Plasma Gas Phase Research Articles

Effects of quenching rate on the plasma gas-phase synthesis of graphene: Insight from the experiments and ReaxFF studies

This investigation analysed the effects of quenching rate on the plasma gas-phase synthesis of graphene. The quenching rate was modulated by the flowrate/type of radial gas whish was injected in the plasma downstream. The experimental results showed that the plasma pyrolysis of acetylene produced spherical carbon nanoparticles. The content graphene flakes in the products increased with the quenching effect, and the layer number of graphene decreased accordingly. Further characterisation confirmed that a high quenching rate increased the crystallinity of the product, reduced the amorphous carbon content, and resulted in better oxidation resistance. The graphene formation pathway was carried out by the molecular dynamics simulations (ReaxFF), focusing on the effect of the quenching rate on graphene growth. As the quenching rate increased, the decrease in the time for surface reactions lowered the generation of five- and seven-membered rings, reducing the possibility of edge growth bending. Besides, an increased quenching rate rapidly lowered the growth temperature and thus retarded the C–H bond breakage at the edges of the carbon clusters. The C–H bonds terminated C–C bond formation at the edges of the carbon clusters, preventing edge growth bending of the carbon clusters, and thus contributing to the growth of lamellar structure. These results suggested that increasing the quenching rate is an effective method for regulating the plasma gas-phase synthesis of graphene.

PLASMA PARAMETRS AND SILICON ETCHING KINETICS IN CF4 + C4F8 + O2 MIXTURE: EFFECT OF CF4/C4F8 MIXING RATIO

In this work, we investigated the influence of fluorocarbon component ratio in the CF4 + C4F8 + O2 gas mixture on electro-physical plasma parameters, steady-state densities of active species and silicon etching kinetics under typical reactive-ion process conditions. The combination of plasma diagnostics (double Langmuir probes, optical emission spectroscopy) and plasma modeling confirmed known peculiarities of plasma chemistry of individual fluorocarbons in the presence of oxygen as well as provided an extended analysis of both fluorine and oxygen atom kinetics in the three-component gas mixture. It was shown that the substitution of CF4 by C4F8 at the constant fraction of O2 a) causes the weak disturbance in electrons- and ions-related plasma parameters (electron temperature, electron density, ion energy flux); b) provides drastically increasing density of polymerizing CFx (x = 1, 2) radicals; and c) results in monotonically decreasing F atoms density. The latter is due to simultaneous changes in both F atom formation rate and their loss frequency, especially in C4F8-rich plasmas. From experiments, it was found that Si etching rate is by more than 85% controlled by its chemical component (in a form of ion-stimulated heterogeneous reaction Si + xF → SiFx) and decreases with increasing C4F8 fraction in a feed gas. The change in effective reaction probability contradicts with the growth of polymer deposition rate and film thickness (as it follows from changes in gas-phase plasma characteristics) but may reflect the weakening of surface passivation by oxygen atoms. For citation: Efremov A.M., Bobylev A.V., Kwon K.-H. Plasma parametrs and silicon etching kinetics in CF4 + C4F8 + O2 mixture: effect of CF4/C4F8 mixing ratio. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 6. P. 29-37. DOI: 10.6060/ivkkt.20246706.6982.

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.

Magnetron sputter deposition of boron carbide in Ne and Ar plasmas

Conventional magnetron sputter deposition of B4C uses Ar as the working gas. Here, we explore the magnetron sputter deposition of B4C with a Ne plasma, which is expected to exhibit larger sputtering yields than Ar. We study properties of films deposited with different substrate tilt angles with the magnetron source operated in either direct-current (DC) or radio-frequency (RF) mode in an Ar or Ne plasma. Results show that the B4C film properties are determined by a combination of sputtering ballistics and effects of the working gas on the plasma discharge and gas phase scattering of depositing species flux. At constant discharge power, deposition rates for Ar and Ne plasmas are similar, which is attributed to balancing effects of a higher ballistic sputtering yield of Ne and lower ion flux to the target. Both depositing B and C neutral species and bombarding ions have higher energies for the case of Ne plasmas. Films deposited with the RF-driven Ne plasma exhibit a uniform non-columnar structure, lowest oxygen impurity content, and highest mass density and mechanical properties at a cost of Ne incorporation and larger compressive residual stress.

Disinfection Efficacy of Electrohydraulic Discharge Plasma against Xanthomonas campestris pv campestris: A Sustainable Seed Treatment Approach.

