Spectroscopic diagnostics of R.F. discharges at moderate pressure and chemical applications—I. Pure nitrogen

A vibro-rotational analysis has been performed of the second positive system (SPS) of N₂ and of the first negative system (FNS) of N⁺₂ emitted by 35 MHz discharges in flowing nitrogen operated at pressures of 5–50 torr and power densities of the order of 1–10 W-cm^-3. The distributions of the vibrational and of the rotational levels follow Boltzmann's law in both the SPS and the FNS with T_v = 4000°K and T_R = 2800°K for the N₂(C³Π_u) state and T_v = 5100°K and T_R = 5800°K for the N⁺₂(B²Σ⁺_g) state and independent of pressure. Kinetic gas temperatures are between 1200 and 2000°K and increase with pressure; electron temperatures are in the range 15,000–9,500°K. The reversal of line intensities of the SPS and of the FNS observed with increasing pressure has been tentatively interpreted. Possible chemical implications of these results have been examined.     

Spectroscopic measurements of non-equilibrium nitrogen plasmas at moderate pressures

A local vibro-rotational analysis of the excited species, produced in a 35 MHz discharge reactor in flowing nitrogen, has been carried out by measuring radial and axial emission intensities of some vibrational sequences and selected rotational lines of the (0,2) band of the second positive system (SPS) of N₂ (C³Π_u - B³Π_g), in the pressure range 5–35 torr.Radial from lateral band or line emission intensities have been obtained by applying Abel's inversion technique to derive the corresponding vibrational and rotational temperatures with the use of Boltzmann plots. General maps of emission intensities and of vibrational and rotational temperature distributions within the reactor have been drawn.It is shown that a decrease of a factor 10³ in the emission intensities from the core to the periphery of the discharge corresponds to a variation in T_V and T_R of only a factor ?2. This result has been interpreted on the basis of the kinetic mechanisms for the excitation and deexcitation of chemical species under discharge conditions. The decrease of _V and the increase of T_R with increasing pressure are interpreted according to V-R (vibration-rotation) energy-transfer mechanisms.     

Measurement of C2 and CH temperatures in argon‐acetylene low‐pressure microwave‐induced plasma

The emission spectra of C₂(d³Π_g–a³Π_u), CH(A²Δ–X²Π), and CH(B²Σ–X²Π) bands are analysed to measure rotational T_rot, vibrational T_vib, and gas temperature T_g from Ar/C₂H₂ (5–20% C₂H₂) microwave‐induced plasma (MIP). In case when helium and hydrogen are used in the gas mixture instead of argon, no significant change in T_rot is noticed. Both studied temperatures are insensitive in terms of the C₂H₂ percentage. From CH(0–0, A²Δ–X²Π) band R₂ branch lines, two T_rot (T_rot ～ 520–580 K for J′ = 3–9 and T_rot ～ 1,700–1,800 K for J′ = 10–17) are determined. The lower T_rot equals the T_g (500–700 K) measured from C₂ bands in this study. The H₂ Fulcher‐α diagonal bands are recorded as well in the H₂/C₂H₂ mixtures and T_rot～750–900 K of the H₂ ground state measured. T_vib ～ 6,000 K in Ar/C₂H₂ MIP is calculated from the integral intensity ratio of C₂(2,1) and C₂(3,2) bands.     

Vibrational Excitation of N2(B,C) and N+2(B) States in N2 and N2 – H2 Flowing Microwave Discharges

The ro‐vibrational spectra of N₂ microwave discharges have been analysed by emission spectroscopy. It is deduced the rotational and vibrational temperatures of N₂ states. The characteristic of vibrational temperature Θ₁ of the N₂ (X, v) ground state has been specifically determined.It has been found that the N₂ (C, B, v') and N⁺₂ (B, v') radiative states are directly excited by electron collisions on the N₂ (X,v) ground state at a N₂ gas pressure of 0.1 Torr (discharge tube of 5 mm I.D, microwave power 100 Watt) with a Θ₁ value near 10⁴ K. At higher gas pressure up to 5 Torr, the N₂ (C, v') states remain alone to be mainly excited by electron collisions on N₂ (X, v). It is considered the excitations of the N₂ (B, v') states by collisions of electrons and N₂ (X,v > 4) vibrational molecules on the N₂ (A) metastable states.With x < 9% H₂ into N₂, it is observed an increase of N₂, 2^nd pos intensity, resulting of an increase of high energy electrons. Inversely, the N₂, 1^st pos intensity decreased, partly following the decrease of low energy electrons (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopic study of an rf discharge in nitrogen

