Desorption of cesium from pyrolytic graphite basal surfaces with strongly non-equilibrium behaviour

A field reversal kinetic study of the desorption of Cs⁺ and Cs from a graphite basal surface (ZYB graphite) gives results that neither follow the Saha-Langmuir equation, nor fulfil the Schottky energy cycle. The non-equilibrium behaviour is due to a lowering of the rate of the ionic desorption, while the neutral desorption at low temperatures is described by normal rate parameters. At high temperatures, the neutral desorption rate constant is dominated by vertical diffusion into the bulk. The unexpected behaviour of the ion desorption is probably coupled to vertical diffusion too. It is suggested that the desorbing ions leave the surface from special positions on the surface, which are reached during the migration out from the bulk.     

Nuclear depolarization of alkali beams during ionization on surfaces

The depolarization of atomic alkali beams (⁶Li,⁷Li,²³Na) during ionization on oxygen covered hot metal surfaces (Ir, Mo, Re, W) has been investigated. The polarization of the ionized beams was detected by a beam foil experiment. The temperature dependence of the observed depolarization is interpreted as due to a relaxation process caused by the interaction of the nuclear moments with fluctuating fields on the surface.     

Thermal desorption and surface lifetimes of bromine and iodine adsorbed on an ionizer of LaB6

Thermal desorption of bromine and iodine from an ionizer surface made of cold pressed and sintered LaB₆ powder has been studien in the temperature interval 800–1300°C. A new technique, where the extraction field is accelerating only during short intervals, has been developed to monitor separately the neutral desorption of readily ionized elements. The technique has been combined with the modulated beam and the modulated voltage methods for measurements of residence times and ionization efficiencies. It has also been combined with the temperature programmed desorption method used for determination of the Arrhenius parameters of desorption. The following values were obtained for l_? and l₀, the activation energies of ionic and neutral desorption, and for the corresponding pre-exponential factors C and D (D = 4C) for halogens): Bromine: l_? = 3.8 eV, l₀ = 4.3 eV, C = 2.0 × 10¹³ s^?1; Iodine: l_? = 3.4 eV, l₀ = 3.7 eV, C = 1.1 × 10¹³ s^?1. The ionization efficiencies measured at 1100°C, 0.95 for bromine and 0.7 for iodine, correspond well to what is given by the Saha-Langmuie equation using a work function of 2.7 eV. All measurements were performed with the number of adsorbed particles well below 10¹⁷ atoms/m². For higher coverages l_? was found to increase linearly by about 0.15 eV for an adsorption of 10¹⁸ atoms/m².     

Field ionization of ozone

Experimental results on the field ionization of ozone at an iridium surface using a magnetic sector atom-probe FIM show that at the lowest field of ~1.5 V/Å only 25% of all ions produced are O⁺₃, while O⁺₂ and a small percentage of O⁺ indicate field induced dissociation of ozone and recombination of atomic oxygen into O₂. At high fields and free space ionization, O⁺₂ is predominant, while the atomic oxygen as a dissociation product escapes without being ionized and cannot be detected. Using pure oxygen as an imaging gas in the FIM, O⁺₂ ions do not dissociate under the same conditions.     

Application of the surface ionization for the detection of secondary particles in the secondary-ion mass spectrometry (SIMS)

A method for postionization in the course of ion sputtering that is based on surface ionization of the sputtered particles is developed. The estimations show that the method allows a significant increase in the sensitivity of the secondary-ion mass spectrometry for several elements. Nonadditive increase in the sputtering coefficient of indium is experimentally studied using the surface-ionization method of postionization when the number of atoms in projectile clusters Bi _m ⁺ (m = 1–7) increases at energies 2–10 keV. Such a scheme for the detection of neutral particles can be used in alternative methods for the surface analysis, in particular, laser evaporation of surface and electron-stimulated desorption.     