The prevalence of plant diseases caused by pathogens such as Xanthomonas campestris pv campestris (Xcc) poses a significant challenge to sustainable agriculture, necessitating the development of effective and eco-friendly disinfection methods. In this study, we investigated the efficacy of electrohydraulic discharge plasma (EHDP) as a promising alternative for disinfection against Xcc, a pathogen responsible for black rot in cruciferous vegetables. Unlike conventional gas-phase plasma, EHDP introduces two pivotal components: gas-liquid interface plasma (GLIP) and its consequential byproduct, plasma-activated water (PAW). While GLIP enables dual-phase production of reactive oxygen and nitrogen species (RONS), PAW is a reservoir of liquid-phase long-lived RONS, thereby enhancing its bactericidal efficacy. In our evaluations, we tested EHDP-induced GLIP and EHDP-induced PAW against Xcc cells in both in vitro (Xcc suspension) and in vivo (Xcc-inoculated cabbage seeds) settings, achieving noteworthy results. Within 15 min, these methods eliminated ∼98% of the Xcc cells in suspension. For in vivo assessments, nontreated seeds exhibited an infection rate of 98%. In contrast, both EHDP treatments showed a significant reduction, with ∼60% fewer seeds infected while maintaining ∼90% germination rate. In addition, the liquid-phase RONS in EHDP-PAW may enhance seed vigor with a faster germination rate within the initial 5 days. Remarkably, around 90% of EHDP-PAW-treated seeds yielded healthy seedlings, indicating dual benefits in bacterial suppression and seed growth stimulation. In contrast, the percentage of healthy seedlings from nontreated, Xcc-inoculated seeds was approximately 70%. Our research demonstrates the feasibility of using eco-friendly EHDP in the seed disinfection process.

Graphene self-folding: Evolution of free-standing few-layer graphene in plasma synthesis

Substrate and catalyst free gas-phase plasma synthesis of freestanding few-layer graphene (FLG) flakes leads to crumpled FLG structures. In this paper, we elucidate a folding-based mechanism and structure-formation process in accordance with literature on the stability of graphene sheets. Transmission electron microscopy is applied to thermophoretically-sampled FLG at various distances from the plasma zone. Single-layer and few-layer graphene were observed, and a morphology pattern evolution could be discerned. A conceptual model of graphene formation and growth is derived, starting from initial rounded single-layer graphene of a few hundred nanometer in diameter to, eventually, self-folded and strongly crumpled FLG.

Experimental study of graphene synthesis by different gas-doped plasma

Plasma gas phase synthesis of graphene method is one-step synthesis, without catalyst, acid, solvent and substrate materials. In this paper, plasma pyrolysis of C2H4 for the preparation of graphene was carried out to investigate the effect of doping H2, CO2, and N2 on the morphology characteristics and chemical reaction properties of the synthesized products at different reaction temperatures ranging from 1500 to 4500 K. It was found that an increase in temperature leads to flatter morphology, less agglomeration, and a decrease in defect density and oxygen content in graphene. The addition of H2, CO2, and N2 gases affected the morphology and defect density of the products. In addition, the high temperature conditions increase the hydrogen atom concentration and etch the edges of graphene, while CO2 slows down the etching process and decreases the defect density. Doping with high enthalpy N2 favors the improvement of crystallinity and defect density at low temperatures, but increases the defect density at high temperatures. These findings contribute to further understanding of the application and optimization of the method of plasma gas phase synthesis of graphene.

Dual Tunability for Uncatalyzed N-Alkylation of Primary Amines Enabled by Plasma-Microdroplet Fusion.

The fusion of non-thermal plasma with charged microdroplets facilitates catalyst-free N-alkylation for a variety of primary amines, without halide salt biproduct generation. Significant reaction enhancement (up to >200×) is observed over microdroplet reactions generated from electrospray. This enhancement for the plasma-microdroplet system is attributed to the combined effects of energetic collisions and the presence of reactive oxygen species (ROS). The ROS (e.g., O2•-) act as a proton sink to increase abundance of free neutral amines in the charged microdroplet environment. The effect of ROS on N-alkylation is confirmed through three unique experiments: (i) utilization of radical scavenging reagent, (ii) characterization of internal energy distribution, and (iii) controls performed without plasma, which lacked reaction acceleration. Establishing plasma discharge in the wake of charged microdroplets as a green synthetic methodology overcomes two major challenges within conventional gas-phase plasma chemistry, including the lack of selectivity and product scale-up. Both limitations are overcome here, where dual tunability is achieved by controlling reagent concentration and residence time in the microdroplet environment, affording single or double N-alkylated products. Products are readily collected yielding milligram quantities in eight hours. These results showcase a novel synthetic strategy that represents a straightforward and sustainable C-N bond-forming process.

