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Combined analysis of optical emission spectroscopy and infrared thermography revealing how liquid properties affect plasma ignition in a dielectric barrier discharge microfluidic system where methane-containing gas interacts with organic liquids. 

Reforming of methane (CH4) is a process to produce syngas (CO/H2) and other value-added chemicals including oxygenates such as methanol (CH3OH). Atmospheric pressure plasmas have the potential to be more energy efficient than traditional reforming methods as value-added chemicals can be synthesized directly in the plasma without requiring an additional step. In this paper, we discuss the results from a computational investigation of the formation of oxygenates by CH4 oxidation in the presence of Ar, including CH3OH and CH2O, in a nanosecond pulsed dielectric barrier discharge. The plasma is formed in a microfluidic channel whose small dimensions are ideal for plasma formation at atmospheric pressure. The production and consumption mechanisms of dominant radicals and long-lived species are discussed in detail for the base case conditions of Ar/CH4/O2 = 50/25/25. CH3OH is produced primarily by CH3O reacting with CH3O and CH3O2 reacting with OH, while CH2O formation relies on reactions involving CH3O and CH3. The most abundant oxygenate formed is CO (produced by H abstraction from CHO). However, the greenhouse gas CO2 is also formed as a by-product. The effects of gas mixture are examined to maximize the CH3OH and CH2O densities while decreasing the CO2 density. Increasing the Ar percentage from 0% to 95% decreased the CH3OH and CH2O densities. At low Ar percentages, this is due to an increase in consumption of CH3OH and CH2O, while at high Ar percentages (>40% Ar), the production of CH3OH and CH2O is decreased. However, both CO and CO2 reached peak densities at 70%–90% Ar. Changing the CH4/O2 ratio while keeping 50% Ar in the discharge led to increased CH3OH and CH2O production, reaching peak densities at 35%–40% CH4. The CO and CO2 densities decreased beyond 20% CH4, indicating that a CH4 rich discharge is ideal for forming the desired oxygenates. 

PFAS degradation in a plasma is modeled by combining calculations of electron impact excitation cross sections and molecular decomposition pathways in a 0-dimensional plasma chemistry model. 

The conversion of methane, CH4, into higher value chemicals using low temperature plasmas is challenged by both improving efficiency and selectivity. One path towards selectivity is capturing plasma produced methyl radicals, CH3, in a solvent for aqueous processing. Due to the rapid reactions of methyl radicals in the gas phase, the transport distance from production of the CH3 to its solvation should be short, which then motivates the use of microplasmas. The generation of CH3 in Ar/CH4/H2O plasmas produced in nanosecond pulsed dielectric barrier discharge microplasmas is discussed using results from a computational investigation. The microplasma is sustained in the channel of a microfluidic chip in which the solvent flows along one wall or in droplets. CH3 is primarily produced by electron-impact of and dissociative excitation transfer to CH4, as well as CH2 reacting with CH4. CH3 is rapidly consumed to form C2H6 which, in spite of being subject to these same dissociative processes, accumulates over time, as do other stable products including C3H8 and CH¬3OH. The gas mixture and electrical properties were varied to assess their effects on CH3 production. CH3 production is largest with 5% CH4 in the Ar/CH4/H2O mixture due to an optimal balance of electron-impact dissociation, which increases with CH4 percentage, and dissociative excitation transfer and CH2 reacting with CH4, which decrease with CH4 percentage. Design parameters of the microchannels were also investigated. Increasing the permittivity of the dielectrics in contact with the plasma increased the ionization wave intensity which increased CH3 production. Increased energy deposition per pulse generally increased CH3 production as does lengthening pulse length up to a certain point. The arrangement of the solvent flow in the microchannel can also affect the CH3 density and fluence to the solvent. The fluence of CH3 to the liquid solvent is increased if the liquid is immersed in the plasma as a droplet or is a layer on the wall where the ionization wave terminates. The solvation dynamics of CH3 with varying numbers of droplets was also examined. The maximum density of solvated methyl radicals CH3aq occurs with a large number of droplets in the plasma. However, the solvated CH3aq density can rapidly decrease due to desolvation, emphasizing the need to quickly react the solvated species in the solvent. 

