High resolution study of anion formation in low-energy electron attachment to SF<Subscript>6</Subscript> molecules in a seeded supersonic beam

Using two variants of the Laser Photoelectron Attachment (LPA) method involving a differentially-pumped, seeded supersonic beam (0.05% and 12.5% of SF₆ molecules in helium carrier gas, nozzle temperatures T₀= 300–600 K, stagnation pressures p₀= 1–5 bar) and mass spectrometric ion detection, we have investigated the energy dependence of anion formation in low-energy electron collisions with SF₆ molecules at high energy resolution. Using the standard LPA method, the yield for SF₆^- as well as SF₅^- and F^- anions was studied with an energy width around 1 meV over the electron energy range 0–200 meV. In addition, a variant of the LPA method with extended energy range (denoted as EXLPA) was developed and applied to measure the yield for SF₆^- and SF₅^- formation over the energy range 0–1.5 eV with an energy width of about 20 meV. The cross-section for formation of SF₆^- decreases by five orders of magnitude over the range 1–500 meV and is only weakly dependent on nozzle temperature. The yield for SF₅^- formation shows — apart from a weak zero energy peak which grows strongly with rising temperature — a broad maximum (located around 0.6 eV for T₀= 300 K and shifting to lower energies with rising T₀) and a monotonical decrease towards higher energies. SF₅^- attachment spectra taken at elevated temperatures exhibit changes with rising stagnation pressure which directly reflect rovibrational cooling of the SF₆ molecules with rising pressure. The SF₅^-/SF₆^- intensity ratio at near-zero energy and the low-energy shape of the broad peak in the SF₅^- spectra are used as thermometers for the internal temperature of the SF₆ molecules in the seeded supersonic beam which (at p₀= 1 bar) are found to be 50–100 K lower than the nozzle temperature. The energy dependence of the yield for F^- formation is similar to that for SF₆^-, but the F^- signals are three to four orders of magnitude lower than those for SF₆^-; in view of the rather high endothermicity of F^- formation the origin of the F^- signals is discussed in some detail.     

Nondissociative electron attachment to molecules and clusters

We present results of effective range theory calculations of nondissociative electron attachment to SF₆ molecules and CO₂ clusters. The first process is strongly influenced by the SF^-₆ virtual state, and the second by vibrational Feshbach resonances associated with electron capture by the long-range polarization field of the cluster with simultaneous vibrational excitation of one molecular unit. We also study how both processes depend on the initial vibrational excitation of the target. We obtain a noticeable dependence of the attachment cross-section on the symmetric stretch vibration of SF₆, although it does not lead to a significant temperature dependence at low electron energies.     

The influence of vibrational excitation on the burning voltage of a pulsed electric discharge in HF laser working media

The burning voltages of an intermediate pressure self-sustained volume discharge (SSVD) in SF₆ and SF₆-C₂H₆ mixtures irradiated by a 10.6 μm pulse TEA CO₂ laser, have been measured on varying the laser fluences over a wide range. The delay between the voltage application and the laser pulse onset is 4 μs, and the laser pulse lasts ∼3 μs. The considerable rise observed in the discharge voltages with increasing absorbed specific laser radiation energy, is due to electron attachment to vibrationally excited molecules of SF₆. Different processes of relaxation of the vibrational energy stored in SF₆ molecules are analyzed and the relevant characteristic times are numerically assessed. The gas heating process owing to vibration-translation energy exchange is qualitatively described in terms of the “thermal explosion”. The relation between the “explosion” and delay times determines the peculiarities of electron attachment to vibrationally excited SF₆ molecules. The burning voltages of a submicrosecond non-irradiated SSVD in the above-mentioned media versus the specific electric energy deposited are also measured. They are compared to those of a laser-illuminated SSVD at commensurable specific laser energy depositions. It is concluded that electron attachment to the discharge-produced vibrationally excited SF₆ molecules is not capable of noticeably affecting the discharge voltages of a submicrosecond non-irradiated SSVD. PACS 42.55 Ks; 52.80     

Total electron scattering cross section of C3F6O at the intermediate-energy region for developing an alternative insulation gas to SF6

Perfluoro methyl vinyl ether (C₃F₆O) is a promising alternative gas to SF₆ for switching applications in the power industry. We measured the total electron scattering cross section (TCS) of C₃F₆O in the intermediate energy region from 15 to 90 eV using a magnetized electron beam apparatus. The overall TCS values were less than 20.8 × 10⁻¹⁶ cm² within the measuring energy region. The measured and observed TCS exhibited some features, a steep increase before 30 eV, the highest value near 30 eV, and a gradual decrease after 30 eV. The total uncertainty was evaluated as 3.5–8.5%, depending on the incident electron energies. These first measurement data of C₃F₆O are useful for understanding both the discharging characteristics and identifying the insulation properties and arc-extinguishing.     

