On the Kinetics of the Active Zone of the Stationary SF6 Beam Discharge Plasma

The paper deals with the impact of intensive electron attachment on the kinetics of the electrons in the active zone of the stationary band-like beam discharge plasma in SF₆ which is an alternative useful plasma medium for “dry etching”. The energy distribution of the electrons in this plasma was obtained by numerically solving the Boltzmann equation which includes apart from elastic collisions, different exciting collision processes, attachment in electron collisions, direct ionization, the ambipolar loss of electrons, Coulomb interaction between electrons and of electrons with ions and the power input to the electrons by the turbulent electric field. In particular, due to the needed fulfilment of the consistent electron particle balance, for an extended region of the turbulence energy density in this plasma a large impact on the electron kinetics of the intensive electron attachment, which is the prevailing electron loss process, was found enforcing independent of the turbulence energy density always a large power input to the electrons, smooth and only slowly decreasing energy distributions even in the energy region of direct ionization.     

Experiments on clusters

In this contribution we discuss four different types of experiments that have been conducted at molecular beams of neutral clusters. The size of particularly stable sodium chloride clusters and their corresponding geometrical structure is inferred from intensity anomalies in mass spectra. This information is obtained either for charged or for neutral clusters depending on whether the clusters are ionized by electron impact or by multiphoton absorption. The important role of fragmentation in mass spectrometry of xenon clusters is revealed by multiphoton ionization; dissociative reactions occurring on the time scale of 10⁻⁷ s with respect to the ionizing event can be analyzed. The solvation energy of negatively charged carbon dioxide clusters as a function of cluster size is obtained from electron attachment spectra. A resonance in the ion yield close to zero eV electron energy signifies that all clusters except for the monomer feature a positive electron affinity. An analysis of the kinetic energy of fragment ions, originating from delayed dissociation of triply charged carbon dioxide clusters, reveals that the size distribution of their fission fragments is extremely symmetric.     

Low energy electron attachment to C<Subscript>60</Subscript>

Low energy electron attachment to the fullerene molecule (C₆₀) and its temperature dependence are studied in a crossed electron beam–molecular beam experiment. We observe the strongest relative signal of C₆₀ anion near 0 eV electron energy with respect to higher energy resonant peaks confirming the contribution of s-wave capture to the electron attachment process and hence the absence of threshold behavior or activation barrier near zero electron energy. While we find no temperature dependence for the cross-section near zero energy, we observe a reduction in the cross-sections at higher electron energies as the temperature is increased, indicating a decrease in lifetime of the resonances at higher energies with increase in temperature.     

Generation of cold electrons in the downstream region of a microwave plasma source with near boundary resonances for production of negative ions

A microwave driven multicusp plasma based volume negative ion source equipped with a magnetic filter is developed. Instead of employing any electrodes or current carrying filaments, microwaves of frequency 2.45 GHz is used to generate plasma by resonance heating mechanisms namely the electron cyclotron resonance (ECR) and upper hybrid resonances (UHR), occurring near the boundary plasma layers. The principal process of negative ion production in hydrogen is dissociative attachment of low energy (0.5–1.0 eV) electrons to vibrationally excited neutral molecules generated from high energy (15–20 eV) electron impact. The source therefore necessitates two distinct spatial regions (a) production and (b) attachment chambers; which would contain electrons with optimum cross section for the aforementioned processes. A biased grid after the magnetic filter further helps to lower down the electron temperature to ≤1 eV which is favorable for the dissociative attachment process.     

Untersuchung der unelastischen Wechselwirkung langsamer monoenergetischer Elektronen mit einfachen Kohlenwasserstoff-Molekülen I.Elektronenanlagerungs-Wirkungsquerschnitte in Abhängikeit von der Elektronenenergie und vom Molekülaufbau

Investigation of the Inelastic Interaction of Slow Monoenergetic Electrons with Simple Hydrocarbon Molecules. I. Dependence of the Electron Attachment Cross Sections on Electron Energy and on Molecular Structure The formation of negative ions from a series of simple hydrocarbons was studied experimentally via an interaction of hydrocarbon molecules with monoenergetic electrons in the range of 0–15 eV. The ion formation is characterized by means of the attachment cross section in dependence on electron energy. Negative ions were formed as well by dissociative electron attachment as by direct electron attachment. The electron attachment is depending on electron energy, molecular seize, and on the number of unsaturated C-C-bonds in the molecule. The formation processes are discussed and the role of negative hydrocarbon ions in the plasma is estimated.     

