Multiple ion scattering

The energy spectra and the angular distributions of noble gas ions, reflected from a metal surface, yield information about a number of important properties of this surface. A large number of investigations have been carried out in the past decades, not only to get insight into the interaction mechanism but also to develop methods for applying of the knowledge gained. To obtain information about the outermost surface layer, it appears necessary to use noble gas ions as primary particles, and to detect the scattered particles in the charged state only; the fraction of noble gas ions reaching the detector, after reflection from target atoms in the second layer, is very small because of the high probability of neutralization. However, this is only valid if the initial energy of the incoming ions is relatively low, namely ? 10 KeV. Under certain experimental circumstances it appears justifiable, down to a lower limit of about 20 eV, to conceive the interaction of these ions with the target atoms as single collisions. The relation between the initial energy and the post-collision energy is then very simple if the collision is an elastic one; it depends upon the scattering angle and upon the ratio of the two given masses only and not upon the interaction potential. The shift of the peaks in an energy spectrum is caused by inelastic collisions and is relatively small in the considered energy region. The causes of this shift will be discussed. As opposed to single collisions, the post-collision energies after a multiple collision depend largely upon the interaction potential. Attention will be paid to the search for these potentials. Utilization of the multiple collision phenomenon in the study of surface geometry is hampered by the vibrational motion of the surface atoms. As a result, the energy spectra are blurred and a shift of the so-called quasi-single and quasi-double peaks can occur. Under certain conditions a third peak emerges which can give additional information about the surface vibrations. The intensity of the scattered ions depends upon the cross section for scattering. Recently it has been shown that the relation between this cross section and the initial energy has an oscillating character for certain combinations of incident ions and target atoms. This phenomenon has very important consequences, e.g. in the use of single ion scattering as an analytical tool. To investigate surface structures it appears that single and multiple ion scattering, combined with LEED and AES, can provide valuable information.     

Theory of ion scattering from single crystals

The scattering of He⁺, Ne⁺ and Ar⁺ ions at 600 eV from Ni(110) in the [11̄0] direction is modeled using classical dynamics. The distributions of final scattering angles of the primary ions are displayed as contour plots over the surface impact zone. From the contour plots the regions of the surface that give rise to scattering at specific angles can be isolated. The majority of the inplane scattering arises from collisions of the primary ion with second layer or “valley” atoms. However, to correctly reproduce the experimental energy distribution curves of Heiland and Taglauer (J. Vacuum Sci. Technol. 9 (1971) 620), we must include a simple collision time correction to account for neutralization of the ion beam. This analysis predicts that the ions which collide with second layer atoms of the solid are preferentially neutralized. The energy distributions due to first layer collisions agree well with experiment. We find that a full molecular three dimensional model is needed to describe all of the ion scattering events since for most of the collisions, the ion is simultaneously interacting with at least two atoms of the solid. However, in agreement with other workers we find only a single collision is responsible for the “binary” peak in the energy distribution. In addition the relative scattering intensity at different angles is dependent on having a three-dimensional solid.     

Investigation of the local atomic arrangement on surfaces using low-energy ion scattering

Ions with energies around 1 keV are well suited for detecting atoms on solid surfaces and for investigating their relative arrangement. This is due to the large scattering cross-sections which are of the order of 10^–2Ų/sr. The conceptually simple method is limited by the fact that interaction potentials and, more so, charge exchange processes are only approximately known. Progress in low-energy ion scattering has recently been made by applying special scattering geometries and by using alkali ions, in addition to noble gas ions.Among the successful applications there are studies of the arrangement of atomic layers on supported catalysts, ordered adsorption systems on metal surfaces, surface reconstruction, and surface disordering due to defects and thermal motion. Energy spectra of recoil atoms and ions convey additional information. The fundamental physical features of low-energy ion scattering are discussed on the basis of examples of recent results.     

Analysis of the outermost atomic layer of a surface by low-energy ion scattering

Noble gas ion scattering is used to study the surface of solid targets. It is shown that this technique can be used to obtain a mass spectrum of the first atomic layer of the surface. Since the outermost atoms will largely determine the chemical reactivity and physical properties of the surface, this is an important property for an analytic tool to have. In addition to reflected ions, high-energy recoil ions are sometimes observed.Both the reflected and the recoil ions provide information about the atomic structure of the surface. The various possibilities of ion scattering are demonstrated for bromine, oxygen, sodium and potassium adsorbed on a Si(111) surface, for halogens adsorbed on Ni(100) and for GaP (110), (111) ($\text{111}$) surfaces. The influence of thermal vibrations of surface atoms and of electronic excitation on the spectra is discussed.     

