Development of secondary ion mass spectroscopy using medium energy C60 ion impact

In this paper, we report time-of-flight (TOF) secondary ion mass spectroscopy using primary C₆₀ ions with an energy range from several tens of keV to several hundreds of keV. Application of the spectroscopy to the analysis of a poly(amino acid) film revealed that characteristic peaks, necessary for identification of the amino acid in proteins, show higher intensities for medium energy C₆₀ (120 keV and 540 keV ) impacts than those for low energy C₆₀ (30 keV ) impacts. This finding demonstrates that medium energy C₆₀ ion impacts are useful for highly sensitive characterization of amino acids.     

Competition of terrace and step-edge sputtering under oblique-incidence ion impact on a stepped Pt(1 1 1) surface

Using molecular-dynamics simulation, we study the sputtering of a Pt(1 1 1) surface under oblique and glancing incidence 5 keV Ar ions. For incidence angles larger than a critical angle ?_c, the projectile is reflected off the surface and the sputter yield is zero. We discuss the azimuth dependence of the critical angle ?_c with the help of the surface corrugation felt by the impinging ion. If a step exists on the surface, sputtering occurs also for glancing incidence ?>?_c. We demonstrate that for realistic step densities, the total sputtering of a stepped surface may be sizable even at glancing incidence.     

On the emission of MoCs molecular ions from Cs irradiated molybdenum surface

The present paper deals with the emission of atomic and molecular ions from elemental molybdenum surface under Cs⁺ bombardment to explore the MCs⁺ formation mechanism with changing Cs surface coverage. Integrated count of MoCs⁺ shows a monotonic increase with increasing primary ion energy (1-5 keV). Change in MoCs⁺ intensity is attributed to the variation of surface work function ? and cesium surface concentration c_Cs due to varying impact energies. Variation of c_Cs has been obtained from the expression, c_Cs ∝ 1/(1 + Y) where Y is the elemental sputtering yield estimated from TRIM calculations. Systematic study of the energy distributions of all species emerging from Mo target has been done to measure the changes in surface work function. Changing slopes of the leading parts of Cs⁺ energy distributions suggest a substantial depletion in surface work function ? with decreasing primary ion energies. Δ? shows a linear dependence on c_Cs. The maximum reduction in surface work function Δ?_max = 0.69 eV corresponds to the highest value of c_Cs = 0.5. A phenomenological model, based on the linear dependence of ? on c_Cs, has been employed to explain the MoCs⁺ data.     

Assessment of approximations for efficient topography simulation of ion beam processes: 10 keV Ar on Si

The main assumption of existing efficient topography simulations is that sputtering is a local process that depends only on the angle of incidence and not on the detailed shape of the surface. If redeposition is considered, sputtered atoms are redeposited and cause no further sputtering when they hit another part of the surface. Furthermore the angular distribution of sputtered atoms follows a cosine law. If ion reflection is considered, ions do not lose energy during backscattering. Using binary collision simulations (IMSIL) and comparing them with results obtained by a topography simulator (IonShaper^®) we show that all these assumptions need refinement for the simulation of nanostructures except the neglect of sputtering by sputtered atoms. In addition we show that a nonlocal model is essential for ion beam induced deposition of narrow structures.     

Study of ion emission from a germanium crystal surface under impact of fast Pb ions in channeling conditions

A thin germanium crystal has been irradiated at GANIL by Pb beams of 29 MeV/A (charge state Q_in = 56 and 72) and of 5.6 MeV/A (Q_in = 28). The induced ion emission from the sample entrance surface was studied, impact per impact, as a function of Q_in, velocity v_in and energy loss ΔE in the crystal. The Pb ions transmitted through the crystal were analyzed in charge (Q_out) and energy using the SPEG spectrometer. The emitted ionized species were detected and analyzed in mass by a time-Of-flight multianode detector (LAG). Channeling was used to select peculiar ΔE values in Ge and hence peculiar Pb ion trajectories close to the emitting entrance surface. The experiment was performed in standard vacuum. No Ge emission was found. The dominating emitted species are H⁺ and hydrocarbon ions originating from the contamination layer on top of the crystal. The mean value 〈M〉 of the number of detected species per incoming Pb ion (multiplicity) varies as (Q_in/v_in)^p, with p values in agreement with previous results. We have clearly observed an influence of the energy deposition ΔE in Ge on the emission from the top contamination layer. When selecting increasing values of ΔE, we observed a rather slow increase of 〈M〉. On the contrary, the probabilities of high multiplicity values, which are essentially connected to fragmentation after emission, strongly increase with ΔE.     

Analysis of the Auger neutralization of He at Cu surfaces in low energy ion scattering

Recently, strong crystal effects in P⁺ were observed for He⁺ and Cu in the Auger neutralization regime, with differences in the ion fraction by up to a factor of three non-equivalent Cu surfaces. In this contribution, it is shown that these findings can quantitatively be described within the jellium model assuming perpendicular velocity scaling of P⁺.     