The absolute populations of the vibrational levels of the B³Πg and C³Π_u states in an rf nitrogen discharge are calculated from the quantum yields of the 1⁺ and 2⁺ systems in the discharge, and the “excitation temperature” of these states is measured. Emission spectroscopic methods are used to determine the vibrational and rotational temperatures of the C³Π_u state, as well as the vibrational temperature of the B³Π_g state. These data are used to estimate the vibrational temperature of the X′∑ _g ⁺ state and the stored energy in the activated nitrogen, and to examine the mechanism by which translational-vibrational degrees of freedom are excited in nitrogen molecules in the discharge.     

Utilization of rotational and vibrational temperatures for plasma diagnostics of high-pressure discharges

In the spectra of high-pressure discharges excited in molecular gases, very intensive molecular spectral bands may usually be observed. We may determine the rotational and vibrational temperatures without difficulty, however, the rotational and vibrational temperatures (T _r, T_v) do not offen equal to the temperature of neutral gas (T ₀) or to that of electrons (T _e). If the collision cross sections of electronic, atomic, and molecular excitation (deexcitation) are known, we may then calculate the dependence of the rotational and vibrational temperatures onT _e,T ₀,N _e and the pressure of the gas. The calculations have been performed for pure N₂ and for an Ar-N₂ mixture at atmospheric pressure. The computed graphs make it possible to determine some of the values 4T _e,T ₀,N _e if the temperaturesT _r andT _v are known.The author wishes to extend his thanks to Prof. V. Truneek for valuable comments and to Mr. A. Struka for the preparation of the diagrams.     

Radiative Transitions and Temperature Time Dependences in Pulse Excited Microwave Discharges – (N2, Ar + N2)

Quantitative spectral and microwave measurements of vibrational temperatures and electron densities were performed for 2400 MHz non-isothermic pulse excited discharges in flowing nitrogen and argon at pressures (60–2700) Pa. A detailed analysis of the N₂ vibrational states population for the N₂ C³Π_u, X¹Σ_g⁺ electronic states has been carried out. The basic difficulties encountered when comparing the spectroscopically determined values of vibrational temperatures with corresponding quantities of the ground electronics state are mentioned and the time resolved dependences of the translational gas temperature in N₂ during the microwave pulse is evaluated. The steady state in the nitrogen pulse excited microwave plasma is reached within 3 · 10^?4 s, but generally, this time depends on the gas pressure in the discharge tube. In the Ar + N₂ mixtures the excitation conditions are complicated by the metastable argon atoms (3P_2,0) creating the nonequilibrium populations of electronic, vibrational and rotational N₂ states.     

Diagnosis of OH radical by optical emission spectroscopy in a wire-plate bi-directional pulsed corona discharge

The emission spectrum of the molecule OH (A²Σ→X²Π, 0–0) during a high-voltage, bi-directional pulsed corona discharge consisting of a gas mixture of N₂ and H₂O in a wire-plate reactor has been successfully recorded under severe electromagnetic interference at atmospheric pressure. The relative vibrational populations and the vibrational temperature of N₂ (C, v′) have also been determined. Due to the difficulty of determining the exact overlapping spectral line shape function of the OH (A²Σ→X²Π, 0–0) and the Δv=+1 vibrational transition band of N₂ (C³Π_u→B³Π_g), a practicable Gaussian form is used for calculating the emission intensity of OH (A²Σ→X²Π, 0-0) and the Δv=+1 vibrational transition band of N₂ (C³Π_u→B³Π_g). The emission intensity of OH (A²Σ→X²Π, 0–0) has been evaluated with a satisfactory accuracy by subtracting the emission intensity of the Δv=+1 vibrational transition band of N₂ (C³Π_u→B³Π_g) from the overlapping spectra. The relative population of OH (A²Σ) has been obtained by the emission intensity of OH (A²Σ→X²Π, 0–0) and Einstein's transition probability. The influences of peak voltage, pulse repetition rate and O₂ flow rate on the relative population of OH (A²Σ) radicals have also been investigated. We found that the relative population of OH (A²Σ) rises with an increase in both the peak applied voltage and the pulse repetition rate. When oxygen is added to an N₂ and H₂O gas mixture, the relative population of OH (A²Σ) radicals decreases exponentially with an increase in added oxygen. The main physicochemical processes involved are also discussed in this paper.     