The nonequilibrium behavior of electron swarms in nonuniform fieldsin SF6

The behavior of electron swarms in nonuniform electric fields in SF₆ has been analyzed by Monte Carlo simulation. Decreasing and increasing electric field configurations have been studied. The spatial variations of the electron mean energy, drift velocity, and ionization and attachment coefficients are calculated for different field slopes and compared with the values calculated assuming equilibrium field conditions. It is found that the nonequilibrium behavior depends on the ratio of the field slope to pressure, and not on the field slope alone. The mean energy and drift velocity are almost the same as the equilibrium values, while the ionization and attachment coefficients show significant nonequilibrium features. The electron and ion distributions along the uniformly decreasing and increasing fields have also been studied     

Clear experimental evidence for p-wave attachment-threshold behavior in electron attachment to chlorine molecules

Using the laser photoelectron attachment method and chlorine molecules in a seeded supersonic beam, we have measured the energy dependence of the cross section for dissociative electron attachment (DA; Cl- formation) over the range 0-195 meV with an energy width of about 1 meV. Our data provide the first clear experimental evidence for p-wave behavior of a DA cross section near zero energy and are in good overall agreement with recent theoretical predictions.     

Microstructural analysis of the cementation process during soiling on glass surfaces in arid and semi‐arid climates

To investigate the soiling behavior of solar energy systems like photovoltaics or concentrated solar power, glass samples were exposed to outdoor conditions in Doha, Qatar for one month. Soil formation on the glass was characterized at microstructural level using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Further, elemental analysis of the crust was done with energy‐dispersive X‐ray spectroscopy (EDX). Small fibrous structures were found on the glass surface and dust particles, providing evidence of a cementation process leading to a strong adhesion of airborne dust particles. In contrast to the common perception, that cementation occurs via the precipitation of salt (sodium chloride) these needle structures were found to be mainly composed of oxides of Si, Mg and Al. This indicates that cementation processes in desert regions are enhanced by the growth of fibrous clay minerals.

Cross section of cemented dust particle, connected via small needles to the glass surface.     

Mass spectrometric investigation of anions formed upon free electron attachment to nucleobase molecules and clusters embedded in superfluid helium droplets

Here we report the first mass spectrometric study of negative ions formed via free electron attachment (EA) to nucleobases (NBs) embedded in helium clusters. Pure and mixed clusters of adenine and thymine have been formed by pickup of isolated NB molecules by cold helium droplets. In contrast to EA of isolated molecules in the gas phase we observe a long-lived parent anion NB- and, in addition, parent cluster ions NB-n up to size n=6. Moreover, we show that a low energy electron penetrating into a doped helium droplet causes efficient damage of the embedded nucleobases via resonant, site selective, dissociative electron attachment.     

Isotope effects in vibrational excitation and dissociative electron attachment of DCl and DBr

The results of calculations of vibrational excitation and dissociative electron attachment cross-sections of DCl and DBr are reported. The calculations are based on the nonlocal resonance model for electron-HCl/HBr scattering. The cross-sections for many initial rovibrational target states were calculated both for the hydrogenated and the deuterated compounds. The calculations reveal an unexpected result: the vibrational excitation cross-section of the deuterated molecule may in some cases be (significantly) larger than that of the hydrogenated compound. This effect is observed when the target molecule is initially excited to a vibrational state the energy of which is close to the threshold of dissociative attachment. Rotational excitation of the target molecule plays a similar role. Isotope effects in dissociative electron attachment are also discussed.     