Crystallographic effects in low energy ion scattering due to local ion-atom neutralisation

New experiments on 1 keV ₄He⁺ ion scattering from Ni {100} and Ni {100} (√2 × √2)R45°?O surfaces show azimuthal anisotropies attributable to variations in ion neutralisation probability for different ion trajectories relative to the position of the surface atoms. These effects are shown to be compatible with a simple localised ion-atom neutralisation mechanism. The results indicate that local neutralization is an important process in substrate shadowing in low energy ion scattering studies of adsorbate structures.     

A consistent interpretation of the atomic and electronic structure of the Si(111)−7×7 surface

A simple mechanism leading to the 7×7 reconstruction of the Si(111) surface is proposed. In this model a charge-density wave with the 7×7 pattern acts as the driving force which precipitates the dehybridisation of the surface atoms. The atoms at the surface form terraces of height ～0.3 Å. This small corrugation of the surface gives rise to a much larger (～3 Å) corrugation of the charge in agreement with recent He atom scattering experiments. The model is also in qualitative agreement with photoemission, optical absorption and ion scattering experiments.     

Application of low energy ion blocking for adsorption site determination of Na Atoms on a Cu(111) surface

Ion blocking in the low keV energy range is demonstrated to be a sensitive method for probing surface adsorption sites by means of the technique of time-of-flight scattering and recoiling spectroscopy (TOF-SARS). Adsorbed atoms can block the nearly isotropic backscattering of primary ions from surface atoms in the outmost layers of a crystal. The relative adsorption site position can be derived unambiguously by simple geometrical constructs between the adsorbed atom site and the surface atom sites. Classical ion trajectory simulations using the scattering and recoiling imaging code (SARIC) and molecular dynamics (MD) simulations provide the detailed ion trajectories. Herein we present a quantitative analysis of the blocking effects produced by sub-monolayer Na adsorbed on a Cu(111) surface at room temperature. The results show that the Na adsorption site preferences are different at different Na coverages. At a coverage θ = 0.25 monolayer, Na atoms preferentially populate the fcc threefold surface sites with a height of 2.7 ± 0.1 Å above the 1st layer Cu atoms. At a lower coverage of θ = 0.10 monolayer, there is no adsorption site preference for the Na atoms on the Cu(111) surface.     

Accommodation coefficients for low-energy ions on metal surfaces

The interaction of low-energy ions (E = 3 to 100 eV) with the surface of a solid cannot be treated in terms of gas dynamics. The scattering of particles at an energy of E _o > 20 eV may be explained in terms of binary collisions with the atoms of the target. The validity of the single collision model with free surface atoms for medium energies from 10 to 100 eV and even down to 1 eV was confirmed on the basis of both experimental and computational data. This paper describes experimental studies of the secondary ion emission from the (100) and (110) faces of a Mo single crystal and both experimental and theoretical studies of alkaline ion accommodation coefficient on polycrystalline Mo within the energy range E = 3 to 50 eV with a varying direction of the primary ion beam from normal to the glancing angle of incidence (ρ = 0 to 75°). On the basis of the retarding potential method using a spherical condenser whose central electrode was the target, we measured the energy distribution of secondary ions. Calculations have been performed for the energy of scattered ions and the high energy portion of accommodation coefficient on the basis of single and double binary collisions using the Born-Mayer potential and taking into consideration the influence of adsorption forces at the surface of the target.     

Simulation of multiple scattering in argon ion collisions with an aluminum target at grazing angles of 5°–10°

A model for calculating the atom scattering from a polycrystalline surface consisting of randomly oriented single crystals is proposed. In the calculation it is possible to distinguish the contribution of scattering from any surface layer, and it also takes into account inelastic energy losses in primary ion collisions with target atoms. A comparison with the measurements shows that the proposed model well describes the peak positions in the energy spectra of the scattered atoms. A comparison of the calculated and experimental peak-to-background ratios for scattering from polycrystalline and amorphous targets allows a conclusion to be made about the degree of order of surface layers in the material under investigation.     