The adsorption and desorption of oxygen on the Pt(110) surface; A thermal desorption and LEED/AES study

The interaction of oxygen with a Pt(110) crystal surface has been investigated by thermal desorption mass spectroscopy, LEED and AES. Adsorption at room temperature produces a β-state which desorbs at ~800 K. Complete isotopic mixing occurs in desorption from this state and it populates with a sticking probability which varies as (1 ? θ)², both observations consistent with dissociative adsorption. The desorption is second order at low coverage but becomes first order at high coverage. The saturationcoverage is 3.5 × 10¹⁴ mol cm^?2. The spectra have been computer analysed to determine the fraction desorbing by first (β₁) and second (β₂) order kinetics as a function of total fractional coverage θ using this fraction as the only adjustable parameter. The β₁ desorption commences at θ ～ 0.25 and β₁ and β₂ contribute equally to the desorption at saturation. The kinetic parameters for β₁ desorption were calculated from the variation of peak temperature with heating rate as ν₁ = 1.7 × 10⁹ s^?1 and E^≠₁ = 32 kcal mole^?1 whereas two different methods of analysis gave consistent parameters ν₂ = 6.5 × 10^?7 cm² mol^?1 s^?1 and E^≠₂ = 29 and 30 kcal mole^?1 for β₂ desorption. The kinetics of desorptior are discussed in terms of the statistics for occupation of near neighbour sites. While many fea tures of the results are consistent with this picture, it is concluded that simple models considering either completely mobile or immobile adlayers with either strong or zero adatom repulsion are not completely satisfactory. The thermal desorption surface coverage has been correlated with the AES measurements and it has been possible to use the AES data for PtO as an internal standard for calibration of the AES oxygen coverage determination. At low temperature (170 K) oxygen populates an additional molecular α-state. Adsorption into the α- and β-states is competitive for the same sites and pre-saturation of the β-state at 300 K excludes the α-state. This, together with the AES observation that the adsorption is enhanced and faster at 450 than 325 K suggests a low activation energy for adsorption into the β-state.     

Molecular beam surface ionization detection: I. Absolute ionization coefficients and work function of “low work function” Pt(8%W) surfaces

Absolute ionization coefficients β have been measured for K on a “low work function” PtW surface by the field reversal method. The modified Langmuir-Saha equation has been fitted by a least-squares procedure to the static surface ionization values as a function of temperature, and ionization coefficients have been computed from the best fit parameter values. The agreement between the two methods is satisfactory at low temperatures, within 9% at β = 0.7–0.8, with the largest error probably lying in the coefficients from static ionization. By a comparison with other methods used for determinations of β < 1 the field reversal method is shown to be as accurate as the apparently most reliable method used for such work, the microbalance method, first used by Schroen 1963. The Richardson plots for the probably graphite coated metal surface are curved. It is shown, that the curvature does not depend on the choice of the spectral emissivity or other possible experimental errors. The only explanation for the curved plots, which appears to be consistent with the experiments, is a true non-linear temperature dependence of the work function, probably due to the semiconducting surface layer. Non-linear leastsquares fits have been used to fit the theoretical expressions to the electron emission current, the surface ionization current and also to a combined quantity, in which the temperature dependence of the work function has been effectively removed. The nature of the PtW surface and some earlier, inconsistent investigations of this surface are also discussed.     

Studies of positron moderation in surface charged rare gas solids

With the use of surface charging the efficiency of a rare gas solid (RGS) positron (e⁺) moderator has been determined as a function of applied electric field. This technique relies on electron (e⁻) capture by adsorbed molecular species such as oxygen. These studies have shown that the emitted e⁺ yield from an RGS moderator can be enhanced by at least a factor of three by negative surface charging or almost totally reduced by positive surface charging. Even under ultra high vacuum conditions significant surface charging of RGS films can occur and such effects should be considered if moderating materials of this type are to be used.     

Isotopic ratio of evaporated ions,critical ionization distances,and ionization regions in the process of the field evaporation of molybdenum at high temperatures

A magnetic mass spectrometer with a field ion source has been used to study the steady-state field evaporation of molybdenum at a temperature of 1000–2000 K. Ions of all seven molybdenum isotopes have been observed in the process of evaporation; only low-charge ions Mo⁺² and Mo⁺ have been detected. The critical ionization distances and ionization regions for single- and double-charge Mo ions have been identified based on the measured ion energies and the experimentally determined intensity of the evaporation field. It has been demonstrated that ions are produced in the process of field evaporation of surface atoms at certain distances from the emitter surface in a very narrow spatial region.     