Numerical study of the effect of gas flow in low pressure inductively coupled Ar/N<Subscript>2</Subscript> plasmas

The effect of gas flow in low pressure inductively coupled Ar/N₂ plasmas operating at the rf frequency of 13.56 MHz and the total gas pressure of 20 mTorr is studied at the gas flows of 5–700 sccm by coupling the plasma simulation with the calculation of flow dynamics. The gas temperature is 300 K and input power is 300 W. The Ar fractions are varied from 0% to 95%. The species taken into account include electrons, Ar atoms and their excited levels, N₂ molecules and their seven different excited levels, N atoms, and Ar⁺, N⁺, N₂ ⁺, N₄ ⁺ ions. 51 chemical reactions are considered. It is found that the electron densities increase and electron temperatures decrease with a rise in gas flow rate for the different Ar fractions. The densities of all the plasma species for the different Ar fractions and gas flow rates are obtained. The collisional power losses in plasma discharges are presented and the effect of gas flow is investigated.     

大气压下氮气介质阻挡微放电中分子振动温度的时间分辨

使用针-板式电极装置,在大气压氮气介质阻挡微放电中,通过对氮分子第二正带系（C3Πu→B3Πg）发射光谱的时间分辨谱线进行分析,根据振动带序发射光谱强度计算得出N2（C,ν）振动温度,并研究了不同压强及放电电压对氮分子（C3Πu）的振动温度时间分辨的影响。实验结果表明：氮分子振动温度的范围为2 000～3 500 K,在每半个放电周期内都呈减小趋势,且正负半周期振动温度差较大,负半周期振动温度始终高于正半周期;振动温度随电压升高而升高,随压强的升高而降低。     

Spectral and Electrical Properties of a Medium Pressure,Low-Power,RF-Generated Postdischarge Nitrogen Plasma Jet

A method for obtaining a medium pressure (p ～ 1 torr), low power (< 100 W), RF-generated plasma jet, suitable for chemical kinetics studies and technological applications is described. Though various supply gases can be used to create the plasma jet, only results on the properties of a nitrogen jet are given in this paper with an emphasis on some spectral and electrical characteristics. The emission spectra of the nitrogen jet are discussed and spatial distributions of the relative concentration of nitrogen or radical impurities emitting species such as N₂(C³Π_u, v' = 0), NH(A³Π_g, v'=0) in the bulk of the postdischarge plasma are calculated from the intensity of their vibrational bands. Electrical space resolved double probe measurements and the spatial distributions of the electron density and temperature in the plasma jet are also presented. Possible applications are shortly discussed.     

High‐resolution stimulated Raman study of the first vibrational hot band of 14N2. Separate observation of the spectra of the ortho and para species.

We present high‐resolution stimulated Raman spectra of the first hot band of nitrogen, ¹⁴N₂, obtained under conditions of low sample pressure and temperature. The use of a Raman optical pumping system allowed us to transfer a significant amount of population to the v = 1 vibrational state, which made possible the observation of the aforementioned hot band with good S/N ratio without resorting to the use of high temperatures or pressures. This has resulted in a more precise and accurate determination of the peak positions than previously existing ones, which in turn has yielded improved values for the molecular constants obtained from the analysis. The rotational selectivity of the pumping process (only one rotational state is initially populated in v = 1), coupled with the negligible probability of nuclear spin interconversion in the time frame of the experiment, has allowed us to observe the hot band spectra of the ortho and para species of ¹⁴N₂ separately. Copyright © 2013 John Wiley & Sons, Ltd.     