Enhancement of NOx production in water by combining an air bubble plasma jet and an external magnetic field

Production of NOx (NO2− + NO3−) in water with an air bubble discharge plasma jet under the influence of an external axial steady magnetic field was investigated experimentally. The gas phase plasma parameters, rotational (Tr), vibrational (Tv) and electronic excitation (Tx) temperatures, and electron density (ne), as well as the liquid phase pH and the concentrations of nitrite (NO2−) and nitrate (NO3−), were measured as a function of treatment time and magnetic field strength. It was found that Tr, Tv, Tx, and ne slightly increased as a function of magnetic field strength in the gas phase plasma. The pH decreased both with treatment time and magnetic field strength. In the maximum field strength of 290 mT, the concentrations of NO2− and NO3− were ∼82% and ∼74%, respectively, greater than with B=0. With B=290 mT, the energy cost for producing NOx was ∼78% lower than with B=0. The energy cost may likely be reduced due to decreasing radial diffusion loss of charged species in the discharge with increasing magnetic field strength.

A novel approach to expedite wound healing with plasma brush of cold flame.

Excessive or persistent infection is a major contributing factor in impeding chronic wound healing. Wound bed preparations using antiseptics do not necessarily target the entire bacterial spectrum, and the highly proliferating granulation tissue may be sensitive to the cytotoxic effects, impairing tissue repair. Non-thermal gas atmospheric pressure plasmas are partially ionized gases that contain highly reactive particles while the gas phase remains near room temperature, thus having the capability of accessing small irregular cavities and fissures and killing bacteria because of the diffusive nature of gas phase plasma species that are chemically reactive, providing an ideal approach to topical wound disinfection. A non-thermal plasma brush device of novel design has been developed that is suitable for clinical application in the disinfection of oral and wound bacteria. In vivo studies have indicated that the plasma brush treatment rendered no harmful effect on healthy skin or tissues, while it could improve wound healing in Pseudomonas aeruginosa biofilm infected wounds exposed to an optimized treatment with argon plus 1% nitrogen (Ar + N2) plasma.

Silicon etching by chlorine plasma: Validation of surface reactions mechanism

The objective of this paper is the validation of a surface reaction mechanism for silicon etching in low-pressure chlorine plasmas. We employ a quasi-one-dimensional fluid model to model the experimental conditions of Khater and Overzet [Plasma Sources Sci. Technol. 13, 466 (2004)]. This model couples self-consistently the plasma fluid equations with the surface reaction mechanism derived from the available literature. Based on the comparison between the experiments and modeling results, the best set of etch yield parameters is proposed for the conditions typical for industrial plasma processing. The influence of these etch yield parameters on the gas-phase plasma is also discussed.

Mass spectroscopy of oxygen plasmas with energetic ions

An experimental study of the plasma gas phase in low pressure radiofrequency discharges of oxygen is presented. The plasma phase has been studied by means of mass spectroscopy of the neutral and of the charged species, directly sampling the plasma gas phase. We also measured the ion energy distributions. We have studied the influence of the operating conditions on the plasma gas-phase composition. Ion density and energy have been measured as a function of discharge parameters. In particular, we have identified operating conditions in low pressure discharges allowing the extraction of ions from the plasma state with energies exceeding 50 eV. This makes plasma processing with energetic oxygen ions feasible in our device.

Heterogeneous Surface Reaction Analysis of Non-Thermal Plasma-Enhanced Spherical MOx/(Ce0.7Ti0.3)O2 Catalyst Desulfurization: Effects of Plasma and MOx Loading on Surface Oxygen Defects

Homogeneous gas-phase plasma reactions and heterogeneous surface reactions are involved in non-thermal plasma-enhanced catalysis, along with a very complicated strengthening mechanism. In this study, we supported CuO, Co3O4, Fe2O3, or NiO on a hydrothermally synthesized spherical (Ce0.7Ti0.3)O2 catalyst, analyzed its active sites, and examined how plasma affects the catalyst surface and influences heterogeneous surface reactions. Loading CuO onto the catalyst led to increases of 5.85 and 13.51% in the proportions of surface Ce3+ and surface O vacancies, respectively. The CuO-loaded catalyst exhibited a significantly higher redox capacity than the other catalysts at 250–290 °C, which promotes SO2 desorption and surface reactions at low temperatures. Treatment with plasma led to increases in the active-to-lattice-oxygen ratio on the catalyst surface (by 19.12%), the defect-induced D-band to F2g band (ID/IF2g) ratio (by 0.443), and the D-band intensity (by a factor of 3.5). Significantly more defects that adsorb plasma-generated oxygen radicals (O* and O2*) and O3, which subsequently oxidize adsorbed pollutant molecules, are present on the catalyst surface. In general, the special surface properties of the spherical CuO/(Ce0.7Ti0.3)O2 catalyst are applicable to a broad number of non-thermal plasma-enhanced catalytic oxidation scenarios.