溴乙烷分子的质量分辨阈值光谱

利用单色双光子(1C2P)技术得到了高精度的溴乙烷分子的质量分辨阈值(MATI)光谱，精确给出了溴乙烷分子的绝热电离势和离子振动频率.从中性基态到离子基态两个自旋-轨道分量X₁ ²E_1/2和X₂ ²E_1/2的绝热电离势分别为83097±3 cm^-1和85452±3 cm^-1，离子基态两个自旋-轨道分量的间隔为2355±6 cm^-1，这些值与文献报道值符合得较好，且精度更高.溴乙烷分子的单色双光子质量分辨阈值光谱展现出丰富的振动结构，这是在溴乙烷分子相继吸收两个光子的过程中波包在解离态势能面上演化的结果.以已有的离子振动谱标识为参考，以中性分子的振动频率为基础，标识了溴乙烷分子的质量分辨阈值光谱，发现观测到的振动模几乎都和溴乙烷分子的解离运动有关，其中还包括一些非全对称模. 关键词： 质量分辨阈值光谱 振动模 单色双光子零动能光谱技术 溴乙烷     

Desorption of carbonium ions from zeolite surfaces; A comparison of reactive surface ionization with field ionization

In comparison with field ionization on platinum the thermal desorption of surface carbonium ions from zeolite surfaces has been investigated mass spectrometrically. CaY-zeolites — forming carbonium ions — were supported by Pt filaments or Pt emitter tips where hydrocarbons are chemisorbed in a non-ionic form. Thermal ion desorption at very low external fields has been observed with stable carbonium ions of triphenylmethyl compounds Ph₃ C-X. This ion desorption was achieved on CaY zeolite surfaces and occurred in the order X  Br > X  Cl > X  OH; however, no ions could be obtained with X  H and X  COOH up to 825°K. On Pt surfaces high fields were required for desorbing molecular ions.     

Cesium ion desorption from graphite surfaces: Kinetics and dynamics of diffusion and desorption steps

The field reversal method was used to study the kinetics of Cs and Cs⁺ desorption from a pyrolytic graphite basal surface. Double-exponential decay was observed especially at high temperatures. Desorption of ions using an external flux from a Cs beam gave the primary rate parameters 2.60 eV and 5.3 × 10¹⁴ s⁻¹, at T = 1100–1600 K. The secondary rate parameters were 0.28 eV and 2.2 × 10⁵ s⁻¹, observed at T = 1250–1600 K. Due to the high sensitivity of the method, the kinetics of desorption of the previously absorbed Cs, diffusing out from the bulk crystal, could also be studied. These processes were more complex, giving the primary rate parameters 1.87 eV and 1.1 × 10¹⁴ s⁻¹, and the secondary rate parameters 2.07 eV and 1.97 × 10¹¹ s⁻¹ for T = 1400–1600 K. The variation of the primary and secondary rates and the field reversal peak heights as functions of retarding field time were also studied, as well as the field reversal peak variation with temperature. These results, as well as the ones found in previous studies of this system, indicate the existence of three adsorbed states on the more or less polycrystalline graphite surface. One apparently ionic state correlates with the diffusing state in the crystallites and with ionic states outside the surface. Conversion processes to and from this state, induced by the external field, were also observed.     