Photolysis of SF6 adsorbed on Si(111)-7 × 7 by monochromatic soft X-ray

Continuous-time photoelectron spectroscopy (PES) and photon-exposure-dependent photon-stimulated desorption (PSD) were employed to investigate the monochromatic soft X-ray-induced dissociation of SF₆ molecules adsorbed on Si(111)-7 × 7 at 30 K (SF₆ dose = 3.4 × 10¹³ molecules/cm², ～ 0.5 monolayer). The photon-induced evolution of adsorbed SF₆ was monitored at photon energies of 98 and 120 eV [near the Si(2p) edge], and sequential valence-level PES spectra made it possible to deduce the photolysis cross section as a function of energy. It was found that the photolysis cross sections for 98 and 120 eV photons are ～ 2.7 × 10^? 17 and ～ 3.7 × 10^?17 cm², respectively. The changes in the F^? and F⁺ PSD ion yields were also measured during irradiation of 120 eV photons. The photon-exposure dependencies of the F^? and F⁺ ion yields show the characteristics: (a) the dissociation of adsorbed SF₆ molecules is ascribable to the substrate-mediated dissociations [dissociative attachment (DA) and dipolar dissociation (DD) induced by the photoelectrons emitting from the silicon substrate]; (b) at early stages of photolysis, the F^? yield is mainly due to DA and DD of the adsorbed SF₆ molecules, while at high photon exposure the F^? formation by electron capture of the F⁺ ion is likely to be the dominant mechanism; (c) the F⁺ ion desorption is associated with the bond breaking of the surface SiF species; (d) the surface SiF is formed by reaction of the surface Si atom with the fluorine atom or F^? ion produced by scission of S–F bond of SF_n (n = 1–6) species.     

NF3预放电参数的研究

本文采用脉冲漂移管——质谱仪方法研究了在准分子激光和电气设备中有重要应用的NF₃气体的预放电参数,包括电子的电附系数、电附速率、负离子种类和质量以及负离子的迁移率等,还测量了电附速率与电子平均能量的关系。 关键词：     

Dissociative electron attachment to CF2Cl2

Using a recently constructed high resolution crossed electron/molecular beam apparatus consisting of a hemispherical electron monochromator and a quadrupole mass spectrometer we have measured the relative production cross sections for CI^– and F^– via electron attachment to CF₂Cl₂. The relative Cl^– cross section is placed on an absolute scale by reference to an absolute rate coefficient using a calibration method involving integration of the measured anion signal. The most efficient Cl^– production process is at about zero energy and its magnitude is resolution limited. The present high resolution value of 6 × 10^–16 cm² compares well with an earlier value reported by Chen and Chantry. A second peak is detected at around 0.8 eV in accordance with some of the earlier beam and swarm measurements. The observed production of F^– has an appearance energy of 1.9 eV and the energy of maximum cross section is 3.36 eV, the latter value comparing well with several previous studies.     

Volume discharge excited by an electron beam in an Ar-SF6 mixture I. Beam-controlled discharge

Beam-controlled current flow is investigated in an Ar-SF₆ mixture at atmospheric pressure. It is shown that electron attachment to SF₆ molecules plays an important role in the charge-dparticle balance, and the attachment constant is determined. The discharge energy properties are studied.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 72–76, July, 1978.     

Plasma with two-negative ions and immobile dust particles: planar and non-planar ion-acoustic wave propagation

By using the hydrodynamic equations of positive and two negative ions, Boltzmann electron density distribution, and Poisson equation with immobile positive/negative dust particles, a cylindrical Korteweg-de Vries (CKdV) equation is derived for small but finite amplitude ion-acoustic waves. At the critical total negative ion concentration and/or the critical density rate of the second-negative ions, the pulses collapse at this limit as nonlinearity fails to balance dispersion. Then the CKdV equation is not appropriate to describe the system. Therefore, the modified CKdV (MCKdV) and extended CKdV (ECKdV) equations are derived at the critical plasma compositions and in the vicinity of the critical plasma compositions, respectively. The physical parameters of two plasma environments (e.g., Xe⁺–F^-–SF₆^-_{6}^{-} and Ar⁺–F^-–SF₆^-_{6}^{-} plasmas) are examined on the wave phase velocity and the nonlinear localized pulse profile. The latter should satisfy necessary condition to exist. The localized pulse of Ar⁺–F^-–SF₆^-_{6}^{-} plasma is much spiky than Xe⁺–F^-–SF₆^-_{6}^{-} plasma. Thus, the mass ratio of the negative-to-positive ions is focused upon and it emphasizes to play an important role on the pulse profile. Dependence of the geometrical divergence on the pulse profile is also investigated, which indicates that the localized pulse damps with time. The implications of our results agrees with the experimental observations.     