Plasma-catalytic ammonia synthesis: Packed catalysts act as plasma modifiers

We studied the plasma-catalytic production of NH3 from H2 and N2 in a dielectric barrier discharge plasma reactor using five different Co-based catalysts supported on Al2O3, namely Co/Al2O3, CoCe/Al2O3, CoLa/Al2O3, CoCeLa/Al2O3 and CoCeMg/Al2O3. The catalysts were characterized via several techniques, including SEM-EDX, and their performance was compared. The best performing catalyst was found to be CoLa/Al2O3, but the differences in NH3 concentration, energy consumption and production rate between the different catalysts were limited under the same conditions (i.e. feed gas, flow rate and ratio, and applied power). At the same time, the plasma properties, such as the plasma power and current profile, varied significantly depending on the catalyst. Taken together, these findings suggest that in the production of NH3 by plasma catalysis, our catalysts act as plasma modifiers, i.e., they change the discharge properties and hence the gas phase plasma chemistry. Importantly, this effect dominates over the direct catalytic effect (as e.g. in thermal catalysis) defined by the chemistry on the catalyst surface.

FEATURES OF PLASMA COMPOSITION AND FLUORINE ATOM KINETICS IN CHF3 + O2 GAS MIXTURE

The effects of initial composition of CHF3 + O2 gas mixture on electro-physical plasma parameters, steady-state densities of active species and fluorine atom kinetics were investigated under the condition of constant gas pressure and input power. The combination of plasma diagnostics by Langmuir probes and model-based analysis of plasma chemistry confirmed known from previous work features of plasma composition in the absence of oxygen (in particular, the domination of HF molecules in a gas phase) as well as demonstrated how the oxygen influences steady-state densities of neutral species through kinetics of both electron-impact and atom-molecular reactions. It was shown that the addition of O2 with a proportional decrease in the content of CHF3 a) results in noticeable changes in electrons- and ions-related plasma parameters (electron temperature, electron density, ion flux); b) provides the effective conversion of fluorocarbon radicals (CHFx, CFx) into such compounds as CFxO, FO and COx; and b) causes an increase in the fluorine atom density up to 50% O2. The last phenomenon contradicts with the change in the total F atom formation rate, but reflects a decrease of their loss frequency in the reaction family of CHFx + F → CFx + HF. The model-based analysis of heterogeneous process kinetics was carried out using the set of tracing parameters based on gas-phase plasma characteristics. It was found that the addition of oxygen lowers the plasma polymerizing ability through both decreasing flux of polymerizing species and accelerating the oxidative destruction of deposited polymer film.

Soft polymerization of hexamethyldisiloxane by coupling pulsed direct‐liquid injections with dielectric barrier discharge

AbstractThis work examines the combination of pulsed direct‐liquid injections with dielectric barrier discharge at atmospheric pressure for the deposition of organosilicon coatings using hexamethyldisiloxane (HMDSO) as the precursor and nitrogen as the carrier gas. In such conditions, deposition relies on the charging of micrometer droplets and their transport toward the substrate by the Coulomb force. The thin‐film morphology and extent of precursor fragmentation are strongly linked to the amount of energy provided by the filamentary discharge to HMDSO droplets. While cross‐linked and smooth coatings were achieved at low energies as in standard gas phase plasma polymers, viscous and droplet‐like structured thin films were deposited at higher energies. The latter material is attributed to the soft polymerization of HMDSO droplets related to plasma–droplet interactions.