The analysis of nitrogen rotational and vibrational bands in a helium microhollow gas discharge

Emission spectroscopy is applied to measure the gas temperature T _g and the vibrational distribution of N₂ (C ³Π_u) and N₂ ⁺(B ²Σ_u ⁺) excited states from a helium microhollow gas discharge (MHGD) at atmospheric pressure. The rotational temperature T _rot of N₂ ⁺ is determined from relative intensity of the R‐branch lines of the N₂ ⁺(B ²Σ_u ⁺–X ²Σ_g ⁺) bands at 427.81 and 419.91 nm and the well‐known Boltzmann plot (BP). Using the same diagnostic technique, the rotationally resolved N₂(C ³Π_u–B ³Π_g) band at 380.49 nm is used to measure T _rot. Under our experimental conditions, T _g is equal to T _rot = 550–650 K for nitrogen molecules and shows a slight increase with the discharge current in the current range 3–10 mA. From the intensity ratio of two consecutive vibrational bands of the same sequence, the N₂(C ³Π_u) and N₂ ⁺(B ²Σ_u ⁺) vibrational temperature T _vib = 3,700–4,000 K is determined. It has been found that N₂ ⁺(B ²Σ_u ⁺) ions have non‐Boltzmann distribution in the helium MHGD, while N₂(C ³Π_u) molecules are populated according to the Boltzmann distribution. Following the Franck–Condon principle, the vibrational distribution of the ground state of N₂(X ¹Σ_g ⁺) molecules has been determined from the N₂(C ³Π_u) distribution using the inversion matrix of elements q _XC(ν ,ν ′).     

Cars measurement of vibrational temperatures in electric discharges

The measurement of vibrational and rotational temperatures of D₂ at the center of an electrical discharge has been demonstrated by a new diagnostic technique: Coherent Anti-Stokes Raman Spectroscopy (CARS). On the assumption of equilibration among vibrational levels, T_v was estimated to be approximately 1050 K, whereas T_r was determined to be near ambient (?400 K).     

Temperature Distributions Across the Plasma Layer of Planar Low Pressure Microwave Plasmas — A Comparative Investigation by Optical Emission Spectroscopy

Nowadays low temperature non-equilibrium plasmas received considerable attention in very different fields of plasma processing. The subject of the present paper is the comparative measurement of neutral gas temperature and optical excitation temperature to analyze the temperature distributions across the plasma layer of H₂ non-equilibrium plasmas (p = 0.2 – 1.5 kPa) with small admixtures of hydrocarbons in a novel planar microwave plasma source (2.45 GHz) used for plasmachemical deposition purposes by means of optical emission spectroscopy. Typical microwave power flux densities into the plasma lie within a range of 2 W cm^?2 to 20 W cm^?2. Results of neutral gas temperature measurements derived from H_α line Doppler profiles are compared with rotational temperatures of H₂ and N₂ molecules. The neutral gas temperature (800–1700 K) corresponds to the rotational temperature of the H₂ molecules (Fulcher band, R 0–0 branch) but shows a more distinct spatial gradient. The rotational temperature of admixtured N₂ molecules (2000–3000 K) is much more higher although Boltzmann distribution was ensured. The spatially resolved measured excitation temperature (1–3 eV) determined with the help of line intensity ratios of admixtured Ar well agrees with Langmuir probe measurements. The reported measurements as a whole demonstrate the feasibility of comparative investigations of different optically determined temperatures for expressive characterization of low pressure microwave plasmas.     

Measurements of spatially resolved electron number densities and modes temperatures using optical emission spectroscopy of atmospheric pressure microplasma jet

The electrical gas discharge parameters of direct-current non-thermal microplasma jet in Ar-2%H₂ flow at open atmospheric air was investigated by using spatially resolved optical emission spectroscopy (OES). The jet was confined from microhollow of tungsten-carbide (～500 μm inner diameter) to a molybdenum foil. Despite its small volume, the atmospheric pressure microplasma jet provides a range of power densities, from low to ～10¹² W m^?3 generated either in rare gases or in molecular gases. A high resolution spectrometer (Jobin-Yvon, Czerny-Turner model THR1000, resolution of 0.001 nm, with focal length of 1.0 m and numerical aperture of 0.13 ? f/7.5) was used to allow registration of OH (A ²Σ⁺, ν = 0 → X ²Π, ν′ = 0) rotational bands at 306.357 nm, Ar I 603.213 nm line and N₂ (C ³Π _u , ν = 0 → B ³Π _g , ν′ = 0) second positive system with the band head at 337.13 nm in order to estimate the rotational temperature from the cathode sheath of the plasma jet to the anode. For currents ranging from 20 to 100 mA and for a particular excited levels, the excitation temperature was measured in the negative glow region either from a Boltzmann plot of Ar I 4p–4s and 5p–4s transitions of excited argon or using the Mo I (from 440 to 450 nm) two-lines method of excited Mo atoms sputtered from the cathode surface, giving 24 000 K (100 mA at 100 μm) and 7000 K (20 mA at 500 μm from the cathode). From the N₂ (C ³Π _u , ν = 0 → B ³Π _g , ν′ = 0) rotational transition the rotational temperature along the positive column was estimated. The vibrational temperature of the bulk plasma (1400 to 4500 K) was estimated for a current varying from 20 to 120 mA using the N₂ second positive system with Δν = ?2. Using the broadening of H _β Balmer line it was possible to estimate the electron number density of the negative glow (10¹⁴ to 10¹⁵ cm^?3) as a function of the current.     

