Reduction of Chemical Reactions in Nitrogen and Nitrogen–Hydrogen Plasma Jets Flowing into Atmospheric Air

The large number of possible chemical reactions represents a severe burdenfor modeling of even relatively simple plasma systems. Reduced sets ofchemical reactions have been obtained for numerical simulations of nitrogenand nitrogen-hydrogen plasma jets flowing into an atmospheric airenvironment. The important or active reactions are determined based on asimplified reduction method. A reaction is considered active if it leadsto higher sensitivities than a specified cutoff sensitivity of 1%. Theactive reactions exert a significant influence on main plasma parameters,such as velocity, temperature, and species concentrations. The sensitivityanalysis for the specified systems shows that two NO reactions, known asZel'dovich reactions (N₂+ONO+N andNO+OO₂+N),⁽¹⁾ are both active in a nitrogenplasma jet. On the other hand, the latter is not active and may be omittedin a nitrogen–hydrogen plasma jet. A nitrogen–hydrogen plasmajet requires contribution of two active charge exchange reactions:N₂+N⁺N⁺ ₂+N andN+H+N+ +H, while only the former is needed in a nitrogen plasmajet. The dissociation reactions are all active in both plasma jets, exceptthe dissociation of OH.     

Effect of excitation states of nitrogen on the surface nitridation of iron and steel in d.c. glow discharge plasma

The plasma nitriding phenomena that occur on the surfaces of iron and steel were investigated. In particular, the correlation between the kinds of nitrogen radicals and the surface nitriding reaction was investigated using a glow‐discharge apparatus. To control the excitation of nitrogen radicals, noble gas mixtures were used for the plasma gas. The highly populated metastables of noble gases selectively produce excited nitrogen molecules (N₂*) or nitrogen molecule ions (N₂⁺). The optical emission spectra suggested that the formation of N₂*‐rich or N₂⁺‐rich plasma was successfully controlled by introducing different kinds of noble gases. Auger electron spectroscopy and XPS were used to characterize the depth profile of the elements and chemical species on the nitrided surface. The nitride layer formed by a N₂⁺‐rich plasma had a much higher nitrogen concentration than that by a N₂*‐rich plasma, likely due to the larger chemical activity of the N₂⁺ species as well as the N₂⁺ sputtering bombardment to the cathode surface. The strong reactivity of the N₂⁺ species was also confirmed from the chemical shift of N 1s spectra for iron nitrides. An iron nitride formed by the N₂⁺‐rich plasma has higher stoichiometric quantity of nitrogen than that formed by the N₂*‐rich plasma. Besides the effect of nitrogen radicals on surface nitridation, the contribution of the chromium in steel to the nitriding reaction was also examined. This chromium can promote a nitriding reaction at the surface, which results in an increase in the nitrogen concentration and the formation of nitride with high nitrogen coordination. Copyright © 2010 John Wiley & Sons, Ltd.     

Numerical Investigation of a Parallel-Plate Atmospheric-Pressure Nitrogen/Ammonia Dielectric Barrier Discharge

In this paper, a planar atmospheric-pressure dielectric barrier discharge (AP-DBD) of nitrogen mixed with ammonia (0?C2?%) is simulated using one-dimensional self-consistent fluid modeling with cell-centered finite-volume method. This AP-DBD is driven by a 30?kHz power source with distorted sinusoidal voltages. The simulated discharge current densities are found to be in good agreement with the experiment data in both phase and magnitude. The simulated results show that the discharges of N₂ mixed with NH₃ (0?C2?%) are all typical Townsend-like discharges because the ions always outnumber the electrons very much which leads to no quasi-neutral region in the gap throughout the cycle. N₂ ⁺ and N₄ ⁺ are found to be the most abundant charged species during and after the breakdown process, respectively, like a pure nitrogen DBD. NH₄ ⁺ increases rapidly initially with increasing addition of NH₃ and levels off eventually. In addition, N is the most dominant neutral species, except the background species, N₂ and NH₃, and NH₂ and H are the second dominant species, which increase with increasing added NH₃. The existence of abundant NH₂ plays an important role in those applications which require functional group incorporation.     