Abstract The electric field distribution in the ionization waves propagating over a microchannel array dielectric surface, with the channels either empty or filled with distilled water, is measured by ps Electric Field Induced Second Harmonic (EFISH) generation. The surface ionization wave is initiated by the atmospheric pressure N2-Ar plasma jet impinging on the surface vertically and powered by ns pulse discharge bursts. The results show that the electric field inside the microchannels, specifically its horizontal component, is enhanced by up to a factor of 2. The field enhancement region is localized within the channels. The vertical electric field inside the channels lags in time compared to the field measured at the ridges, indicating the transient reversal of the ionization wave propagation direction across the channels (toward the jet). This is consistent with the phase-locked plasma emission images and confirmed by the kinetic modeling predictions, which show that the ionization wave “jumps” over the empty channels and propagates into the channels only after the jump between the adjacent ridges. When the channels are filled with water, the wave speed increases by up to 50%, due to the higher effective dielectric constant of the surface. No evidence of a significant electric field enhancement near the dielectric surface (ceramic or water) has been detected, within the spatial resolution of the present diagnostic, ~100 μm. 

Low-temperature plasmas (LTPs) are essential to manufacturing devices in the semiconductor industry, from creating extreme ultraviolet photons used in the most advanced lithography to thin film etching, deposition, and surface modifications. It is estimated that 40%–45% of all process steps needed to manufacture semiconductor devices use LTPs in one form or another. LTPs have been an enabling technology in the multidecade progression of the shrinking of device dimensions, often referred to as Moore’s law. New challenges in circuit and device design, novel materials, and increasing demands to achieve environmentally benign processing technologies require advances in plasma technology beyond the current state-of-the-art. The Department of Energy Office of Science Fusion Energy Sciences held a workshop titled Plasma Science for Microelectronics Nanofabrication in August 2022 to discuss the plasma science challenges and technical barriers that need to be overcome to continue to develop the innovative plasma technologies required to support and advance the semiconductor industry. One of the key outcomes of the workshop was identifying a set of priority research opportunities (PROs) to focus attention on the most strategic plasma science challenges to address to benefit the semiconductor industry. For each PRO, scientific challenges and recommended strategies to address those challenges were identified. This article summarizes the PROs identified by the workshop participants. 

Abstract Atmospheric pressure plasma jets (APPJs) are increasingly being used to functionalize polymers and dielectric materials for biomedical and biotechnology applications. Once such application is microfluidic labs-on-a-chip consisting of dielectric slabs with microchannel grooves hundreds of microns in width and depth. The periodic channels, an example of a complex surface, present challenges in terms of directly and uniformly exposing the surface to the plasma. In this paper, we discuss results from computational and experimental investigations of negative APPJs sustained in Ar/N₂mixtures flowing into ambient air and incident onto a series of microchannels. Results from two-dimensional plasma hydrodynamics modeling are compared to experimental measurements of electric field and fast-camera imaging. The propagation of the plasma across dry microchannels largely consists of a sequence of surface ionization waves (SIWs) on the top ridges of the channels and bulk ionization waves (IWs) crossing over the channels. The IWs are directed into electric field enhanced vertices of the next ridge. The charging of these ridges produce reverse IWs responsible for the majority of the ionization. The propagation of the plasma across water filled microchannels evolve into hopping SIWs between the leading edges of the water channels, regions of electric enhancement due to polarization of the water. Positive, reverse IWs follow the pre-ionized path of the initial negative waves. 

