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

The electron-stimulated desorption (ESD) yields and energy distributions for potassium (K) and cesium (Cs) atoms have been measured from K and Cs layers adsorbed at 300 K on oxidized molybdenum surfaces with various degrees of oxidation. The measurements were carried out using a time-of-flight method and surface ionization detector. The ESD appearance threshold for K and Cs atoms is independent of the molybdenum oxidation state and is close to the oxygen 2s level ionization energy of 25 eV. Additional thresholds for both K and Cs atoms are observed at about 40 and 70 eV in ESD from layers adsorbed on an oxygen monolayer-covered molybdenum surface; they are associated with resonance processes involving Mo 4p and 4s excitations. The ESD energy distributions for K and Cs atoms consist of single peaks. The most probable kinetic energy of atoms decreases in going from cesium to potassium and with increasing adsorbed metal concentration; it lies in the energy range around 0.35 eV. The K and Cs atom ESD energy distributions from adlayers on an oxygen monolayer-covered molybdenum surface are extended toward very low kinetic energies. The data can be interpreted by means of the Auger stimulated desorption model, in which neutralization of adsorbed alkali-metal ions occurs after filling of holes created by incident electrons in the O 2s, Mo 4s or Mo 4p levels.     

Electron stimulated desorption induced by the scanning tunneling microscope

The use of the scanning tunneling microscope (STM) as an excitation source and a probe of electron stimulated desorption on the atomic scale is reviewed. The case of H desorption from H-terminated Si(001) is examined in detail. Experimental results on excitation thresholds, desorption cross-sections, isotope effects and site-selectivities are presented. Evidence for mechanisms involving direct electronic and hot ground-state desorption, as well as a novel multiple-vibrational excitation mechanism is discussed. Using the latter mechanism, the ultimate resolution limit of selective single atom desorption is achieved. New results on desorption from Si dihydride, including a proposed mechanism for the STM-induced H/Si(001)-3 × 1 to 2 × 1 conversion, are presented. Possible applications of STM-induced desorption in nanofabrication are considered.     

Electron stimulated desorption of O2 from gadolinia-doped ceria surfaces

The interactions of gas phase oxygen with gadolinia-doped ceria (GDC) surfaces are investigated by electron stimulated desorption (ESD). The primary desorbed cationic species related to molecular oxygen adsorption is O₂⁺. The threshold energy for ESD of O₂⁺ is 13–14 eV, indicating electron impact ionization of molecular oxygen bound at oxygen vacancies. Dependence of O₂⁺ velocities upon incident electron energy and substrate temperature reveals the dominant influence of the effective charge of the adsorption complex. The O₂⁺ velocity distribution is bimodal, and the onset of the faster components at room temperature is related to the balance between fluxes of incident electrons and secondary electron emission, causing effective hole production and neutralization of trapped electrons at surface states.     

Electron stimulated desorption of CO molecules from chemisorbed CO layers on Ru(001): a comparison of the distributions of translational and internal energies

The translational and internal energies of CO desorbed by electron impact from well-ordered × layers on Ru(001) are investigated with time-of-flight techniques and resonance enhanced multiphoton ionization (REMPI) spectroscopy. We discriminate four desorption channels with different translational and internal energy distributions. Translational and vibrational energies are positively, crrelated; rotational and vibrational–translational energies are negatively correlated. The microscopic origins of these correlations are discussed.     

Mechanisms of metastable N2 and Kr electron stimulated desorption from N2---Kr double layer and mixed films

Desorption of metastable particles from layered and mixed films, composed of N₂ and Kr, is induced by the impact of 6–50 eV monoenergetic electrons. From yield functions and time-of-flight analysis of the metastable particles emanating from these films, N*₂ and Kr* are identified as the desorbing species. Basic mechanisms responsible for their desorption are discussed. It is suggested that the desorption of Kr* arises from dissociation of transitory [Kr·N₂]* excimers. The desorption of N*₂ can arise from cavity expulsion, intramolecular vibrational energy transfer (with or without prior electronic excitation energy transfer from Kr excitions to N₂) and the dissociation of [Kr·N₂]* excimers.     