The Influence of Small Hydrogen Admixtures up to 5?% to a Low Pressure Nonuniform Microwave Discharge in Nitrogen

We present the results of spectroscopic and 2D modeling study of the influence of hydrogen addition to non-uniform nitrogen plasma of electrode microwave discharge. The axial intensity distributions of the H_?? line and N₂ (2⁺: C³??_u????B³??_g, 1⁺: B³??_g????A³?? _u ⁺ ) and N₂ ⁺ (1^?: B²?? _u ⁺ ???X²?? _g ⁺ ) molecular bands are recorded for different incident microwave power input and hydrogen content. The corona model is used to determine electric field strength in nitrogen discharge from the intensity ratio of 2⁺ and 1^? system of nitrogen bands. By means of 2D modeling spatial distributions of nitrogen molecules in C³??_u state, microwave field strength, electron density, concentrations of N₂ ⁺, N₄ ⁺ are determined in nitrogen and in nitrogen?Chydrogen mixtures. The concentration of N₂H⁺ ions in nitrogen?Chydrogen mixtures is determined also. The general conclusion of 2D modeling is in agreement with experimental results and shows that the influence of hydrogen addition to discharge is related to the fast conversion reactions of nitrogen ions (N₂ ⁺, N₄ ⁺) to N₂H⁺ ion. These ion conversions lead to the change of ion plasma components transport properties, to the modification of microwave field strength in plasma, and consequently, to the alternation of all plasma parameters.     

Nitrogen incorporation in saturated aliphatic C6–C8 hydrocarbons and ethanol in low‐pressure nitrogen plasma generated by a hollow cathode discharge ion source

Ion/molecule reactions of saturated hydrocarbons (n‐hexane, cyclohexane, n‐heptane, n‐octane and isooctane) in 28‐Torr N₂ plasma generated by a hollow cathode discharge ion source were investigated using an Orbitrap mass spectrometer. It was found that the ions with [M+14]⁺ were observed as the major ions (M: sample molecule). The exact mass analysis revealed that the ions are nitrogenated molecules, [M+N]⁺ formed by the reactions of N₃⁺ with M. The reaction, N₃⁺ + M → [M+N]⁺ + N₂, were examined by the density functional theory calculations. It was found that N₃⁺ abstracts the H atom from hydrocarbon molecules leading to the formation of protonated imines in the forms of R′R″C?NH₂⁺ (i.e. C–H bond nitrogenation). This result is in accord with the fact that elimination of NH₃ is the major channel for MS/MS of [M+N]⁺. That is, nitrogen is incorporated in the C–H bonds of saturated hydrocarbons. No nitrogenation was observed for benzene and acetone, which was ascribed to the formation of stable charge‐transfer complexes benzene????N₃⁺ and acetone????N₃⁺ revealed by density functional theory calculations. Copyright © 2016 John Wiley & Sons, Ltd.     

Kinetic study of low-pressure H2 multipole discharge

This paper is devoted to the study of kinetic equilibrium among electrons, H₂ molecules, H atoms, and positive H⁺, H ₂ ⁺ , and H ₃ ⁺ ions in a multipole discharge working under low-pressure (1- to 15-m Torr) and moderated current conditions. In such a discharge used either as a H⁺ or a H^– ion source or for plasma-surface interactions, the dependence of the densities of these species versus experimental parameters is of a great interest. In the present situation, the electron energy distribution function (e.e.d.f.) is largely nonmaxwellian. The kinetic model that determines the densities of the plasma species is self-consistently coupled to the e.e.d.f. calculated through the use of the Boltzmann equation. The influence of the main processes, volume ones, and those involving plasma walls is emphasized. An attempt is made to use the profiles of Balmer lines obtained experimentally in order to determine absolute concentrations of H atoms and H ₂ ⁺ ions. Results derived from the experiment are compared to results of the model. Such an analysis of Balmer line shapes appears to be an interesting way to determine, by anin situ nonintrusive method, the absolute concentration of H atoms.     