Spontaneous Raman scattering: a useful tool for investigating the afterglow of nanosecond scale discharges in air

Nanosecond scale discharges are considered an interesting way for assisting combustion by enhancing either flame stabilization or ignition. Better understanding of energy deposit and radical species production processes is still required under pressure conditions normally encountered in combustion. The purpose of the present paper is to show that spontaneous Raman scattering, seldom used to investigate nanosecond pulsed discharges, is a useful measurement method for investigating the energy deposit of these discharges. The advantage of spontaneous Raman scattering is described by analyzing N₂ and O₂ spectra during the post-discharge of a filamentary nanosecond air discharge under atmospheric pressure, using phase-locked average spectra. The main advantages of spontaneous Raman scattering measurements are that they allow line-wise probing of different species with the same experimental setup and the determination of vibrational distribution by comparison with theoretical modeling over a wide range of vibrational levels (from v=0 to v=20 for N₂). The model proposed takes into account the high level of vibrational excitation and the strong non-equilibrium observed, allowing the characterization of the vibrational relaxation over the complete post-discharge duration. Although the rotational structure is not resolved, the rotational temperature and thus translational temperature are determined with a moderate uncertainty for T above 500 K.     

The rotational spectrum of 13C2HD in the ground and excited bending states

The pure rotational spectrum of ¹³C₂HD was recorded in the range 100–700 GHz. Lines belonging to the ground vibrational state were observed from J^″ = 1 to J^″ = 11. Several absorption lines were also detected in the bending states v₄ = 1 (Π), v₅ = 1 (Π), v₄ = 2 (Σ⁺ and Δ), v₅ = 2 (Σ⁺ and Δ), v₄ = v₅ = 1 (Σ^?, Σ⁺ and Δ), v₄ = 3 (Π and Φ) and v₅ = 3 (Π and Φ). The transition frequencies measured in this work were fitted together with all the infrared lines available in the literature. The global fit allowed a very accurate determination of the vibrational, rotational and ?-type interaction parameters for the bending states of this molecule.     

Diode-laser spectroscopy of supersonic free jets

A supersonic-free-jet infrared spectrometer has been constructed for investigation of molecular vibrational spectra at low rotational and vibrational temperatures. The sensitivity of measurement in a pulsed jet is increased by employing a phase-sensitive detection method synchronized with the pulse frequency. The performance of the spectrometer is examined for the absorption lines of the NH₃ v ₂ band. A rotational temperature as low as 16K is attained when seeded in He. Cold-jet spectra are demonstrated for thev ₃ bands of PF₅,³⁴SF₆, and¹⁸²WF₆.     

Excited-state photoelectron spectra of the one-photon forbidden C3IIg rydberg state of molecular oxygen

The Rydberg C³II_g, state of molecular oxygen, which is one-photon forbidden from the ground electronic state, has been studied by means of (2 + 1) multiphoton ionization (MPI) ion-current and photoelectron spectroscopic techniques in the laser wavelength region 287–289 nm. Excitedstate photoelectron spectra have been observed at different rotational levels of the C³Π_gv' = 2 state of O₂, and show marked deviation from the Franck-Condon distribution generally expected in ionization of Rydberg electrons. Namely, in addition to main photoelectron peaks due to Δv = 0 transitions, other vibrational peaks are also observed with considerable intensities. The v⁺= 2 photoelectron peak shows different angular dependence from the other vibrational peaks. The rotational structure in the MPI ion-current spectrum of O₂ is well interpreted in terms of the rotational constants of the X²Π_g ground electronic state of O₂⁺.