Electron energy distribution function in a hollow-cathode glow discharge in mixtures of nitrogen with electronegative gases

The electron energy distribution function (EEDF) in a hollow-cathode glow discharge in mixtures of nitrogen with electronegative gases is investigated. It is shown that small admixtures of SF₆ or CCl₄ to nitrogen significantly increase the number of electrons in the energy range 2–6 eV, which corresponds to the inverse part of the EEDF. In nitrogen with small admixtures of F₂ or NF₃, the EEDF differ slightly from that calculated for pure nitrogen. The EEDF in these mixtures substantially depends on electron attachment to electronegative gas molecules.     

The influences of gas and electron temperatures on electron attachment in gas electrical discharges

Various electron attachment processes are reviewed, emphasising the way in which the rates and products of some selected reactions vary with the attaching gas temperatureT _g, the temperature,T _e, and the energy of the attaching electrons. The examples illustrating the variety of reactions are the efficient dissociative attachment reaction to CCl₄, attachment to SF₆ which involves both dissociative and non-dissociative attachment, attachment to CHCl₃ which requires activation energy, and attachment to CCl₃Br which results in both Cl- and Br- product ions. A model has been presented which is able to quantitatively explain the difference influences ofT _g andT _e on the rates of some of these reactions. Also described are the unusually efficient attachment properties of the fullerene molecules C₆₀ and C₇₀ as revealed by our FALP experiments, noting that these molecules have potential importance as efficient suppressers of electrical breakdown through gases such as those used to insulate high voltage devices. We emphasise throughout this paper the importance of an understanding of the separate influences of gas and electron temperature on attachment reactions for the modelling of practical gas discharge media such as etchant plasmas. We dedicate this paper to Professor Jan Janča on the occasion of his sixtieth birthday in recognition of his major contributions to gas discharge physics.     

Data and modeling of negative ion transport in gases of interest for production of integrated circuits and nanotechnologies

We review techniques to prepare, evaluate and apply sets of cross section and transport data for negative ions that are required for the modeling of collisional non-equilibrium plasmas used for processing of microelectronic circuits. We collect and discuss the transport coefficients and cross section sets.We have compiled data for negative ions in CF₄ and CF₄-related negative ions in rare gases. In addition, we consider data for F⁻ and CF₃⁻ in rare gases. Furthermore, we analyze the cross sections of halogen negative ions in rare gases and other molecules. This is followed by the data for SF₆ related ions in SF₆ and in rare gases. The cross section for scattering of O⁻ in O₂ has been derived from the transport data and used to make calculations of the transport properties. Finally we give a brief discussion of the availability of the data for H⁻ ions in H₂. We have derived cross sections in several cases but the basic aim is to show the basic features of transport coefficients. In particular we discuss the need to represent properly some details such as the non-conservative nature of transport coefficients and the anisotropy of diffusion. Application of approximate theories and representations of cross sections are also discussed.     

ESR study on the structure of the ethylene radical cation stabilized in frozen SF6 and some fluoroalkanes: An evidence for a twisted structure

ESR spectra of the ethylene radical cation were detected at cryogenic temperatures in SF₆, C₂F₆ and C₃F₈. From the unusually small hyperfine couplings estimated for¹H and¹³C, it has been shown that the ethylene radical cation has a non-planar structure with a torsional angle in the range of 8°–23°. Upon annealing the sample at a temperature above 93 K, the ethylene radical cation in SF₆ changed into a monofluoroethyl radical through charge recombination with fluoride anion or SF ₆ ^? .     

A study of the electron quenching of excimers in a KrF* laser excited by a coaxial electron beam

Measurements of the output energy, the optical pulse length and the build-up time of the laser pulse, obtained with a coaxially e-beam pumped KrF^* laser, were performed varying the total gas fill pressure, the F₂ content and the e-beam current from 1–5 bar, 0.1–0.8% and 13.3–26.6 kA, respectively. The maximum specific extraction energy amounts to 64 J/l. The large range of measurements, especially at low F₂ concentrations, reveals the necessity to extend the kinetics of the F₂ chain in the usual computer model. With the introduction of electron quenching of KrF^* and ArF^* by dissociative attachment the predictions are also for low F₂ concentration in agreement with experiments.     