Electron-stimulated desorption of cesium atoms from cesium layers deposited on a germanium-coated tungsten surface

The yield and energy distribution of Cs atoms from cesium layers adsorbed on germanium-coated tungsten were measured, using the time-of-flight technique with a surface-ionization-based detector, as a function of the energy of bombarding electrons, germanium film thickness, the amount of adsorbed cesium, and substrate temperature. The threshold for the appearance of Cs atoms is ～30 eV, which correlates well with the germanium 3d-level ionization energy. As the electron energy increases, the Cs atom yield passes through a broad maximum at ～120 eV. For germanium film thicknesses from 0.5 to 2 monolayers, resonance Cs yield peaks were observed at electron energies of 50 and 80 eV, which can be related to the tungsten 5p and 5s core-level ionization energies. As the cesium coverage increases, the Cs atom yield passes through a flat maximum at monolayer coverage. The energy distribution of Cs atoms follows a bell-shaped curve. With increasing cesium coverage, this curve shifts to higher energies for thin germanium films and to lower energies for thick films. The Cs energy distribution measured at a substrate temperature T = 160 K exhibits two bell-shaped peaks, namely, a narrow peak with a maximum at ～0.35 eV, associated with tungsten core-level excitation, and a broad peak with a maximum at ～0.5 eV, deriving from the excitation of the germanium 3d core level. The results obtained can be described within a model of Auger-stimulated desorption.     

Configuration dependence of photon stimulated ion desorption from methyl ester compounds induced by core excitation

Photon stimulated ion desorption (PSID) from methyl ester terminated self-assembled monolayer (MHDA-SAM, HS(CH₂)₁₅COOCH₃) and methyl mercaptoacetate (MA, HSCH₂COOCH₃) on Ag has been investigated using soft X-ray in the C and O K-edge regions. In MHDA-SAM on Ag, site-selective ion desorption has been clearly observed at resonant core excitations of C_1s, O_1s(OCH₃) → σ^∗(OCH₃) and O_1s(OCH₃) → σ^∗(COCH₃). Ion intensity in MA on Ag is obviously reduced for (n = 1-3) at C_1s, O_1s(OCH₃) → σ^∗(OCH₃) excitations, and no site-selective reaction at O_1s(OCH₃) → σ^∗(COCH₃) excitations has been observed. These reactions may be influenced by configurational difference of reactive sites. It is suggested that surface effects on the selective reaction due to positioning methyl ester group near the surface plays an important role.     

Electron-stimulated desorption of cesium atoms from cesium layers adsorbed on tungsten coated by a gold film

Physics of the Solid State - The yield and energy distributions of cesium atoms escaping in electron-stimulated desorption (ESD) from cesium layers adsorbed on tungsten coated by a gold film have...     

Transmission of low-energy (< 10 eV) O ions through Au films on TiO2(110)

In an attempt to identify the fundamental processes that influence ion transport through metallic surface layers, we have studied the transmission of O⁺ ions through discontinuous Au films adsorbed on TiO₂(110). A low energy (< 10 eV) O⁺ ion beam is generated via electron stimulated desorption when an Au-dosed TiO₂(110) substrate is bombarded with a focused 250 eV electron beam. Low energy ion scattering data indicate that Au evaporated under ultrahigh vacuum conditions at 300 K forms three-dimensional clusters on TiO₂(110). As the Au coverage increases, the formation of Au clusters on TiO₂(110) blocks a fraction of the TiO₂ surface and the O⁺ yield is attenuated. However, for high coverages (≥30% Au covered substrate) the O⁺ signal decreases at a faster rate than the TiO₂ open area fraction. We attribute the attenuation of the O⁺ yield for high Au coverages mainly to blocking of O⁺ by Au clusters, to deflection of trajectories by the image force between ions and Au clusters, and to charge transfer between desorbing O⁺ and neighboring Au clusters.     

Zone specificity in low energy electron stimulated desorption of Cl from reconstructed Si(1 1 1)-7 × 7:Cl surfaces

Diffraction in electron stimulated desorption has revealed a propensity for Cl⁺ desorption from rest atom vs. adatom areas and unfaulted vs. faulted zones of Cl-terminated Si(1 1 1)-(7 × 7) surfaces. We associate the 15 eV ± 1 eV threshold with ionization of Si-Cl σ-bonding surface states and formation of screened two-hole states with Si 3s character. Similar specificity is observed from A and B reconstructions. This can be due to reduced screening in unfaulted regions and increased hole localization in Si back-bonds within faulted regions.     