Extremely low-energy projectiles for SIMS using size-selected gas cluster ions

A new cluster time-of-flight secondary ion mass spectrometry (TOF-SIMS) was developed using a size-selected gas cluster ion as a projectile. Since a large gas cluster ion can generate many low-energy constituent atoms in a collision with the surface, it causes multiple and ultra low-energy sputtering. The mean kinetic energy of constituent atoms is provided by dividing the acceleration energy of the gas cluster ion by the number of constituent atoms. Therefore, the sputtering can be controlled to minimize the decomposition of sample molecules and substrate material by precisely adjusting the number of constituent atoms (the cluster size) and/or acceleration energy of the gas cluster ion. The cluster size was selected on the basis of the time-of-flight method using two ion deflectors attached along the ion-beam line. A high resolution of 11.7 was achieved for the cluster size/size width (M/ΔM) of Ar-cluster ions.     

Structure investigation of the nitrogen induced Cu(110)−(2 × 3) phase with 180° low energy impact collision ion scattering spectroscopy

The 180° low energy impact collision ion scattering spectroscopy with detection of noble gas neutrals (180°-NICISS) has been used to investigate the nitrogen saturated Cu(110) surface, which is known to exhibit a (2 × 3) diffraction pattern. The nitrogen induced (2 × 3) phase appears to be the result of a surface reconstruction of a new missing row type, in which every third 100 row of Cu atoms of the first layer is missing. The 180° NICISS patterns further indicate within an accuracy of 0.1–0.2 Å, that the double periodicity in the [1 0] direction is not due to the reconstruction of the Cu surface. Its origin has to be found in the arrangement of the N atoms.     

Adsorption of gases studied by secondary ion emission mass spectrometry

The adsorption of an active gas, like oxygen, on the surface of a metal or an alloy leads to an intensification of the positive ion emission produced by sputtering. In the present paper this phenomenon (called chemical ion emission) is observed by blowing the gas on the surface of the sample while it is sputtered. The general features of the chemical effect on M⁺ ion production are discussed in terms of coverage resulting from equilibrium between the rate of atoms sticking to the surface and the sputtering rate of adsorbed atoms, and in terms of ionization probability depending upon the coverage. Examples are given for pure metals (Al, W, Ni) and alloys (NiCr, CuBe, CuAl, …). Attention is drawn to the effects observed on nickel single crystals (100) and (110). At a critical coverage an incorporation process takes place, producing both changes in the work function and in the ionization probability. These results, largely consistent with those obtained by classical methods, show that secondary ion emission can be used for adsorption studies. Finally, investigations of metal-oxygen interaction by the dynamic method (present work) and the static method of secondary ion mass analysis will be discussed and compared.     

A comparison of ion scattering spectra and molecular dynamics simulations at the surface of silicate glasses

Molecular dynamics simulations are correlated with experimental ion scattering spectra to elucidate the surface structure and composition of fused silica and potassium trisilicate glass. The ion scattering spectra and molecular dynamics simulations both show that the oxygen atoms dominate the surface monolayer of fused silica. The ion scattering spectra of fracture surfaces of potassium trisilicate glass show a large potassium signal with little scattering signal from the oxygen or silicon atoms indicating a predominance of potassium in the surface monolayer. This local enrichment of potassium in the surface monolayer is due to their shielding of the charged silicate tetrahedra at the surface. This is also consistent with the simulations.     

Investigation of oxygen adsorption on Cu(110) by low-energy ion bombardment

The interaction of molecular oxygen with a Cu(110) surface is investigated by means of low energy ion scattering (LEIS) and secondary ion emission. The position of chemisorbed oxygen relative to the matrix atoms of the Cu(110) surface could be determined using a shadow cone model, from measurements of Ne⁺ ions scattered by adsorbed oxygen atoms. The adsorbed oxygen atoms are situated 0.6 ± 0.1 Å below the midpoint between two adjacent atoms in a 〈100〉 surface row. The results of the measurements of the ion impact desorption of adsorbed oxygen suggest a dominating contribution of sputtering processes. Ion focussing effects also contributes to the oxygen desorption. The ion induced and the spontaneous oxygen adsorption processes are studied using different experimental methods. Sticking probability values obtained during ion bombardment show a strong increase due to the ion bombardment.     

Estimation of ion scattering by atomic chains on single crystal surfaces

Estimation of ion movement close to atomic chains taking into account the elastic and inelastic energy losses and vacancy type imperfections was performed on the basis of a model of binary interactions of ions with the atoms of a crystal.

An analysis of results shows that at scattering by atomic chains a phenomenon which makes a substantial contribution to scattering by the single crystal surface the inelastic energy losses exceed the single scattering ones by a factor of 5–6.     

