Optical Emission Spectra Research Articles

Optical Diagnostics of Discharges in and in Contact With Liquids

ABSTRACTDischarges in liquids have been the subject of intensive investigations for a broad range of applications and involve highly coupled and complex phenomena with timescales ranging from picoseconds to seconds and length scales from micrometers to centimeters. This review focuses on some of the challenges in optical diagnostics of discharges in and in contact with liquids; this includes the interpretation of optical emission spectra, the inherently stochastic nature of many discharge phenomena including the initial stages of plasma ignition, and the large gradients in species and plasma properties interfacing with a dynamic liquid interface. We report recent notable advances, controversies in interpretations of diagnostics, and remaining opportunities.

Theoretical analysis of argon 2p states' density ratios for nanosecond plasma optical emission spectroscopy

A theoretical analysis of excited argon state densities responsible for optical emission spectra of atmospheric pressure argon plasma is presented for its use in plasma diagnostics. Nanosecond pulsed barrier discharges are simulated using spatially one- and two-dimensional fluid-Poisson models using the reaction kinetics model presented by Stankov et al. [1], which considers all ten argon 2p states (Paschen notation) separately. The very first (single) discharge and repetitive discharges with frequencies from 5 kHz to 100 kHz are considered. A semi-automated procedure is utilized to find appropriate 2p states for electric field determination using an intensity ratio method, which is based on a time-dependent collisional-radiative model. The fluid simulations in combination with the semi-automated procedure are used to quantify the sensitivity of selected 2p-state ratios to given preionization of the gas. A highly sensitive time-correlated single photon counting experiment shows clearly that the selected ratio is sensitive to the electric field variation in the streamer head, yet additional calibration is needed for absolute values determination. Different approaches for effective lifetime determination are tested and applied also to measured data. The influence of radial and axial 2p state density integration on the intensity ratio method is discussed. The above mentioned models and procedures result in a flexible theory-based methodology applicable for development of new diagnostic techniques.

Fabrication and Characterization of Micro-Arc Oxidation Films on β-Titanium Alloy in Silicate and Silicate/Glycerin Electrolyte

Micro-arc oxidation (MAO) films were fabricated on the Ti-39Nb-6Zr alloy at different voltages in the silicate and silicate/glycerin electrolyte. Their morphology, phase structure and composition were characterized by scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). It was found that the glycerin additive in the silicate electrolyte improved the compactness of the MAO film. The corrosion resistance was evaluated, and the influence of glycerin additive in electrolyte on the growth of micro-arc oxidized film was revealed by optical emission spectra.

Effects of Tube Diameter and Gas Flow Rate on the Discharge Dynamics Characteristics and Reactive Species of Nanosecond Pulsed Discharge Plasma in Contact With Water

ABSTRACTThe use of millimeter quartz tubes to generate non‐thermal plasma in contact with liquid is widely applied in medicine, such as the effective disinfection of catheter tubes and tooth cavities. Here, the effects of tube diameter and gas flow rate on discharge dynamics and reactive species characteristics of nanosecond pulse needle‐water discharge are studied using an ICCD camera and optical emission spectra. The discharge diffusion is increased significantly by an appropriate combination of tube diameter and gas flow rate. Besides, the discharge intensity, emission spectra intensities of reactive species, gas temperature, and electron density increase with the increase of quartz tube diameter and gas flow rate, which contributes to enhance the production of OH and H2O2 species in aqueous samples.

Growth of homoepitaxial single crystal diamond by microwave plasma CVD in H2-CH4-O2 gas mixtures at high microwave power densities

Single crystal diamond growth by microwave plasma assisted CVD in oxygen-containing gas mixtures is attractive in view of possibility to realize a prolonged non-stoped synthesis process and to minimize defects and impurities in the produced material. We studied the homoepitaxial diamond growth on (100) oriented substrates in H2-CH4-O2 environment at high pressures (300 Torr) and high microwave power density (≈400 W/cm3) at variable O2 content (up to 3.5 %) in the plasma. A low-coherence optical interferometry and optical emission (OE) spectroscopy was used to measure in situ the growth rate and probe the plasma chemistry, respectively. Depending on CH4 content the growth rate dependence on the concentration [O2] either shows a maximum at certain [O2], or a monotonic decline, up to complete stop of the growth at some critical O2 percentage (specific for each methane content) in the mixture. We found CH, Hβ, C2 and C3 lines in OE spectra from the plasma to monotonically quenched with O2 adding, particularly, disappearance of the C2 line coincidences with growth rate going to zero. High-quality homoepitaxial diamond layers were produced at moderate growth rate at optimal gas composition and characterized with Raman spectroscopy. Moreover, a significant reduction in the stress on (111) oriented substrates owing to O2 addition was observed.