The use of highly organized molecular films as electron scattering targets: spectroscopic and desorption measurements of selective bond rupture in organic films

In-situ FT-IR spectroscopic and desorption detection schemes have been used to observe, characterize and quantify electron-induced modifications of self-assembled monolayers (SAMs) of organic molecules chemisorbed to highly ordered metal surfaces. In the case of n-alkanethiol SAMs/Au(111) surfaces, the cross-sections for C---H bond rupture at the terminal methyl groups have onsets with incident energies near E_i7 eV and well-resolved maxima at E_i10 eV, indicating that dissociative electron attachment is the primary step of the excitation-dissociation process. The systematic differences between the depletion of the ---CH₃ and ---CH₂-functional groups on the surface, detected using infrared spectroscopy, show that molecular desorption of entire n-alkane chains is not a significant process, despite the S---Au(111) bond being the weakest of the system. The dissociation cross-sections increase with increasing chain length, indicating that the dissociation dynamics are strongly affected by the distance to the metal substrate, presumably via a dipole-damping process; we have used this behaviour to estimate that the excited state lifetimes for these systems are 2–10 fs. Chemisorption of “target” species to stable metal substrates appears to be a general approach for the study of electron-molecule interactions and condensed phase processes in molecular systems at ambient temperatures.     

Modeling of laser-induced excitation and ionization in cesium atoms

A theoretical model is presented to describe kinetics of the plasma formation in cesium undergone to resonant laser excitation (D_1,2 line). The model is based on a rate equations approach where the following populations are considered: ground state (6s level), laser excited level (6p), a series of high excited levels close to the ionization limit, and the electron density. We show temporal evolution of these populations and provide an explanation of the kinetic governing the ionization path-ways. Moreover, we compare the behavior of the electron density as a function of the laser power with the experimental data by Hunnenkens et al. This comparison for the electron density with irradiation time is proved a good agreement with the experimental results.     

Electron stimulated desorption of CO from

The electron impact behavior of CO adsorbed on was investigated. The desorption products observed were neutral CO, CO⁺, and O⁺. After massive electron impact residual carbon, C/W = 0.15, but not oxygen was also found, suggesting that energetic neutral O, not detected in a mass analyzer must also have been formed. Formation of β-CO, i.e., dissociated CO with C and O on the surface was not seen. The total disappearance cross section varies only slightly with coverage, ranging from 9 × 10 ⁻¹⁸ cm² at low to 5 × 10⁻¹⁸ cm² at saturation (CO/W = 0.75). The cross section for CO⁺ formation varies from 4 × 10⁻²² cm² at satura to 2 × 10⁻²¹ cm² at low coverage. That for O⁺ formation is 1.4 × 10⁻²² cm² at saturation and 2 × 10⁻²¹ cm² Threshold energies are similar to those found previously [J.C. Lin and R. Gomer, Surf. Sci. 218 (1989) 406] for and CO/Cu₁/W(110) which suggests similar mechanisms for product formation, with the exception of β-CO on clean W(110). It is argued that the absence or presence of β-CO in ESD hinges on its formation or absence in thermal desorption, since electron impact is likely to present the surface with vibrationally and rotationally activated CO in all cases; β-CO formation only occurs on surfaces which can dissociate such CO. It was also found that ESD of CO led to a work function increase of the remaining Pd₁/W(110) surface of 500 meV, which could be annealed out only at 900 K. This is attributed to surface roughness, caused by recoil momentum of energetic desorbing entities.     

Effect of deposition of samarium atoms on the electron-stimulated desorption of cesium and samarium atoms from the surface of tungsten coated by gold and cesium

It has been shown that deposition of Sm atoms on W(100) surface coated by several monolayers of gold and cesium affects noticeably the yield of Cs atoms in electron-stimulated desorption (ESD) from this surface. The measurements have been performed by the time-of-flight method with a surface-ionization detector. The paper reports on the first observation of ESD of Sm atoms from the tungsten surface coated by layers of gold and cesium. The ESD threshold for Sm atoms, E _e = 57 eV, coincides with that for Cs atoms and corresponds to the energy of the Au 5p _3/2 core level. The dependence of the ESD yield of Sm atoms on the bombarding electron energy E _e follows a resonance pattern in the form of a narrow peak located in the range 57 ≤ E _e ≤ 66 eV. Deposition of Sm atoms at room temperature (～300 K) reduces (by a factor of about two) the ESD yield of Cs atoms for 600 s, and deposition of Sm atoms at 160 K reduces the ESD of Cs atoms down to zero already for 270 s. This difference finds explanation in the study of the change the structure of the top layer of the (Au + Cs)/W surface coating undergoes under cooling of the surface from 300 to 160 K.     