Abstract Sterilization of skin prior to surgery is challenged by the reservoir of bacteria that resides in hair follicles. Atmospheric pressure plasma jets (APPJs) have been proposed as a method to treat and deactivate these bacteria as atmospheric plasmas are able to penetrate into structures and crevices with dimensions similar to those found in hair follicles. In this paper, we discuss results from a computational investigation of an APPJ sustained in helium flowing into ambient air, and incident onto a layered dielectric similar to human skin in which there are idealized hair follicles. We found that, depending on the location of the follicle, the bulk ionization wave (IW) incident onto the skin, or the surface IW on the skin, are able to launch IWs into the follicle. The uniformity of treatment of the follicle depends on the location of thefirst entryof the plasma into the follicle on the top of the skin. Typically, only one side of the follicle is treated on for a given plasma pulse, with uniform treatment resulting from rastering the plasma jet across the follicle over many pulses. Plasma treatment of the follicle is sensitive to the angle of the follicle with respect to the skin, width of the follicle pocket, conductivity of the dermis and thickness of the underlying subcutaneous fat layer, the latter due to the change in capacitance of the tissue. 

Abstract Ozone, O₃, is a strong oxidizing agent often used for water purification. O₃is typically produced in dielectric barrier discharges (DBDs) by electron-impact dissociation of O₂, followed by three-body association reactions between O and O₂. Previous studies on O₃formation in low-temperature plasma DBDs have shown that O₃concentrations can drop to nearly zero after continued operation, termed the ozone-zero phenomenon (OZP). Including small (<4%) admixtures of N₂can suppress this phenomenon and increase the O₃production relative to using pure O₂in spite of power deposition being diverted from O₂to N₂and the production of nitrogen oxides, N_xO_y. The OZP is hypothesized to occur because O₃is destroyed on the surfaces in contact with the plasma. Including N₂in the gas mixture enables N atoms to occupy surface sites that would otherwise participate in O₃destruction. The effect of N₂in ozone-producing DBDs was computationally investigated using a global plasma chemistry model. A general surface reaction mechanism is proposed to explain the increase in O₃production with N₂admixtures. The mechanism includes O₃formation and destruction on the surfaces, adsorption and recombination of O and N, desorption of O₂and N₂, and NO_xreactions. Without these reactions on the surface, the density of O₃monotonically decreases with increasing N₂admixture due to power absorption by N₂leading to the formation of nitrogen oxides. With N-based surface chemistry, the concentrations of O₃are maximum with a few tenths of percent of N₂depending on the O₃destruction probability on the surface. The consequences of the surface chemistry on ozone production are less than the effect of gas temperature without surface processes. An increase in the O₃density with N-based surface chemistry occurs when the surface destruction probability of O₃or the surface roughness was decreased. 

Electronegative inductively coupled plasmas (ICPs) are used for conductor etching in the microelectronics industry for semiconductor fabrication. Pulsing of the antenna power and bias voltages provides additional control for optimizing plasma–surface interactions. However, pulsed ICPs are susceptible to capacitive-to-inductive mode transitions at the onset of the power pulse due to there being low electron densities at the end of the prior afterglow. The capacitive (E) to inductive (H) mode transition is sensitive to the spatial configuration of the plasma at the end of the prior afterglow, circuit (matchbox) settings, operating conditions, and reactor configurations, including antenna geometry. In this paper, we discuss results from a computational investigation of E–H transitions in pulsed ICPs sustained in Ar/Cl2 and Ar/O2 gas mixtures while varying operating conditions, including gas mixture, pulse repetition frequency, duty cycle of the power pulse, and antenna geometry. Pulsed ICPs sustained in Ar/Cl2 mixtures are prone to significant E–H transitions due to thermal dissociative attachment reactions with Cl2 during the afterglow which reduce pre-pulse electron densities. These abrupt E–H transitions launch electrostatic waves from the formation of a sheath at the boundaries of the plasma and under the antenna in particular. The smoother E–H transitions observed for Ar/O2 mixture results from the higher electron density at the start of the power pulse due to the lack of thermal electron attaching reactions to O2. Ion energy and angular distributions (IEADs) incident onto the wafer and the dielectric window under the antenna are discussed. The shape of the antenna influences the severity of the E–H transition and the IEADs, with antennas having larger surface areas facing the plasma producing larger capacitive coupling. Validation of the model is performed by comparison of computed electron densities with experimental measurements.