energy distribution is respectively characterized with a Residual Field Energy Analyzer and a Time-of-Flight Neutral Particle Analyzer. To determine the elemental/charge content of the plasma, the passive method of time-resolved optical emission spectroscopy is used. The time dependence of the integral flow of plasma emission from the discharge is registered by a photodetector. Using a filter allows the photodetector to measure spectral line intensities. To record a wide variety of plasma events several video diagnostics are used. It includes slow video cameras and one high-speed camera in the visible range including Hα.

Rare earth effect on laser produced plasma dynamics during pulsed laser deposition of doped cobalt ferrite

The addition of rare earth elements the ferrites can lead to significant changes in structural, magnetic and electric properties of bulk materials and also of thin films deposited by pulsed laser deposition. The present study relies on the analysis of the laser induced plasma of three sets of cobalt ferrite targets doped with various concentrations of RE elements (Dy, Gd, Yb) and proposes a correlation of the derived results with structural investigations of the films obtained during the same experiment. ICCD imaging and space-and time-resolved optical emission spectroscopy techniques were used to obtain information on the dynamics and excitation temperatures of various species found in the laser produced plasmas (LPP). Initial investigations on the global behavior of the LPP revealed that the addition of RE reduced the drift velocities of the formed plasma structures, the lowest ones being observed for the targets doped with the heaviest RE (Yb). Space-and time-resolved spectroscopy measurements applied for all main elements (Fe, Co and RE - both neutral and ionic species) showed a complex dynamic system, with decreased/increased kinetic energies for neutrals/ions at high dopant concentrations, suggesting a possible re-sputtering effect at the films surface. The individual excitation temperatures of the main elements derived from Boltzmann plots increased as the RE content was augmented via radiative collision events due to their larger diameters compared with Co, Fe or O. The spatial distribution of electron temperature can be explained by the charge separation occurring with the addition of RE in the investigated systems.

Effects of frequency and pulse width on electron density, hydrogen peroxide generation, and perfluorooctanoic acid mineralization in a nanosecond pulsed discharge gas-liquid plasma reactor

Plasma electron density and temperature were characterized in a continuous flowing gas-liquid film reactor with argon carrier gas by time-resolved optical emission spectroscopy. The plasma parameters were studied as a function of time for varying pulse widths and frequencies. Pulse frequency was varied between 1 and 10 kHz at 16 kV (input voltage) and 40 ns (pulse width) using an Eagle Harbor Technologies, Inc. (EHT) power supply and 5–100 kHz using an Airity Technologies, LLC (AT) power supply. The pulse width was varied between 40 and 200 ns at 16 kV, 2 kHz with the EHT power supply. Optimal frequencies of 5 and 20 kHz were observed for peak electron density with EHT and AT power supplies, respectively. The peak electron density increased with increasing pulse width between 40 and 200 ns using the EHT power supply. Hydrogen peroxide exiting the reactor in the liquid phase increased with discharge power irrespective of the power supply or pulse parameters. Mineralization of 12.5, 50, and 200 ppm perfluorooctanoic acid (PFOA) dissolved in DI water to fluoride (F−) correlated to the peak electron density. Glycerol, a liquid-phase hydroxyl radical scavenger, depleted hydrogen peroxide but did not affect PFOA mineralization. CO, a gas-phase hydroxyl radical scavenger, led to a reduction in the formation of F− production, suggesting hydroxyl radicals in the gas-liquid film play a necessary, but not singular, role in mineralization of PFOA.

Influence of pulsed gas injections on the stability of Townsend dielectric barrier discharges in nitrogen at atmospheric pressure

This work investigates the effects of pulsed nitrogen gas injections on the stability of Townsend dielectric barrier discharges operated in continuous nitrogen gas flows at atmospheric pressure. For single-pulse injections with pulse durations lower than the continuous gas residence time (∼50 ms), current–voltage characteristics reveal homogeneous discharges with a single current peak per half-cycle of the applied voltage. However, a sudden decrease of the discharge power over time combined with a temporary transition from homogeneous to filamentary discharge is observed for longer pulses at fixed pulsed gas flows and for higher pulsed gas flows at fixed pulse duration. In addition, for multiple pulsed gas injections with repetition frequencies between 0.1 and 10 Hz, discharge destabilisation increases with the number of pulses. Time-resolved optical emission spectroscopy reveals that, over the single pulse time scale, temporal variations of the emission intensities are longer than the expected residence times of the continuous and pulsed gas flows. Furthermore, a rise of oxygen impurities can be seen over both single and multiple-pulses time scales. Two-dimensional gas flow simulations reveal that pulsed injections introduce sharp and narrow temporal gas velocity profiles over the range of experimental conditions investigated, with no cumulative effects in the discharge cell from one pulse to the other. However, pulsed operation introduces significant changes in the neutral gas composition with time scales comparable to those revealed by electrical and optical diagnostics. In such conditions, the outgassing of impurities adsorbed on surfaces located upstream of the discharge cell plays a vital role in Townsend discharges’ physics and characteristics.