Effects of discharge parameters on plasma acceleration and transmission characteristics of a coaxial gun operated in gas-prefilled mode

The effects of discharge parameters on the discharge process and plasma transport characteristics of a coaxial gun in the gas-prefilled mode are studied. The plasma optical intensity and ejection velocity are measured by photodiodes, the optical emission spectrum is taken by a spectroscopic system, and the plasma evolution in the transport process is captured by a high-speed camera. The plasma acceleration characteristics under different discharge parameters show that the velocity and electron density of the ejection plasma are mainly determined by the pre-filled pressure and discharge current, which is consistent with the snowplow model. The kinetic energy of ejection plasma can be significantly increased by reducing the outer loop inductance, which is conducive to increasing the energy utilization efficiency. The time-varying images of plasma radiation and the plasma density at different transport locations illuminate the transmission characteristics of coaxial gun discharge plasma. The results show that the snowplow effect continues to play a role in the plasma transport process, and the plasma accumulation is induced by the combination of shock wave compression. The current-driven magneto hydrodynamics instability occurs during the transport process, and the luminous signal of the plasma current sheet oscillates periodically. In addition, the plasma impact effect is obvious and the gas retarding effect is enhanced with the increase in the gas pressure. These results give us a more comprehensive view of the coaxial gun discharge process and plasma transport and provide a certain reference for optimizing the parameters selection and physical design of coaxial gun discharge plasma characteristics.

Influence of bias voltage and oxygen addition on the discharge aspects of a diffuse argon plume in an atmospheric pressure plasma jet

A remote plasma, also referred to as a plasma plume (diffuse or filamentary), is normally formed downstream of an atmospheric pressure plasma jet. In this study, a diffuse plume is formed by increasing the bias voltage (U b) applied to the downstream electrode of an argon plasma jet excited by a negatively pulsed voltage. The results indicate that the plume is filamentary when U b is low, which transits to the diffuse plume with increasing U b. The discharge initiated at the rising edge of the pulsed voltage is attributed to the diffuse plume, while that at the falling edge contributes to the filament in the plume. For the diffuse plume, the discharge intensity decreases with the increasing oxygen content (C o). Fast photography reveals that the diffuse plume results from a negative streamer, which has a dark region near the nozzle with C o = 0%. However, the dark region is absent with C o = 0.5%. From the optical emission spectrum, the electron density, electron excitation temperature, gas temperature, and oxygen atom concentration are investigated.

Insight into the synergistic effect between plasma and oxygen vacancy in direct oxidation of CH4 to CH3OH by molecular O2 at mild condition

The direct conversion of methane into the value-added chemical methanol using molecular oxygen was investigated via plasma catalysis under mild condition. An efficient synergistic effect between plasma and catalyst was achieved using an oxygen vacancy-rich ZnO/Al2O3 catalyst. A high methanol selectivity of 48.5 % and a high synergy factor of 2.1 could be achieved simultaneously over ZnO/Al2O3 R300 catalyst. The presence of oxygen vacancies played a crucial role in methanol formation. A close relationship between oxygen vacancy content and methanol selectivity was established. In situ DRIFT and optical emission spectra were employed to identify key intermediates, and a plausible reaction mechanism was proposed. The CH3 and CH3O species were the key intermediates on the catalyst surface. The oxygen vacancy could efficiently adsorb the O radicals and accelerate the formation of CH3O species. This work offers insights into the rational engineering of efficient catalyst for plasma catalysis process.

Enhancement of OH spectra in atmospheric pressure plasma jet by femtosecond laser

A helium (He) atmospheric pressure plasma jet (APPJ) system with a single electrode was configured. A pulsed light of femtosecond (fs) laser was irradiated at the guided streamer of He APPJ through an objective lens to generate the laser induced plasma (LIP) inside the He APPJ. The optical emission spectra of LIP were measured as the light energy of the fs laser increased. The spectra of hydroxyl molecules and atomic oxygen were enhanced when the fs laser energy exceeded 114 μJ. The plasma parameters of LIP inside the APPJ were determined using He collisional-radiative model. Electron temperature and density increased to ∼7.2 eV and 1.7×1014 cm−3, respectively. The dominant processes underlying the enhancement were discussed in the interaction of fs laser and He APPJ.