Molecular and atomic oxygen adsorption on the kinked Pt(321) surface

Oxygen adsorption and desorption were characterized on the kinked Pt(321) surface using high resolution electron energy loss spectroscopy, thermal desorption spectroscopy and Auger electron spectroscopy. Some dissociation of molecular oxygen occurs even at 100 K on the (321) surface indicating that the activation barrier for dissociation is smaller on the Pt(321) surface than on the Pt(111) surface. Molecular oxygen can be adsorbed at 100 K but only in the presence of some adsorbed atomic oxygen. The dominance of the v(OO) molecular oxygen stretching mode in the 810 to 880 cm^?1 range indicates that the molecular oxygen adsorbs as a peroxo-like species with the OO axis parallel or nearly parallel to the surface, as observed previously on the Pt(111) surface [Gland et al., Surface Sci. 95 (1980) 587]. The existence of at least two types of peroxo-like molecular oxygen is suggested by both the unusual breadth of the v(OO) stretching mode and breadth of the molecular oxygen desorption peak. Atomic oxygen is adsorbed more strongly on the rough step sites than on the smooth (111) terraces, as indicated by the increased thermal stability of atomic oxygen adsorbed along the rough step sites. The two forms of adsorbed atomic oxygen can be easily distinguished by vibrational spectroscopy since oxygen adsorbed along the rough step sites causes a v(PtO) stretching mode at 560 cm^?1, while the v(PtO) stretching mode for atomic oxygen adsorbed on the (111) terraces appears at 490 cm^?1, a value typical of the (111) surface. Two desorption peaks are observed during atomic oxygen recombination and desorption from the Pt(321) surface. These desorption peaks do not correlate with the presence of the two types of adsorbed atomic oxygen. Rather, the first order low temperature peak is a result of the fact that about three times more atomic oxygen can be adsorbed on the Pt(321) surface than on the Pt(111) surface (where only a second order peak is observed). The heat of desorption for atomic oxygen decreases from about 290kJ/mol (70 kcal/mol) to about 196 kJ/mol (47 kcal/mol) with increasing coverage. Preliminary results concerning adsorption of molecular oxygen from the gas phase in an excited state are also briefly discussed.     

Positron scattering and ionization of neon atoms—theoretical investigations

Although positron scattering with inert gas atoms has been studied in theory as well as in experiment, there are discrepancies. The present work reports all the major total cross sections of e+-neon scattering at incident energies above ionization threshold, originating from a complex potential formalism. Elastic and cumulative inelastic scatterings are treated in the complex spherical e+-atom potential. Our total inelastic cross section includes positronium formation together with ionization and excitation channels in Ne. Because of the Ps formation channel it is difficult to separate out ionization cross sections from the total inelastic cross sections. An approximate method similar to electron-atom scattering has been applied to bifurcate ionization and cumulative excitation cross sections at energies from threshold to 2000 eV. Comparisons of present results with available data are made. An important outcome of this work is the relative contribution of different scattering processes, which we have shown by a bar-chart at the ionization peak.     

Electron-stimulated desorption of europium atoms from the surface of oxidized tungsten: Concentration dependence of the low-energy peak

The nature of electron-stimulated desorption of europium atoms Eu⁰ at low incident electron energies E _e (～30 eV) and the specific features of the dependence of the yield of europium atoms Eu⁰ on their concentration on the surface of oxidized tungsten are discussed. The crucial stage is found to be the primary event of vacancy creation in the inner 5p shell of the europium adatom. As follows from estimates, only the first of the two possible ionization scenarios (intratomic electron transfer to the outer shell of the Eu adatom or ejection of the knocked-out electron into vacuum) results in Eu⁰ desorption. The concentration threshold of the Eu⁰ yield is determined.     

Absolute cross-section measurements of inner-shell ionization

Cross section ratios for K- and L-shell ionization of thin silver and gold targets by positron and electron impact have been determined at projectile energies of 30–70 keV. The experimental results are confirmed by calculations in plane wave Born approximation (PWBA) which include an electron exchange term and account for the deceleration or acceleration of the incident projectile in the nuclear field of the target atom. We report first absolute cross sections for K- and L-shell ionization of silver and gold targets by lepton impact in the threshold region. We have measured the corresponding cross sections for electron (e^–) impact with an electron gun and the same experimental set-up.     

