Plasma activation of N-2, CH4 and CO2: an assessment of the vibrational non-equilibrium time window

Vibrational excitation potentially enhances the energy efficiency of plasma dissociation of stable molecules and may open new routes for energy storage and process electrification. Electron, vibrational and rotational temperatures were measured by in situ Thomson and Raman scattering in order to assess the opportunities and limitations of the essential vibration-translation non-equilibria in N-2, CO2 and CH4 plasma. Electron temperatures of 1.1-2.8 eV were measured in N-2 and CH4. These are used to confirm predominant energy transfer to vibrations after an initial phase of significant electronic excitation and ionization. The vibrational temperatures initially exceed rotational temperatures by almost 8000 K in N-2, by 900 K in CO2, and by 300 K in CH4. Equilibration is observed at the 0.1 ms timescale. Based on the vibrational temperatures, the vibrational loss rates for different channels are estimated. In N-2, vibrational quenching via N atoms is identified as the dominant equilibration mechanism. Atomic nitrogen population reaches a mole fraction of more than 1%, as inferred from the afterglow emission decay, and explains a gas heating rate of 25 K mu s(-1). CH4 equilibration at 1200 K is predominantly caused by vibrational-translational relaxation in CH4-CH4 collisions. As for CO2, vibrational-translational relaxation via parent molecules is responsible for a large fraction of the observed heating, whereas product-mediated VT relaxation is not significantly contributing. It is suggested that electronic excitation, followed by dissociation or quenching contributes to the remaining heat generation. In conclusion, the time window to profit from vibrational excitation under the present conditions is limiting practical application.</p

N, NH, and NH2 radical densities in a remote Ar-NH3-SiH4 plasma and their role in silicon nitride deposition

The densities of N, NH, and NH2 radicals in a remote Ar-NH3-SiH4 plasma used for high-rate silicon nitride deposition were investigated for different gas mixts. and plasma settings using cavity ringdown absorption spectroscopy and threshold ionization mass spectrometry. For typical deposition conditions, the N, NH, and NH2 radical densities are on the order of 1012 cm-3 and the trends with NH3 flow, SiH4 flow, and plasma source current are reported. We present a feasible reaction pathway for the prodn. and loss of the NHx radicals that is consistent with the exptl. results. Furthermore, mass spectrometry revealed that the consumption of NH3 was typically 40%, while it was over 80% for SiH4. On the basis of the measured N densities we deduced the recombination and sticking coeff. for N radicals on a silicon nitride film. Using this sticking coeff. and reported surface reaction probabilities of NH and NH2 radicals, we conclude that N and NH2 radicals are mainly responsible for the N incorporation in the silicon nitride film, while Si atoms are most likely brought to the surface in the form of SiHx radicals. [on SciFinder (R)

The importance of thermal dissociation in CO2 microwave discharges investigated by power pulsing and rotational Raman scattering

The input power of a CO2 microwave plasma is modulated at kHz rate in scans of duty cycle at constant average power to investigate gas heating dynamics and its relation to dissociation efficiency. Rotational temperature profiles obtained from rotational Raman scattering reveal peak temperatures of up to 3000 K, while the edge temperature remains cold (500 K). During the plasma \u27OFF\u27-period, the gas cools down convectively, but remains overall too hot to allow for strong overpopulation of vibrational modes (2200 K in the core). Fast optical imaging monitors plasma volume variations and shows that power density scales with peak power. As dissociation scales with observed peak rotational temperature, it is concluded that thermal processes dominate. A simple 0D model is constructed which explains how higher power density favors dissociation over radial energy transport. Thermal decomposition is reviewed in relation to quenching oxygen radicals with vibrationally excited CO2, to reflect on earlier reported record efficiencies of 90%.</p

How the alternating degeneracy in rotational Raman spectra of CO2 and C2H2 reveals the vibrational temperature