Spatially resolved temperature measurements in a furnace atomization plasma excitation spectrometry source

Spatially resolved atomic emission intensities from helium, and molecular emission intensities from OH and N⁺₂ have been measured in a furnace atomization plasma excitation spectrometry (FAPES) source. He I emission at 388.86 nm was used to monitor the spatial structure of the plasma in the source while increasing the radio frequency (r.f.) power applied to its center electrode. At higher r.f. power the He I emission intensity increased significantly while its spatial structure remained relatively unchanged. The He I emission was found to be most intense adjacent to the center electrode. Some less intense emission was observed adjacent to the graphite cuvette wall and some very weak emission was seen throughout the volume of the source. These observations suggest that the FAPES source operates as an r.f. glow discharge.Emission intensities from the OH (0-0) rotational A ²Σ⁺ → X ²Π_i and N⁺₂ (0-0) rotational B ²Σ⁺_o → ²Σ⁼_g bands were used to monitor the effects of increasing the r.f. power applied to the center electrode of the source. From these measurements, rotational temperatures for these molecules were calculated. The intensity measurements showed that there is a significant thermal gradient in the source with OH rotational temperatures ranging between 680 and 1050 K and N⁺₂ rotational temperatures ranging between 580 and 1920 K with 60 W r.f. power applied to the center electrode. At higher r.f. powers there is an increase in rotational temperatures and an increase in the dissociation of molecular species in the FAPES source.Lead excitation temperatures were calculated using the line ratio method by measuring the emission of the Pb I 280.119 and 283.306 nm lines at different r.f. powers. The temperature was found to increase monotonically with r.f. power over the range of 35 to 75 W.     

Effects of the Pulse Polarity on Helium Plasma Jets: Discharge Characteristics,Key Reactive Species,and Inactivation of Myeloma Cell

In this paper, we report the effects of the pulse polarity on the plasma jet’s discharge characteristics, particularly, on the production of the reactive oxygen and nitrogen species (RONS) and the inactivation efficiency of myeloma cells, for the purpose of identifying and elucidating the correlation between the dose of RONS and cell viability. Experimental results reveal that the positive plasma jet has a longer length than that for negative plasma jet with the equivalent pulse power. The positive pulse plasma jet would produce higher production of the excited reactive species (OH(A), N₂(C), N₂⁺(B), He(3s³S), O(3p⁵P)), the positive ions (N⁺, O⁺, N₂⁺, O₂⁺), and the aqueous species O₂^?, OH, and ONOO^?, while negative plasma jet would generate higher concentration of the negative ions (OH^?, O₂^?, NO₂^?, NO₂^?) and the aqueous species NO₂^? and NO₃^?. Additionally, the myeloma cells treated by positive plasma jet results in more cell apoptosis and more CD95 expression compared to negative plasma jet, indicating the impact for the cell apoptosis is more significant in the cellular response to the positive plasma jet. By comparing and analyzing the different doses of RONS to the responses of myeloma cells under positive and negative pulse plasma jet, our findings suggest the cell viability has a positive correlation with the concentration of the concentration of ONOO^? and the concentration ratio of H₂O₂ to NO₂^?, implying the high concentrations for ONOO^? and H₂O₂ might be responsible for the inactivation of myeloma cancer cells.     

Characterization of a capillary dielectric barrier plasma jet for use as a soft ionization source by optical emission and ion mobility spectrometry

This paper presents the characterization of a source for soft ionization of organic molecules. This source is based on a plasma jet established at the end of a capillary dielectric barrier discharge at atmospheric pressure. He, Ne and Ar as pure gas or with different concentrations of N₂ are used as buffer gas for the plasma jet. Spectroscopic emission measurements are carried out along the plasma jet in and outside the capillary. The intensity variation of N₂⁺ lines, for example emission at 391.4 and 427.8 nm, can be associated with the protonation process which is the basis for the soft ionization. The mechanism of the N₂⁺ production outside the capillary, which is relevant for the protonation of molecules and sustains the production of primary ions, is investigated. The response signal of the ions in a nitrogen atmosphere was measured with an ion mobility spectrometer (IMS).     