悬浮型微波共振探针在电负性容性耦合等离子体中电子密度的测量

本文首先利用悬浮型微波共振探针测量了Ar等离子体的电子密度,并与朗缪尔双探针的测量结果进行了比较,表明了微波共振探针在低密度等离子体测量的可行性.对40.68 MHz单射频容性耦合Ar/SF₆和SF₆/O₂等离子体的测量结果表明:电负性气体SF₆掺入Ar等离子体显著降低了等离子体电子密度,但随着增加SF₆的流量,电子密度表现为缓慢下降;而O₂掺入SF₆等离子体中,电子密度则随着O₂流量的增加表现为持续的下降.另外,40.68 MHz/13.56 MHz双频激发的SF₆/O₂容性耦合离子体的电子密度并不随低频功率的变化而变化.本文对上述的实验现象进行了初步的解释.     

Study of the SF 6 − ion lifetime in a rf quadrupole trap

We use an experimental apparatus to study SF ₆ ^– ions lifetimes. These ions are created inside a quadrupole rf trap by charge exchange between highly excited argon atoms and SF₆ molecules. Ions are observed from 200 s up to 15 ms after their creation time. In order to explain experimental results, collisions with SF₆ molecules and the influence of ionized core of argon are taken into account. A part of SF ₆ ^– ions are stabilized by the last influence. These results evidence a radiative stabilization phenomenon, the lifetime of which is estimated at about 5 ms.Equipe de Recherche associée au C.N.R.S. 0898Laboratoire associé au C.N.R.S. 0282     

Observation of simultaneous ν1(SF6) + ν3(NF3) and ν2(SF6) + ν3(NF3) transitions enhanced by the resonance dipole-dipole interaction with the ν1 + ν3 and ν2 + ν3 states of the SF6 molecule

IR spectra of the solution of SF₆ molecules in liquid NF₃ at 84 K have been recorded. In a solvent transmission window of 1500–1750 cm⁻¹, two wide absorption bands with pronounced peaks in the high-frequency part are observed. The profile of these bands is explained by the influence of the resonance dipole-dipole (RDD) interaction of the states of the simultaneous transition ν₁(SF₆) + ν₃(NF₃) and ν₂(SF₆) + ν₃(NF₃) with the states (ν₁ + ν₃) and (ν₂ + ν₃) of the SF₆ molecules, respectively. The use of three isotopic modifications ³²SF₆, ³³SF₆, and ³⁴SF₆ has allowed us to vary the resonance detuning and thus to change the strength of the RDD interaction. With the liquid near the melting point being represented as a close-packed cubic crystal, the profile was calculated and its spectral characteristics were determined. The frequencies of the main peaks coincide with the experimental values accurate to the error.     

Non-Maxwellian Electron Velocity Distribution Resulting from Electron-SF6 Attachment Collisions

A model reaction system is considered consisting of a heat bath of argon atoms (c) and small concentrations of SF₆-molecules (m) and electrons (e) (number densities: n_e ? n_m ? n_c). Within the model the time behaviour of the electron velocity distribution function is studied under the influence of elastic electron-argon collisions and electron SF₆ attachment collisions. On the basis of the distribution function time-dependent macroscopic quantities (kinetic electron temperature. nonequilibrium rate constant of the attachment reaction) are calculated.     

Dissociative electron attachment to CF<Subscript>3</Subscript>Cl

We have performed an extensive experimental study of dissociative electron attachment (DEA) to CF₃Cl. Exploiting the recently developed velocity slice imaging technique, we have recorded both angular distributions and kinetic energy release of the product fragment anions of Cl⁻ and F⁻. The DEA process is dominated by the formation of resonances the symmetry of which have been explored and compared with earlier measurements. A new resonance has been identified in the F⁻ formation channel.     

Energy and pressure dependence of the CO2 laser induced dissociation of sulfur hexafluoride

Low pressure SF₆ with its isotopes in natural abundance was irradiated by a pulsed CO₂ laser operated on theP20 line (10.6 μm band). Dissociation yields of³²SF₆ and³⁴SF₆ were measured separately. If the radiation is focussed into the cell, the dissociation yield is proportional to the 3/2 power of the laser energy, as was derived under general conditions and confirmed experimentally. The reaction probabilityP(Φ), the fraction of molecules dissociated by an energy flux Φ, was measured using parallel light. For both isotopes,P(Φ) saturates at high energy flux close toP=1. At a lower flux (2 J cm⁻²), the dissociation probability of³²SF₆ displays a threshold, whereas the dissociation probability of³⁴SF₆ is a very steep function of Φ over the whole range of fluxes.P(Φ) at the higher energy flux was measured in a cavity absorption cell, in which up to 80% of the molecules were dissociated by a single pulse. Below 0.2 mbar SF₆ the dissociation yields for both isotopes are pressure independent. Above 2 mbar the isotopic selectivity is completely lost. Addition of hydrogen always decreases the dissociation yields.