Low energy electron attachment to formic acid

Using a high resolution electron energy monochromator low energy electron attachment to formic acid is studied for the first time by means of mass spectrometric detection of the product anions. The largest dissociative electron attachment (DA) cross-section produces HCOO ^-+H with weaker channels for OH^- and O^- becoming apparent at higher incident energies. Received 23 January 2002 and Received in final form 9 February 2002 Published online 13 September 2002     

Labyrinthine island growth during Pd/Ru(0001) heteroepitaxy

Using low energy electron microscopy we observe that Pd deposited on Ru only attaches to small sections of the atomic step edges surrounding Pd islands. This causes a novel epitaxial growth mode in which islands advance in a snakelike motion, giving rise to labyrinthine patterns. Based on density functional theory together with scanning tunneling microscopy and low energy electron microscopy we propose that this growth mode is caused by a surface alloy forming around growing islands. This alloy gradually reduces step attachment rates, resulting in an instability that favors adatom attachment at fast advancing step sections.     

Bond- and site-selective loss of H- from pyrimidine bases

Electron attachment to gas phase thymine and uracil leads to H- loss within a broad and structured feature in the energy range between about 5 and 12 eV consisting of 4 overlapping resonances. By using thymine and uracil methylated at the N1 and N3 positions, respectively, and taking into account recent results from partly deuterated thymine, we find that by tuning the electron energy, H- loss turns out to be not only bond selective, i.e., (C-H) versus (N-H) bonds, but also site selective (N1 versus N3 site). Such a bond and site selectivity by energy has not been observed before in dissociative electron attachment. Implications for the mechanism of strand breaks observed in plasmid DNA are considered.     

The Rate Constant for Dissociative Electron Attachment to Ozone Revisited

The rate constant for dissociative electron attachment to ozone has been derived over the energy range from about 0 to 10 eV using recently measured and also corrected cross section data. The new rate constant data sets for two partial dissociative channels, as well as for the total dissociative electron attachment, are compared with previously reported values, and existing discrepancies are discussed.     

Dissociative electron attachment to phosphoric acid esters: the direct mechanism for single strand breaks in DNA

We use dibutyl phosphate to simulate the behavior of the phosphate group in DNA towards the attack of low energy electrons. We find that the compound undergoes effective dissociative electron attachment within a low energy resonant feature at 1 eV and a further resonance peaking at 8 eV. The dissociative electron attachment (DEA) reactions are associated with the direct cleavage of the C-O and the P-O bond but also the excision of the PO-, PO3-, H2PO3- units. For the phosphate group coupled in the DNA network these reactions represent single strand breaks. We hence propose that the most direct mechanism of single strand breaks occurring in DNA at subexcitation energies (< 4 eV) is due to DEA directly to the phosphate group.     

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     

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.     

丝氨酸异构体的电子-分子形状共振态及其解离动力学理论研究

Shape resonances of electron-molecule system formed in the low-energy electron attachment to four low-lying conformers of serine (serine 1, serine 2, serine 3, and serine 4) in gas phase are investigated using the quantum scattering method with the non-empirical model potentials in single-center expansion. In the attachment energy range of 0-10 eV, three shape resonances for serine 1, serine 2, and serine 4 and four shape resonances for serine 3 are predicted. The one-dimensional potential energy curves of the temporary negative ions of electron-serine are calculated to explore the correlations between the shape resonance and the bond cleavage. The bond-cleavage selectivity of the different resonant states for a certain conformer is demonstrated, and the recent experimental results about the dissociative electron attachment to serine are interpreted on the basis of present calculations.     

A Model for the Bulk Plasma in an RF Chlorne Discharge

A model has been constructed to describe the electrical characteristics of the central bulk plasma region in a 13.56-MHz parallel-plate discharge in chlorine at pressures of about 1 torr. This region is modeled as a volume-controlled plasma with the electron balance dominated by single-step electron-impact ionization and attachment and with the electron energy distribution function in equilibrium with the local instantaneous electric field. Relationships between the ionization frequency, the attachment frequency, the electron drift velocity, and the electric field are provided by solutions of the Boltzmann equation for mixtures of Cl2 and Cl which result from Cl2 dissociation. From a measured current waveform and Cl2/Cl density ratio, the model generates the local electric-field waveform, the time-varying electron density, and the power density in the central portion of the bulk plasma. The calculated time-averaged power input per unit discharge length compares well with experimentally determined values.