Hybrid Monte Carlo — Fluid model for studying the effects of nitrogen addition to argon glow discharges

A computer model is developed for describing argon/nitrogen glow discharges. The species taken into account in the model include electrons, Ar atoms in the ground state and in the 4s metastable levels, N₂ molecules in the ground state and in six different electronically excited levels, N atoms, Ar⁺ ions, N⁺, N₂⁺, N₃⁺ and N₄⁺ ions. The fast electrons are simulated with a Monte Carlo model, whereas all other species are treated in a fluid model. 74 different chemical reactions are considered in the model. The calculation results include the densities of all the different plasma species, as well as information on their production and loss processes. The effect of different N₂ additions, in the range between 0.1 and 10%, is investigated.     

Deposition of Diamondlike Carbon Film and Mass Spectrometry Measurement in CH4/N2 RF Plasma

The deposition of diamondlike carbon (DLC) film and the measurements of ionic species by means of mass spectrometry were carried out in a CH₄/N₂ RF (13.56 MHz) plasma at 0.1 Torr. The film deposition rate greatly depended on both CH₄/N₂ composition ratio and RF power input. It was decreased monotonically as CH₄ content decreased in the plasma and then rapidly diminished to negligible amounts at a critical CH₄ content, which became large for higher RF power. The rate increased with increasing RF power, reaching a maximum value in 40% CH₄ plasma. The predominant ionic products in CH₄/N₂ plasma were NH⁺ ₄ and CH₄N⁺ ions, which were produced by reactions of hydrocarbon ions, such as CH⁺ ₃, CH⁺ ₂, CH⁺ ₅, and C₂H⁺ ₅ with NH₃ molecules in the plasma. It was speculated that the production of NH⁺ ₄ ion induced the decrease of C₂H⁺ ₅ ion density in the plasma, which caused a reduction in higher hydrocarbon ions densities and, accordingly, in film deposition rate. The N⁺ ₂ ion sputtering also plays a major role in a reduction of film deposition rate for relatively large RF powers. The incorporation of nitrogen atoms into the bonding network of the DLC film deposited was greatly suppressed at present gas pressure conditions.     

Spatially resolved spectroscopic measurements of a dielectric barrier discharge plasma jet applicable for soft ionization

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry and as ionization source for ion mobility spectrometry. It turned out that dielectric barrier discharge ionization could be regarded as a soft ionization technique characterized by only minor fragmentation similar to atmospheric pressure chemical ionization (APCI). Mainly protonated molecules were detected. In order to characterize the soft ionization mechanism spatially resolved optical emission spectrometry (OES) measurements were performed on plasma jets burning either in He or in Ar. Besides to spatial intensity distributions of noble gas spectral lines, in both cases a special attention was paid to lines of N₂⁺ and N₂. The obtained mapping of the plasma jet shows very different number density distributions of relevant excited species. In the case of helium plasma jet, strong N₂⁺ lines were observed. In contrast to that, the intensities of N₂ lines in Ar were below the present detection limit. The positions of N₂⁺ and N₂ distribution maxima in helium indicate the regions where the highest efficiency of the water ionization and the protonation process is expected.     

Surface analysis of nitride layers formed on Fe‐based alloys through plasma nitride process

Nitriding phenomena that occur on the surfaces of pure Fe and Fe? Cr alloy (16 wt% Cr) samples were investigated. An Ar + N₂ mixture‐gas glow‐discharge plasma was used so that surface nitriding could occur on a clean surface etched by Ar⁺ ion sputtering. In addition, the metal substrates were kept at a low temperature to suppress the diffusion of nitrogen. These plasma‐nitriding conditions enabled us to characterize the surface reaction between nitrogen radicals and the metal substrates. The emission characteristics of the band heads of the nitrogen molecule ion (N₂⁺) and nitrogen molecule from the glow‐discharge plasma suggest that the active nitrogen molecule is probably the major nitriding reactant. AES and angle‐resolved XPS were used to characterize the thickness of the nitride layer and the concentration of elements and chemical species in the nitride layer. The thickness of the nitride layer did not depend on the metal substrate type. An oxide layer with a thickness of a few nanometers was formed on the top of the nitride layer during the nitriding process. The oxide layer consisted of several species of N_x‐Fe_y‐O, NO⁺, and NO₂^?. In the Fe? Cr alloy sample, these oxide species could be reduced because chromium is preferentially nitrided. Copyright © 2009 John Wiley & Sons, Ltd.     