Degradation of ciprofloxacin hydrochloride in a multiphase mixed system by subaquatic gas-liquid discharge plasma

In recent years, antibiotic pollution has become a serious threat to human health. In this study, a gas-liquid discharge plasma is developed to degrade ciprofloxacin hydrochloride in a multiphase mixed system containing inorganic and organic impurities. The discharge characteristics are analyzed by diagnosing the applied voltage and discharge current waveforms, as well as the optical emission spectra. The work investigates how degradation efficiency is affected by applied voltage, gas flow rate, treatment time, initial concentration as well as the addition of γ-Al2O3 pellets and peanut straw. After 70 min, the degradation efficiency of ciprofloxacin hydrochloride in the multiphase mixed system reached 99.6%. Its removal efficiency increases as the initial concentration decreases and the applied voltage increases. Besides, there is still a good degradation efficiency of ciprofloxacin hydrochloride with the addition of peanut straw. The degradation mechanism of ciprofloxacin hydrochloride is investigated through the analysis of degraded intermediates and reactive species.

Ozone production in nanosecond pulsed dielectric barrier discharge in synthetic air: The effect of pulse width

This work investigates the effect of pulse width on the characteristics of electrical discharge, optical emission spectra and ozone production in a water electrode DBD using a modulable nanosecond pulsed power supply. Results show that the increase of pulse width tpw slightly increases the spectral intensity and the rotational temperature Trot, with a typical Trot of 299 ± 5 K at an applied peak voltage Vp of 18.6 kV and a tpw of 400 ns. The electronic excitation temperature Texc increases linearly with Vp and gradually with tpw, while the electron density ne shows a non-linear relationship with tpw. Results also show that an increase in tpw slightly increases the energy density. At low energy densities (SIE <50 J/L), increasing tpw can improve ozone generation efficiency, reaching a maximum of 99.64 ± 0.87 g/kWh at 33.60 ± 1.53 J/L at a tpw of 900 ns. This investigation provides substantial insight into the nanosecond pulsed ozone production.

Optical emission spectroscopy as a method for evaluating the change in Si etching structures profile in ICP SF6/C4F8 plasma: Microstructures

In this work, a method for in situ diagnostics of the etching profile of silicon structures (etching window sizes 15–400 μm) using optical emission spectroscopy was proposed. To determine the relationship between the etching profile and plasma parameters, the influence of technological parameters on the etching characteristics (vertical and lateral etching rate, selectivity in relation to photoresist, and sidewall angle) was studied. As a general parameter, which reflects the changes in plasma characteristics depending on the selected technological parameters, the parameter X (C/F ratio in SF6/C4F8 plasma) was introduced. Based on the results obtained, a general pattern between the lateral etching rate, sidewall angle, and optical emission spectra was identified. Thus, ranges of X values, at which the lateral etching rate does not exceed 5 nm/min for 15–30 μm structures and 15 nm/min for 100 μm structures, were estimated: 0.38 ≤ X ≤ 0.77 and 0.28 ≤ X ≤ 0.46, respectively. For 250–400 μm structures, ranges of X values, at which the sidewall angle is acute, straight, and obtuse, were determined: 0.16 ≤ X &amp;lt; 0.29, 0.29 ≤ X ≤ 0.41, 0.41 &amp;lt; X ≤ 0.75, respectively.

Plasma surface treatment of amorphous Ga2O3 thin films for solar-blind ultraviolet photodetectors

Recently, amorphous gallium oxide (a-Ga2O3) thin films are gaining more and more attention due to their advantages of low cost and low temperature growth. However, a-Ga2O3 solar-blind ultraviolet photodetectors are plagued by issues such as slow response speed and high dark current. In this work, radio frequency magnetron sputtering was used for a-Ga2O3 deposition, and a novel approach of plasma treatment (including oxygen, argon and hydrogen plasmas) was employed to tailor the device performance using a plasma-enhanced chemical vapor deposition system. It is demonstrated that: (i) the oxygen atoms and ions in the oxygen plasma effectively reduce the oxygen vacancy concentration and improve the respond speed of a-Ga2O3 photodetectors; (ii) the argon ions in the argon plasma create additional defects (such as dangling bonds and oxygen vacancies) and improve the responsivity of a-Ga2O3 photodetectors; (iii) the hydrogen atoms in the hydrogen plasma may incorporate into the film and form an ultra-thin passivation layer near the surface, which gives rise to a balance between responsivity and response speed. Finally, through the detailed analysis of the optical emission spectra and photoelectric performance, the underlying physical mechanism based on the energy band diagram has been proposed to interpret the obtained experimental results.