Far-out surface science: radiation-induced surface processes in the solar system

Interplanetary space is a cosmic laboratory for surface scientists. Energetic photons, ions and electrons from the solar wind, together with galactic and extragalactic cosmic rays, constantly bombard surfaces of planets, planetary satellites, dust particles, comets and asteroids. Many of these bodies exist in ultrahigh vacuum environments, so that direct particle–surface collisions dominate the interactions. In this article, we discuss the origins of the very tenuous planetary atmospheres observed on a number of bodies, space weathering of the surface of asteroids and comets, and magnetospheric processing of the surfaces of Jupiter's icy satellites. We emphasize non-thermal processes and the important relationships between surface composition and the gas phase species observed. We also discuss what laboratory and computational modeling should be done to support the current and future space missions––e.g. the Genesis mission to recover solar wind particles, the Cassini mission to probe Saturn, the Europa Lander mission to explore the subsurface ocean hypothesis, and the Pluto/Kuiper Express to sample the outer reaches of the solar system.     

Electron stimulated desorption of oxygen from nickel

Electron Stimulated Desorption (ESD) of O⁺ ions from oxygen-covered Ni(100) has been investigated at 390 K and 500 eV primary energy. The ion energy distribution is found to peak at 7.5 eV and to extend to 11 eV, over our whole exposure range (0–1000 L). The 7.5 eV peak height as a function of exposure shows that desorption takes place both in the chemisorption and the oxidation region. Emission of O⁺ occurs preferentially along the surface normal, with a base width of ≈ 60°. No azimuthal structure is observed. Additional electron energy dependent measurements clearly show a threshold near the oxygen 2s level.     

Desorption of metastable species induced by electronic excitation at the surface of solid krypton with physisorbed hydrogen

The effect of the physisorbed hydrogen molecules on the electron stimulated desorption of metastables from the surface of solid Kr was investigated. At the clean surface of solid Kr, the desorption of Kr metastables occurs only through an excimer dissociation mechanism. Physisorption of hydrogen molecules causes the following effects: (1) the total desorption yield of the metastable species increased by an order of magnitude or more; (2) metastable Kr, which is probably desorbed through the cavity ejection mechanism, emerges; (3) metastable Kr by excimer dissociation is also enhanced; and (4) a new metastable species, which seems to be composed of metastable hydrogen molecule, appears.     

Radiation stabilization of U5+ in CaO matrix and its thermal stability: Electron paramagnetic resonance and thermally stimulated luminescence studies

Electron paramagnetic resonance (EPR) evidence is presented for the radiation stabilization of pentavalent uranium in CaO matrix. From the theoretical predictions ofg value for U⁵⁺ in axial symmetries, it was concluded that U⁵⁺ at Ca²⁺ site is associated with a second neighbour charge compensating Ca²⁺ vacancy. EPR measurements also revealed the presence of Mn²⁺, Mn⁴⁺ and Cu²⁺ impurities in the samples. The thermal stability of U⁵⁺ was investigated using EPR and thermally stimulated luminescence (TSL) techniques. The TSL and EPR studies on gamma irradiated uranium doped calcium oxide samples had shown that the intense glow peak at 540 K is associated with the reduction in the intensity of EPR signal of U⁵⁺ ion around this temperature. This peak is associated with the process U⁵⁺+hole→U^6+*→U⁶⁺+hv. The activation energy for this process was determined to be 1.4eV.     

Electron-stimulated desorption of europium atoms from an oxidized tungsten surface

The yield of europium atoms in electron-stimulated desorption from Eu layers adsorbed on the surface of oxidized tungsten was studied with a surface-ionization detector as a function of the incident-electron energy, surface coverage by europium, and degree of tungsten oxidation. The yield of Eu atoms measured as a function of electron energy exhibits a distinct resonant character with peaks at electron energies corresponding to europium and tungsten core-level ionization energies. The peaks associated with the europium ionization reach a maximum intensity at europium coverages less than 0.1 and decrease subsequently to zero with increasing coverage, while the peaks due to tungsten ionization pass through the maximum intensity at a monolayer europium coverage. The coverage corresponding to the maximum europium atom yield grows with increasing tungsten oxidation. The results obtained are accounted for by the formation of the europium and tungsten core excitons. In the first case, the particles desorb in the reverse motion toward the surface of the oxidized tungsten; in the second, they desorb as a result of repulsion between the tungsten core exciton and the EuO molecule.