Gas-phase parameters and densities of atomic species in Cl2 + O2 + Ar plasma: Effects of O2/Ar and Cl2/Ar mixing ratios

In this work, we investigated the effects of Cl2/Ar (at the constant fraction of O2) and O2/Ar (at the constant fraction of Cl2) mixing ratios in Cl2 + O2 + Ar gas system on plasma parameters, gas-phase chemistry and steady-state densities of atomic species under the condition of inductively coupled RF (13.56 MHz) plasma. The combination of plasma diagnostics by Langmuir probes and optical emission spectroscopy together with 0-dimensional plasma modeling were applied to compare two different gas mixing regimes in respect to a) electrons- and ions-related plasma parameters; b) steady-state densities of plasma active species; and c) formation kinetics for Cl and O atoms. It was found that both gas mixing regimes are characterized by the domination of Cl2+ and Cl + over O2+ and O+ ions as well as by much higher densities of Cl− compared with O−. A decrease in Cl2/Ar ratio at constant fraction of O2 provides the stronger increase in the electron density (due to the deeper fall in plasma electronegativity) as well as influences both Cl and O atom densities. The latter is mostly due to the change in electron-impact kinetics while the role of stepwise processes involving ClO species is almost negligible due to their low density. Oppositely, the feature of the O2/Ar gas mixing regime is the possibility to adjust O atom density under the condition of [Cl] ≈ const. It was found that the model demonstrated the acceptable agreement with experiments in respect to both O and Cl atom densities.

Plasma–Solution Junction for the Formation of Carbon Material

The solution plasma process (SPP) can provide a low-temperature reaction field, leading to an effective synthesis of N-doped graphene with a high N content and well-structured planar structure. However, the interactions at the plasma–solution interface have not been well understood; therefore, it needs to be urgently explored to achieve the modulation of the SPP. Here, to address the knowledge gap, we experimentally determined the physical parameters of the spital distribution in the plasma phase, plasma–gas phase, and gas–liquid phase of the SPP by the Langmuir probe system with modification. Based on the assumption that plasma can act similarly to semiconductors with the Fermi level above the vacuum level, an energy band diagram of the plasma–solution junction could be proposed for the first time. It was observed that the Fermi level of the organic molecule could determine the magnitude of electron temperature in plasma, i.e., benzene produced the highest electron temperature, followed by phenol, toluene, and aniline. Finally, we found that the electron temperature at the interface could induce quenching, leading to the formation of multilayer large-size-domain carbon products. It provided significant evidence for achieving nonequilibrium plasma modulation of carbon nanomaterial synthesis.

Effect of nitrogen doping on the structure and electrochemical properties of vertical graphene sheets prepared by HWP-CVD

3D nitrogen-doped vertically-oriented graphene nanosheets (3D N/VGs) were controllably prepared by helicon wave plasma chemical vapor deposition (HWP-CVD) employing argon, methane, and nitrogen by varying the N2 flow rate (RN2) without any catalyst and substrate heating during the growth. The effect of plasma gas phase species on the growth structure of N/VGs thin films was studied. The influence of nitrogen doping content on the structure and properties of VGs was analyzed. A growth model for the preparation of N/VGs by HWP-CVD was proposed. The results show that the elevated doping content of nitrogen atoms promotes enhanced CH4 dissociation and access to more H atoms, leading to an elevated nanosheet number density and a reduced growth rate. More excited N atoms could be embedded into the C vacancy to replace the missing C atom and restore the hexagonal network and increasing the nitrogen content. N/VGs with lower defect densities obtained with enhanced doping of nitrogen. The effective average distance between defects increases with nitrogen content, and the tunneling phenomenon is apparent, increasing resistance. Electrochemical performance tests showed that VGs with high nitrogen atomic content have higher specific capacitance and rate performance, up to 1340 μF/cm2 and 91.7%, respectively.

Coupling plasma physics and chemistry in the PIC model of electric propulsion: Application to an air-breathing, low-power Hall thruster

This work represents a first attempt to include the complex variety of electron-molecule processes in a full kinetic particle-in-cell/test particle Monte Carlo model for the plasma and neutral gas phase in a Hall thruster. Particular emphasis has been placed on Earth’s atmosphere species for the air-breathing concept. The coupling between the plasma and the gas phase is self-consistently captured by assuming the cold gas approximation and considering gas-wall and gas recycling from the walls due to ion neutralization. The results showed that, with air molecular propellants, all the most relevant thruster performance figures degraded relative to the nominal case using Xe propellant. The main reasons can be ascribed to a reduced ionization cross-section, a larger gas ionization mean free path due to lighter mass air species, and additional electron collisional power losses. While vibrational excitations power losses are negligible, dissociation and electronic excitations compete with the ionization channel. In addition, for molecular oxygen, the large dissociation leads to even faster atoms, further reducing their transit time inside the discharge channel. Future studies are needed to investigate the role of non-equilibrium vibrational kinetics and metastable states for stepwise ionization.