Target heating and plasma dynamics during hot magnetron sputtering of Nb

In this work, the direct current (DC) hot magnetron sputtering (HMS) of Nb has been studied and compared with the conventional cold magnetron sputtering (CMS) discharge. Particularly, these two magnetron systems were investigated in terms of current–voltage trends, behaviour of spectral lines, target temperature, and deposition rate. The current–voltage evolution showing strong variations over time in the HMS system was used to monitor the moment when thermionic emission becomes considerable. Meanwhile, thanks to the time-resolved optical emission spectroscopy (OES), the dynamics of plasma particles and the population of their electronic levels were analysed as a function of the target temperature. The target temperature was measured owing to both pyrometry and OES-based approach, i.e. by fitting an emission spectrum baseline. Finally, in the HMS configuration used in this work, the deposition rate up to 100 nm min−1 was obtained at the applied power density of 30 W cm−2, which is three times higher than the maximum power density applicable to the classical CMS system. However, with further increase in the power density, the deposition rate values were found to be saturated, which is likely caused by a significant increment in a number of thermal electrons in the discharge area.

Time-resolved measurement of radical populations in extreme-ultraviolet-light-induced hydrogen plasma

We have investigated hydrogen plasma induced by intense extreme ultraviolet (EUV) radiation by measuring the plasma parameters and population density of radicals, which is expected to clean the tin contamination on the optics in EUV sources, using a time-resolved optical emission spectroscopy. The obtained electron density was n e = (2 ± 0.4) × 1013 cm−3, and the electron temperature was T e = 1 ± 0.2 eV. The electron density was five orders of magnitude higher than that of previous study. The radical population density determined by the experiment was consistent with that calculated with a collisional radiative model, showing excitation and recombination are dominant production processes.

Deposition phenomena of diamond-like carbon coating on inner surface of circular metal tube by nanopulse plasma chemical vapor deposition

A method of depositing a diamond-like carbon (DLC) film on the inner surface of a circular metal tube by chemical vapor deposition using a nanopulse power source was developed. Because the nanopulse power source can supply rapidly rising and falling high-voltage nanopulses of nanosecond order, a stable plasma can be obtained even in small-diameter tubes by applying a high gas pressure of more than 100 Pa. DLC films were successfully deposited on the inner surfaces of metal tubes of 14 mm diameter and 300 mm length (21% aspect ratio), and of 40 mm diameter and 300 mm length. To understand the plasma state inside the tubes to determine appropriate DLC film deposition conditions, wavelength- and time-resolved optical emission spectroscopy of the plasma generated inside the tubes and numerical simulation were performed. Results of these investigations and characterization clarified that one nanopulse power source introduced to tubes generates glow and after-glow discharges at μs time intervals. It was further clarified that these discharges in combination with high-repetition pulses, suggested together contribute to the effective ionization of gas. Thus, the high speed and high source gas yield of DLC film deposition inside the tubes were confirmed.

Study by Optical Spectroscopy of Bismuth Emission in a Nanosecond-Pulsed Discharge Created in Liquid Nitrogen.

Time-resolved optical emission spectroscopy of nanosecond-pulsed discharges ignited in liquid nitrogen between two bismuth electrodes is used to determine the main discharge parameters (electron temperature, electron density and optical thickness). Nineteen lines belonging to the Bi I system and seven to the Bi II system could be recorded by directly plunging the optical fibre into the liquid in close vicinity to the discharge. The lack of data for the Stark parameters to evaluate the broadening of the Bi I lines was solved by taking advantage of the time-resolved information supported by each line to determine them. The electron density was found to decrease exponentially from 6.5 ± 1.5 × 1016 cm−3 200 ns after ignition to 1.0 ± 0.5 × 1016 cm−3 after 1050 ns. The electron temperature was found to be 0.35 eV, close to the value given by Saha’s equation.

Plasma plume evolution of a capillary discharge based pulsed plasma thruster: An optical diagnosis study

This paper studied the plasma plume evolution process of a capillary discharge based pulsed plasma thruster. Time-resolved imaging and optical emission spectroscopy were applied to investigate the plume morphology and plasma species characteristics. It showed that ionized particles (mainly C II and F II) were accelerated early in the pulse and neutral particles (mainly C I and F I) later. An optical time-of-flight (OTOF) method was developed using a photodiode array combined with narrow bandpass filters. The equivalent streaming velocity of the plasma plume was evaluated with the OTOF technique. Measurements of individual species showed that both the ionized and the neutral species could be effectively accelerated by gasdynamic forces, and the ionized particles could reach a higher velocity. A Doppler shift measurement of the plasma plume was also performed to compare it with the findings from the OTOF method. The plasma plume streaming velocity of a thruster with a discharge energy of 5 J was measured and found to be (25.34 ± 0.17) km/s (OTOF) and (22.36 ± 4.02) km/s (Doppler shift). In addition, differences between the operation processes of the capillary discharge based pulsed plasma thruster and the electromagnetic pulsed plasma thruster were analyzed.