Deep impurity-center ionization by far-infrared radiation

An analysis is made of the ionization of deep impurity centers by high-intensity far-infrared and submillimeter-wavelength radiation, with photon energies tens of times lower than the impurity ionization energy. Within a broad range of intensities and wavelengths, terahertz electric fields of the exciting radiation act as a dc field. Under these conditions, deep-center ionization can be described as multiphonon-assisted tunneling, in which carrier emission is accompanied by defect tunneling in configuration space and electron tunneling in the electric field. The field dependence of the ionization probability permits one to determine the defect tunneling times and the character of the defect adiabatic potentials. The ionization probability deviates from the field dependence e(E) ∝ exp(E ²/E _c ² ) (where E is the wave field, and E _c is a characteristic field) corresponding to multiphonon-assisted tunneling ionization in relatively low fields, where the defects are ionized through the Poole-Frenkel effect, and in very strong fields, where the ionization is produced by direct tunneling without thermal activation. The effects resulting from the high radiation frequency are considered and it is shown that, at low temperatures, they become dominant. Fiz. Tverd. Tela (St. Petersburg) 39, 1905–1932 (November 1997)     

Electron-stimulated desorption of potassium and cesium atoms from an oxidized molybdenum surface

The yield and energy distributions of potassium and cesium atoms emitted in electron-stimulated desorption (ESD) from a molybdenum surface, oxidized to different extent and maintained at 300 K, have been measured by the time-of-flight technique with a surface ionization detector. The ESD threshold for potassium and cesium atoms lies around 25 eV, irrespective of molybdenum oxidation state. In the case of molybdenum coated by an oxygen monolayer, secondary thresholds at ∼40 and ∼70 eV have been observed, as well as atomic energy distribution tailing down to very low energies. The most probable kinetic energies of the atoms are a few tenths of one eV. The results are explained within a model involving Auger neutralization of the adsorbed alkali metal ions after the filling of the 2s O, 4s Mo, and 4p Mo core holes. The possibility of ESD of a neutral species as a result of oxide-cation core-level ionization has been demonstrated for the first time. Fiz. Tverd. Tela (St. Petersburg) 39, 758–761 (April 1997)     

Electron-stimulated desorption of atomic oxygen from polycrystalline Ag

Emission of neutral oxygen atoms from an oxygen-charged polycrystalline Ag wire has been examined by using electron-stimulated desorption (ESD) in conjunction with threshold ionization detection (appearance potential). A quadrupole mass spectrometer (QMS) was used to detect the neutral oxygen atoms, but the ionizer was operated in the appearance potential (AP) mode to make it possible to distinguish the oxygen atoms from products formed by collision of the oxygen atoms with the walls. Loss of the reactive oxygen atoms was also minimized by enclosing the ESD chamber in fused silica. With a primary beam energy of 100 eV, the ESD cross section for oxygen atom desorption was found to be 7 × 10^-19cm² at 100 °C, and an ESD threshold was found to exist below 34 eV. Flash desorption of oxygen allowed estimation of the bulk diffusivity of oxygen through polycrystalline Ag. A value of 2.64 × 10^-6cm²s^-1 at 500 °C was obtained.     

Effects of the Chodura sheath on tungsten ionization and emission in tokamak divertors

The decay of the electric potential in the sheath region in tokamak divertors occurs on a scale length on the order of the main ion gyroradius (Chodura sheath) due to magnetic fields lines intersecting the divertor plates at grazing incidence. As a consequence, high-Z impurities like tungsten ionize within the sheath region in attached plasma conditions. The modification of the electron distribution in the sheath region must thus be taken into account to accurately model ionization and emission of impurities within the sheath region. To that end, an analytical expression of the distribution of the vertical ionization path for impurities sputtered from divertor plasma-facing components is derived. This expression is then used to estimate the fraction of neutral impurities ionizing within the sheath and the average vertical ionization path, and to derive an effective SXB (the number of ionizations per emitted photon) coefficient which includes the effects of the variation of the electron distribution in the sheath region. These results are applied to tungsten impurities sputtered from divertor plates. It is shown that the SXB coefficient for neutral tungsten is significantly reduced in high-density attached divertor plasma conditions (n_e ≳ 5 × 10¹³ cm⁻³) because of the ionization of neutral tungsten well within the sheath region.