Comparison of the Active Species in the RF and Microwave Flowing Discharges of N<Subscript>2</Subscript> and Ar–20 %N<Subscript>2</Subscript>

We report a detailed comparison between RF and microwave (HF) plasmas of N₂ and Ar–20 %N₂ as well as in the corresponding afterglows by comparing densities of active species at nearly the same discharge conditions of tube diameter (5–6 mm), gas pressure (6–8 Torr), flow rate (0.6–1.0 slm) and applied power (50–150 W). The analysis reveals an interesting difference between the two cases; the length of the RF plasma (~25 cm) is measured to be much longer than that of HF (6 cm). This ensures a much longer residence time (10^?2 s) of the active species in the N₂ RF plasma [compared to that (10^?3 s) of HF], providing a condition for an efficient vibrational excitation of N₂(X, v) by (V–V) climbing-up processes, making the RF plasma more vibrationally excited than the HF one. As a result of high V–V plasma excitation in RF, the densities of the vibrationally excited N₂(X, v > 13) molecules are higher in the RF afterglow than in the HF afterglow. Destruction of N₂(X, v) due to the tube wall is estimated to be very similar between the two system as can be inferred from the γ_v destruction probability of N₂(X, v > 3–13) on the tube wall (2–3 × 10^?3 for both cases) obtained from a comparison between the density of N₂(X, v > 3–9) in the plasmas to that of the N₂(X, v > 13) in the long afterglows. Interestingly enough, densities of N-atoms and N₂(A) metastable molecules in the afterglow regions, however, are measured to be very similar with each other. The measured lower density of N₂ ⁺ ions than expected in the HF afterglow is rationalized from a high oxygen impurity in our HF setup since N₂ ⁺ ions are very sensitive to oxygen impurity .     

Ion formation processes in the afterpeak time regime of pulsed glow discharge plasmas

The formation of ions following the termination of power in a pulsed glow discharge ion source is investigated. The populations of ionized species containing sputtered atoms M⁺, M ₂ ¹ :, and MAr⁺ are observed to maximize after the termination of discharge power. Collisions involving sputtered atoms and metastable argon atoms, Penning and associative ionization, are considered to be responsible for the formation of ions in the discharge afterpeak time regime. The domination of these ion formation processes during the afterpeak time regime is supported by the results from investigations of discharge operating parameters, metastable argon atom quenching, and ion kinetic energy distributions.     

Understanding the flowing atmospheric-pressure afterglow (FAPA) ambient ionization source through optical means

The advent of ambient desorption/ionization mass spectrometry (ADI-MS) has led to the development of a large number of atmospheric-pressure ionization sources. The largest group of such sources is based on electrical discharges; yet, the desorption and ionization processes that they employ remain largely uncharacterized. Here, the atmospheric-pressure glow discharge (APGD) and afterglow of a helium flowing atmospheric-pressure afterglow (FAPA) ionization source were examined by optical emission spectroscopy. Spatial emission profiles of species created in the APGD and afterglow were recorded under a variety of operating conditions, including discharge current, electrode polarity, and plasma-gas flow rate. From these studies, it was found that an appreciable amount of atmospheric H₂O vapor, N₂, and O₂ diffuses through the hole in the plate electrode into the discharge to become a major source of reagent ions in ADI-MS analyses. Spatially resolved plasma parameters, such as OH rotational temperature (T_rot) and electron number density (n_e), were also measured in the APGD. Maximum values for T_rot and n_e were found to be ~1100 K and ~4 × 10¹⁹ m^–3, respectively, and were both located at the pin cathode. In the afterglow, rotational temperatures from OH and N₂⁺ yielded drastically different values, with OH temperatures matching those obtained from infrared thermography measurements. The higher N₂⁺ temperature is believed to be caused by charge-transfer ionization of N₂ by He₂⁺. These findings are discussed in the context of previously reported ADI-MS analyses with the FAPA source.     