Time-resolved optical emission spectroscopy in CO2 nanosecond pulsed discharges

Nanosecond repetitively pulsed discharges at atmospheric pressure have shown comparatively high performances for CO2 reduction to CO and O2. However, mechanisms of CO2 dissociation in these transient discharges are still a matter of discussion. In the present work, we have used time-resolved optical emission spectroscopy to investigate the CO2 discharge progression from the initial breakdown event to the final post-discharge. We discover a complex temporal structure of the spectrally resolved light, which gives some insights into the underlying electron and chemical kinetics. We could estimate the electron density using the Stark broadening of O and C lines and the electron temperature with C+ and C++ lines. By adding a small amount of nitrogen, we could also monitor the time evolution of the gas temperature using the second positive system bands of N2. We conclude that the discharge evolves from a breakdown to a spark phase, the latter being characterised by a peak electron density around 1018 cm−3 and a mean electron temperature around 2 eV. The spark phase offers beneficial conditions for vibrationally enhanced dissociation, which might explain the high CO2 conversion observed in these plasma discharges.

Spatial characteristics of nanosecond pulsed micro-discharges in atmospheric pressure He/H2O mixture by optical emission spectroscopy

Atmospheric pressure micro-discharges in helium gas with a mixture of 0.5% water vapor between two pin electrodes are generated with nanosecond overvoltage pulses. The temporal and spatial characteristics of the discharges are investigated by means of time-resolved imaging and optical emission spectroscopy with respect to the discharge morphology, gas temperature, electron density, and excited species. The evolution of micro-discharges is captured by intensified CCD camera and electrical properties. The gas temperature is diagnosed by a two-temperature fit to the ro-vibrational OH(A2Σ+–X2Π, 0–0) emission band and is found to remain low at 425 K during the discharge pulses. The profile of electron density performed by the Stark broadening of H α 656.1-nm and He I 667.8-nm lines is uniform across the discharge gap at the initial of discharge and reaches as high as 1023 m−3. The excited species of He, OH, and H show different spatio-temporal behaviors from each other by the measurement of their emission intensities, which are discussed qualitatively in regard of their plasma kinetics.

Time-Resolved Optical Emission Spectroscopy Reveals Nonequilibrium Conditions for CO2 Splitting in Atmospheric Plasma Sustained with Ultrafast Microwave Pulsation

Among the pool of Power-to-X technologies, plasmas show high potential for the efficient use of intermittent renewable energies. High efficiencies of CO$_{2}$ conversion have been reported while using microwave plasmas at vacuum conditions which are, however, not suitable for CO$_{2}$ mitigation at industrial scales. Here we show that ultrafast pulsation of microwaves allow significant improvements of energy efficiencies during CO$_{2}$ splitting at atmospheric pressure as compared to continuous wave operation of the microwave source. Moreover, by the interrogation of the plasma with time-resolved optical emission spectroscopy we can, for the first time, observe the evolution of the vibrational and rotational temperatures and define a time window where nonequilibrium can be expected at the beginning of the pulse of an atmospheric CO$_{2}$ microwave plasma. In spite of the evidence of nonequilibrium in our system, thermal mechanism appears to dominate the CO$_{2}$ dissociation. It is shown that a fine control of the energy deposition in the plasma is possible with ultrafast pulsation of the microwave energy supply.

From the molten bridge rupture to the local thermal equilibrium arc: optical emission spectroscopy of electric arcs during contacts opening

We investigate by time-resolved optical emission spectroscopy the properties of electric arcs forming at the opening of Cu contacts and with a current of a few kA. The systematic observation of well-resolved transitions demonstrates that the dense Cu vapor that results from the rupture of the molten metal bridge between the contacts expands rapidly. Solving the radiative transfer equation through the line-of-sight to fit the lineshape of the detected spectra, we obtain that both the pressure and the temperature of the Cu-dominated plasma increase during the first 100 µs of arcing. At the same time, the peak wavelength and broadening of Cu I transitions exhibit a non-monotonic time-dependence. In particular, both the blueshift and narrowing of these transitions by Stark effect during the first 40 µs of arcing demonstrate a decrease in electron temperature. This result leads us to the conclusion that it takes at least 40 µs for the arc to be at local thermal equilibrium after the rupture of the molten metal bridge.

Space-and time-resolved optical investigations on ns-laser produced plasmas on various geological samples

Experimental and theoretical investigations were performed on transient plasmas generated by ns-laser ablation on ten mineral samples. Space-and time-resolved optical emission spectroscopy and ICCD fast camera imaging were implemented to understand the kinetics of the ablated particles and how the samples physical properties can be reflected by those of the plasma plume. Strong correlations were found between the global and individual plasma velocity and the melting temperature of the geomaterials. The thermal energy of the plasma expressed through the excitation temperature of the ejected particle is correlated with the same target physical parameter, results corelated with the presence of strong thermal ejection mechanisms. To better understand the global empirical laws, we implemented the fractal model to interpret the results. The model manages to emulate the target-plasma correlations using a multifractal hydrodynamic approach and adequately calibrating the theoretical model on the empirical tools used to describe the laser produced plasmas.