Model calculations of atom-surface scattering

The elastic scattering of light mass, thermal-energy atoms from simple surfaces is investigated. The surface is represented by the model of a single planar square array of hard spheres. The effect of the surface potential well is treated semiclassically by simply shifting the energy of the incident atom ; furthermore a constant imaginary term is added to the energy to account for inelastic scattering and adsorption. As in the multiple scattering formalism of LEED the total scattering matrix of the lattice is expanded in terms of the individual gas atom-surface atom t-matrices. Propagation of the incident atom on the surface is described in terms of a one particle Green's function propagator with complex energy. The terms in the multiple scattering series are summed to all orders, by using standard matrix inversion techniques. The size of the matrix to be inverted limits to ten the total number of phase shifts that are included in the calculation. Thermal effects are included through angle dependent Debye-Waller factors.Model calculations have been performed to study the intensity of the specular and the diffracted beams as a function of the angles of incidence. The importance of surface temperature (introduced by the Debye-Waller factors), the incident energy and the depth of the potential well of the gas-surface interaction are discussed. The main feature of the results is the decrease of the intensity of the specular beam in going from glancing incidence to normal incidence and the presence of structure due to the appearance and disappearance of diffracted beams across the surface. The azimuthal behavior of the specular beam is in agreement with experimental observations.     

Ion velocity distribution function in intrinsic gas at cryogenic gas temperatures

The influence of elastic scattering on the ion distribution function in the plasma of an intrinsic gas in weak fields has been considered. An analytical expression valid for cryogenic temperatures of atoms has been obtained. The reduced He⁺–He, Ar⁺–Ar mobilities as functions of the temperature of atoms in a range of 4–1000 K have been calculated in the approximation of the zero field taking into account elastic collisions; the calculated dependences well agree with the available experimental data. It has been demonstrated that elastic collisions play an important role in the formation of the ion distribution function at low temperatures. The results of measurement of the ion mobility in the limit of the zero field at low temperatures can be used to obtain data on the ratio of elastic scattering and resonance charge exchange cross sections.     

Low-energy neon-ion scattering and neutralization on first and second layers of a Ni(001) surface

The scattering and neutralization of 2.4 and 5 keV Ne⁺ ions on the Ni(001) surface have been studied by time-of-flight (TOF) and electrostatic analyzer (ESA) techniques. The scattering yield of neutrals plus ions (by TOF) is strongly dependent on crystal orientation, in one direction being reduced by the shadowing of 2nd layer atoms by 1st layer atoms, or in another being increased by focussing of ions onto the 2nd layer by 1st layer atoms. Ion yields (by ESA) show little of this variation since the ions are largely neutralized on scattering from the second layer. The results thus demonstrate and explain the first layer selectivity of low-energy ion scattering by ESA for a case in which there is no shadowing of second layer atoms by the first layer. On the other hand, the ability to measure and distinguish first and second layer scattering of neutrals and ions by TOF suggests the possibility of composition analysis of individual layers of single crystal alloys and compound semiconductors.     

Dynamics of low-energy electron attachment to formic acid

Low-energy electrons (<2 eV) can fragment gas phase formic acid (HCOOH) molecules through resonant dissociative attachment processes. Recent experiments have shown that the principal reaction products of such collisions are formate ions (HCOO-) and hydrogen atoms. Using first-principles electron scattering calculations, we have identified the responsible negative ion state as a transient pi* anion. Symmetry considerations dictate that the associated dissociation dynamics are intrinsically polyatomic: a second anion surface, connected to the first by a conical intersection, is involved in the dynamics and the transient anion must necessarily deform to nonplanar geometries before it can dissociate to the observed stable products.     

Calculations of low-energy electron diffraction intensities from the polar faces of ZnO

If it is assumed that surface compounds obtained by gas adsorption on metal single crystals faces, are formed by adsorption of atoms on the “sites” of an undisturbed substrate, or of a slightly disturbed substrate, one is lead also to assume that the structures of surface compounds have high symmetries. For well-defined coincidence mesh between the surface compound and the substrate, by applying the 2D space groups (with or without a colored character), information can be obtained concerning the distribution of the adsorbed atoms, or the reconstruction of the substrate. In order to be able to go as far as a complete model, it is necessary to know the concentration of the adsorbed atoms accurately. The hypothesis of a high symmetry has been applied to simple surface compounds: the models of the structures which have been obtained are compared with previously proposed models.