Contribution of Discharge Excited Atomic N,N2*, and N2+ to a Plasma/Liquid Interfacial Reaction as Suggested by Quantitative Analysis

Electric-discharge nitrogen comprises three main types of excited nitrogen species-atomic nitrogen (N_atom), excited nitrogen molecules (N₂*), and nitrogen ions (N₂⁺) – which have different lifetimes and reactivities. In particular, the interfacial reaction locus between the discharged nitrogen and the water phase produces nitrogen compounds such as ammonia and nitrate ions (denoted as N-compounds generically); this is referred to as the plasma/liquid interfacial (P/L) reaction. The N_atom amount was analyzed quantitatively to clarify the contribution of N_atom to the P/L reaction. We focused on the quantitative relationship between N_atom and the produced N-compounds, and found that both N₂* and N₂⁺, which are active species other than N_atom, contributed to P/L reaction. The production of N-compounds from N₂* and N₂⁺ was enhanced upon UV irradiation of the water phase, but the production of N-compounds from N_atom did not increase by UV irradiation. These results revealed that the P/L reactions starting from N_atom and those starting from N₂^* and N₂⁺ follow different mechanisms.     

Influence of the Excited States of Atomic Nitrogen N(<Superscript>2</Superscript>D), N(<Superscript>2</Superscript>P) and N(R) on the Transport Properties of Nitrogen. Part II: Nitrogen Plasma Properties

In this paper, the calculated values of the viscosity and thermal conductivity of nitrogen plasma are presented taking into account five (e, N, N⁺, N₂ and N₂⁺) or eight (e, N(⁴S), N(²P), N(²D), N(R), N⁺, N₂ and N₂⁺) species. The calculations are based on the supposition that the temperature dependent probability of occupation of the states is given by the Boltzmann factor. The domain for which the calculations are performed, is for p = 1 and 10 atm in the temperature range from 5,000 K to 15,000 K. Classical collision integrals are used in calculating the transport coefficients and we have introduced new averaged collision integrals where the weight associated at each interacting species pair is the probable collision frequency. The influence of the collision integral values and energy transfer between two different species is studied. These results are compared which those of published theoretical studies.     

Characterization of the Active Species in the Afterglow of a Nitrogen and Helium Atmospheric-Pressure Plasma

The concentrations of the neutral active species in the afterglow of a nitrogen and helium atmospheric-pressure plasma have been determined by optical emission and absorption spectroscopy and by numerical modeling. For operation with 10 Torr N₂ and 750 Torr He, at 15.5 W/cm³ rf power, 30.4 L/min flow rate, and a neutral temperature of 50°C, the plasma produced 4.8×10¹⁵ cm^–3 of ground state nitrogen atoms, N(⁴S), 2.1×10¹³ cm^–3 of N₂(A³_u), 1.2×10¹² cm^–3 of N₂(B³_g), and 3.2×10⁹ cm^–3 of N₂(C³_u). The concentration of nitrogen atoms and metastable state nitrogen molecules, N₂(A), increased gradually with the rf power and the nitrogen partial pressure. Both the model and experiments indicate that ground-state nitrogen atoms are the dominant active species in the afterglow beyond 2.0 ms.     

One-Step Synthesis of Silicon Oxynitride Films Using a Steady-State and High-Flux Helicon-Wave Excited Nitrogen Plasma

A steady-state and high-flux helicon-wave excited N₂ plasma was used to oxynitride Si substrates for the synthesis of silicon oxynitride (SiON) films. X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) have been extensively used to characterize surface quality of the SiON films, and it is found that a large amount of nitrogen (N) can be incorporated into the films. The result of XPS depth profiles shows that the N concentration is high near the surface and the oxide/Si interface. In the UPS spectra, absence of the reappearance of surface states suggests a resistance to clustering of the oxynitride layer. The N₂ flux and Ar mixture quantity can facilitate tuning of the dissociation characteristics in N₂ discharge. By modulating the N₂ fractions, the N⁺ density reaches maximum at a N₂/(N₂ + Ar) flow-rate ratio of 0.5, resulting in incorporation of more N atoms into the SiON films. Considering the easy control of N₂ plasma, our work opens up a new avenue for achieving high-yield SiON films at low temperature.