ESPRESSO reveals blueshifted neutral iron emission lines on the dayside of WASP-76 b

Context. Ultra hot Jupiters (gas giants with Teq &gt; 2000 K) are intriguing exoplanets due to the extreme physics and chemistry present in their atmospheres. Their torrid daysides can be characterised using ground-based high-resolution emission spectroscopy. Aims. We search for signatures of neutral and singly ionised iron (Fe I and Fe II, respectively) in the dayside of the ultra hot Jupiter WASP-76 b, as these species were detected via transmission spectroscopy in this exoplanet. Furthermore, we aim to confirm the existence of a thermal inversion layer, which has been reported in previous studies, and attempt to constrain its properties. Methods. We observed WASP-76 b on four epochs with ESPRESSO at the VLT, at orbital phases shortly before and after the secondary transit, when the dayside is in view. We present the first analysis of high-resolution optical emission spectra for this exoplanet. We compare the data to synthetic templates created with petitRADTRANS, using cross-correlation function techniques. Results. We detect a blueshifted (−4.7 ± 0.3 km s−1) Fe I emission signature on the dayside of WASP-76 b at 6.0σ. The signal is detected independently both before and after the eclipse, and it is blueshifted in both cases. The presence of iron emission features confirms the existence of a thermal inversion layer. Fe II was not detected, possibly because this species is located in the upper layers of the atmosphere, which are more optically thin. Thus the Fe II signature on the dayside of WASP-76 b is too weak to be detected with emission spectroscopy. Conclusions. We propose that the blueshifted Fe I signature is created by material rising from the hot spot to the upper layers of the atmosphere, and discuss possible scenarios related to the position of the hotspot. This work unveils some of the dynamic processes ongoing on the dayside of the ultra hot Jupiter WASP-76 b through the analysis of the Fe I signature from its atmosphere, and complements previous knowledge obtained from transmission studies. It also highlights the ability of ESPRESSO to probe the dayside of this class of exoplanets.

Studies of dynamic spatio-temporal processes of electrons in a 50 kHz/5 MHz dual-frequency dielectric barrier discharge plasma at atmospheric pressure

Dual-frequency excitation of dielectric barrier discharge (DBD) plasma reactors, where the plasma is generated by a low-frequency (LF) source and modulated by a radio-frequency (RF) source, have been widely adopted in the low-pressure regime. However, the impacts of the RF voltage and LF voltage amplitudes on the plasma parameters, including the spatiotemporal distributions of ion and electron densities, electron dynamics, and gas temperatures, remain poorly understood in the atmospheric pressure regime. The present work addresses this issue by conducting joint experimental and simulation studies for an atmospheric-pressure 50 kHz/5 MHz dual-frequency driven DBD plasma reactor based on phase-resolved optical emission spectra and a drift–diffusion model. The results demonstrate that the dynamic spatiotemporal behaviors of electrons change dramatically as the voltage of the RF component increases from 50 V to 300 V with the voltage of the LF component fixed at 1 kV. Moreover, the RF component is further demonstrated to modulate other plasma characteristics, such as particle densities, gas temperature, and argon emissions. These results contribute toward the tailoring of the non-equilibrium and nonlinear plasma parameters obtained under atmospheric pressure conditions.

(Invited) Influence of Y6 Aggregation on Energetics and Charge Generation in High Performance OPV Blends

We investigated the origin of the high ratio of open circuit voltage to charge transfer state energy (eVOC/ECT) of OPV polymer blends consisting of the electron donating polymer PM6 and the non-fullerene electron acceptor Y6. PM6-Y6 and related donor-acceptor OPV blends exhibit remarkable optoelectronic properties and record power conversion efficiencies in part because of their unusually high eVOC/ECT ratios, which is believed to be related to the small energetic offset of the HOMO levels of PM6 and Y6. In this study, we varied the amount of Y6 in PM6 blends as a means to control the aggregation of Y6 molecules. We examined the corresponding influence that Y6 aggregation has on the energetic offsets and the charge generation efficiency of the materials by probing the appearance of polaron absorption signals in the mid-infrared using time-resolved infrared spectroscopy. Furthermore, we examined the optical absorption and emission spectra of the PM6-Y6 blends over the range of compositions to correlate the efficiency of charge generation with the signatures of Y6 aggregation in the optical spectra. We observed an abrupt transition around 30 mass% Y6 content at which polarons were efficiently generated by charge separation from PM6 to Y6. Comparison to composition dependent GIWAXS studies of PM6-Y6 blends revealed the formation of Y6 aggregates around the same 30 mass% threshold. These observations demonstrate that aggregation of Y6 molecules is required for charge separation to occur from PM6 to Y6 as measured through the mid-infrared absorption of polarons in the TRIR spectra. Although charges were efficiently generated in blends with only 30 mass% Y6 content, OPV device studies revealed that 50-60 mass% Y6 was needed to reach optimized short-circuit current and OPV device efficiency because these measurements convolve charge generation with charge transport. These findings clarify the optoelectronic properties of the novel class of Y6 acceptors and emphasize the importance of molecular aggregation for tuning the energetics of high performance systems that minimize energy offsets for maximum OPV power conversion efficiencies.