The contribution of higher vibrational levels to the rotational spectrum of linear polyatomic molecules with a center of symmetry (CO2 and C2H2) is assessed. An apparent nuclear degeneracy is analytically formulated by vibrational averaging and compared to numerical averaging over vibrational levels. It enables inferring the vibrational temperature of the bending and asymmetric stretching modes from the ratio of even to odd peaks in the rotational Raman spectrum. The contribution from higher vibrational levels is already observable at room temperature as g e/o=0.96/0.04 for CO2 and g e/o=1.16/2.84 for C2H2. The use of the apparent degeneracy to account for higher vibrational levels is demonstrated on spectra measured for a CO2 microwave plasma in the temperature range of 300-3500 K, and shown to be valid up to 1500 K.</p

Residual gas entering high density hydrogen plasma: rarefaction due to rapid heating

The observations illustrate the general significance of rapid molecule heating in high density hydrogen plasma for estimating molecular processes and how this affects Fulcher spectroscopy

A rotational Raman study under non-thermal conditions in a pulsed CO2 glow discharge

The implementation of \u27in situ\u27 rotational Raman spectroscopy is realized for a pulsed glow discharge in CO2 in the mbar range and is used to study the rotational temperature and molecular number densities of CO2, CO, and O2. The polarizability anisotropy of these molecules is required for extracting number densities from the recorded spectra and is determined for incident photons of 532 nm. The spatiotemporally-resolved measurements are performed in the same reactor and at equal discharge conditions (5-10 ms on-off cycle, 50 mA plasma current, 6.7 mbar pressure) as in recently published work employing \u27in situ\u27 Fourier transform infrared (FTIR) spectroscopy. The rotational temperature ranges from 394 K to 809 K from start to end of the discharge pulse and is constant over the length of the reactor. The discharge is demonstrated to be spatially uniform in gas composition, with a CO2 conversion factor of 0.15 ± 0.02. Rotational temperatures and molecular composition agree well with the FTIR results, while the spatial uniformity confirms the assumption made for the FTIR analysis of a homogeneous medium over the line-of-sight of absorption. Furthermore, the rotational Raman spectra of CO2 are related to vibrational temperatures through the vibrationally averaged nuclear spin degeneracy, which is expressed in the intensity ratio between even and odd numbered Raman peaks. The elevation of the odd averaged degeneracy above thermal conditions agrees well with the elevation of vibrational temperatures of CO2, acquired in the FTIR study

Residual gas entering high density hydrogen plasma: rarefaction due to rapid heating

The interaction of background molecular hydrogen with magnetized (0.4&nbsp;T) high density (1–5&nbsp;×&nbsp;10 20 &nbsp;m −3 ) low temperature (∼3&nbsp;eV) hydrogen plasma was inferred from the Fulcher band emission in the linear plasma generator Pilot-PSI. In the plasma center, vibrational temperatures reached 1&nbsp;eV. Rotational temperatures obtained from the Q( v&nbsp;=&nbsp;1) branch were systematically ∼0.1&nbsp;eV lower than the Q( v&nbsp;=&nbsp;0) branch temperatures, which were in the range of 0.4–0.8&nbsp;eV, typically 60% of the translational temperature (determined from the width of the same spectral lines). The latter is attributed to preferential excitation of translational degrees of freedom in collisions with ions on the timescale of their in-plasma residence time. Doppler shifts revealed co-rotation of the molecules with the plasma at an angular velocity an order of magnitude lower, confirming that the Fulcher emission connects to background molecules. A simple model estimated a factor of 90 rarefaction of the molecular density at the center of the plasma column compared to the residual gas density. Temperature and density information was combined to conclude that ion-conversion molecular assisted recombination dominates plasma recombination at a rate of 1&nbsp;×&nbsp;10 −15&nbsp;m 3&nbsp;s −1 . The observations illustrate the general significance of rapid molecule heating in high density hydrogen plasma for estimating molecular processes and how this affects Fulcher spectroscopy.</p