Effect of dielectric material on the uniformity of nanosecond pulsed dielectric barrier discharge

Dielectric barrier discharge (DBD) is considered as a promising technique to produce large volume uniform plasma at atmospheric pressure, and the dielectric barrier layer between the electrodes plays a key role in the DBD processes and enhancing discharge uniformity. In this work, the uniformity and discharge characteristics of the nanosecond (ns) pulsed DBD with dielectric barrier layers made of alumina, quartz glass, polycarbonate (PC), and polypropylene (PP) are investigated via discharge image observation, voltage-current waveform measurement and optical emission spectral diagnosis. Through analyzing discharge image by gray value standard deviation method, the discharge uniformity is quantitatively calculated. The effects of the space electric field intensity, the electron density (N e), and the space reactive species on the uniformity are studied with quantifying the gap voltage U g and the discharge current I g, analyzing the recorded optical emission spectra, and simulating the temporal distribution of N e with a one-dimensional fluid model. It is found that as the relative permittivity of the dielectric materials increases, the space electric field intensity is enhanced, which results in a higher N e and electron temperature (T e). Therefore, an appropriate value of space electric field intensity can promote electron avalanches, resulting in uniform and stable plasma by the merging of electron avalanches. However, an excessive value of space electric field intensity leads to the aggregation of space charges and the distortion of the space electric field, which reduce the discharge uniformity. The surface roughness and the surface charge decay are measured to explain the influences of the surface properties and the second electron emission on the discharge uniformity. The results in this work give a comprehensive understanding of the effect of the dielectric materials on the DBD uniformity, and contribute to the selection of dielectric materials for DBD reactor and the realization of atmospheric pressure uniform, stable, and reactive plasma sources.

Machine learning-based prediction of the electron energy distribution function and electron density of argon plasma from the optical emission spectra

Machine learning-based prediction of the electron energy distribution function and electron density of argon plasma from the optical emission spectra

Formation mechanism of bright and dark concentric-ring pattern in dielectric barrier discharge

In this work, a bright and dark concentric-ring pattern is reported in a dielectric barrier discharge for the first time. The spatiotemporal dynamics of the bright and dark concentric-ring pattern are investigated with an intensified charge-coupled device and photomultiplier tubes. The results indicate that the bright and dark concentric-ring pattern is composed of three concentric-ring sublattices. These are bright concentric-ring structures, dark concentric-ring structures and wider concentric-ring structures, respectively. The bright concentric-ring structures and dark concentric-ring structures are alternately distributed. The bright concentric-ring structures are located at the centre of the wider concentric-ring structures. The wider concentric-ring structures first form from the outer edge and gradually develop to the centre. The essence of all three concentric-ring structures is the individual discharge filaments. The optical emission spectra of different sublattices are acquired and analysed. It is found that the plasma parameters of the three concentric-ring sublattices are different. Finally, the formation mechanism of the bright and dark concentric-ring pattern is discussed.

Optical emission characterization of an atmospheric pressure dielectric barrier discharge in nitrogen: Evolution of CN emissions during PTFE etching

AbstractThe present work investigates the etching of coated polytetrafluoroethylene (PTFE) films using an atmospheric pressure dielectric barrier discharge operating in nitrogen in a filamentary regime. For different treatment durations, the optical emission spectra were recorded over time. Most of the emissions are attributed to the N2 second positive system. The presence of CN is also observed, and its emissions rise with the exposure time of PTFE. This rise is attributed to the density of CN produced. The X‐ray photoelectron spectroscopy surface characterization suggests two etching regimes. This is linked with a change in slope in the intensity evolution of the optical emissions of the CN. At longer times, a fluorinated deposit on the electrode is observed, confirming a different nature of the etched material.