On the origin of the LEIS signal in TOF- and in ESA-LEIS

The ion fraction analysis of ⁴He⁺ ions backscattered from various faces of copper single crystals is performed by using time-of-flight (TOF) and electrostatic analyzer (ESA) low-energy ion scattering (LEIS) techniques. When an experiment that integrates over 2π azimuth (typical ESA-LEIS setup) is used, the yield of ions backscattered from the Cu(1 1 0) surface may be given by projectiles penetrated much deeper than just one or two monolayers. The threshold energy for reionization processes for ⁴He⁺ and Cu found earlier by TOF-LEIS is experimentally confirmed by ESA-LEIS.     

Molecular dynamics simulations to explore the effect of chemical bonding in the keV bombardment of Si with C60, Ne60 and Ne60 projectiles

Depth profiling experiments using secondary ion spectrometry (SIMS) have shown effects that are characteristic to the pairing of the projectile with a Si target. Previous molecular dynamics simulations demonstrate that this unusual behavior is due to the fact that strong covalent bonds are formed between the C atoms in the projectile and the Si atoms in the target, which result in the implantation of carbon into the solid. The focus of this paper is to understand how the formation of chemical bonds affects the net sputtered yield. The results of molecular dynamics simulations of the keV bombardment of Si with C₆₀, Ne₆₀ and ¹²Ne₆₀ at normal incidence are compared over a range of incident kinetic energies from 5 to 20 keV. The net yields with Ne₆₀ and ¹²Ne₆₀ are significantly greater than with C₆₀ at all incident kinetic energies, with ¹²Ne₆₀ having the largest values. Application of the mesoscale energy deposition footprint (MEDF) model shows that the initial deposition of energy into the substrate is similar with all three projectiles. Snapshots of the initial pathway of the projectile atoms through the substrate show a similar lateral and vertical distribution that is centered in the region of the energy footprint. Therefore, the reason for the reduced yield with C₆₀ is that the C atoms form bonds with the Si atoms, which causes them to remain in the substrate instead of being sputtered.     

SIMS analysis of xenon and krypton in uranium dioxide: A comparison of two models of gas-phase ionisation

Reasonable detection limits in secondary ion mass spectrometry (SIMS) analysis of inert gases in solids may be achieved by gas-phase ionisation. For Xe in UO₂ Desgranges and Pasquet (D&P) have recently reported that the ion intensity can be enhanced significantly using ion bombardment in combination with an oxygen jet directed at the sputtered area. A similar effect was reported by Portier et al. for Kr in UO₂. The enhancement was attributed to ionisation by an interaction with oxygen atoms and molecules (D&P model). The proposed mechanism is at variance with a recently outlined model of gas-phase ionisation involving charge transfer between the ejected atoms and the incoming primary ions. The purpose of this study was to clarify these contradictory views by a reanalysis of the original data. Access to all relevant original data was kindly provided by L. Desgranges. In contrast to expectation based on the D&P model, step-wise increases in the flow rate of the oxygen jet did not result in an immediate response of . Instead, transient yield changes were observed, with characteristic rise times that were even longer for Xe⁺ than for uranium specific signals. This observation invalidates the idea that ionisation of Xe atoms is due to interaction with oxygen molecules of the jet. Recalling well known transient phenomena in ion-bombardment induced photon emission, it is argued that the enhancement effect may be associated with the increase in the oxidation state of the sample, as a result of which the fraction of Xe (or Kr) atoms leaving the sample in an electronically excited state is presumably increasing, thus enlarging the effective cross section for charge transfer. Alternatively, the enhancement may be due to a lowering of the ejection velocity of rare gas atoms, possibly caused by the increase in near-surface sample oxidation. A second problem with the D&P study is the use of as a reference signal. Literature data as well as new results reveal that and UO⁺ secondary ions dominate the SIMS spectrum of oxidised uranium at energies <60 eV, the U⁺ fraction amounting to only 1% or less. Other issues are (i) the significant variation of the sample erosion rate that occurred upon deliberate changes of the mean primary ion current density, (ii) the associated bombardment induced, progressive oxygen depletion of the sample, (iii) the presence of a background superimposed on the Xe⁺ signals, a significant effect at low current densities and (iv) the space-charge broadening of the primary ion beam at high beam currents. Eliminating all these interfering factors, the (reduced) ionisation probabilities of Xe⁺ were found to be in accordance with gas-phase ionisation by charge exchange, even in the pressure of excessive oxygen flooding.     

LEIS: A reliable tool for surface composition analysis?

Different single and polycrystalline surfaces of Cu and Ag have been investigated by time-of-flight low-energy ion scattering using ⁴He⁺ ions. The fraction of ions that survived single scattering from the outermost surface layers, P⁺, was measured in different neutralization regimes. At low energies, a distinct difference in P⁺ was observed for non-equivalent Cu crystal surfaces for projectiles backscattered in a single collision. The polycrystalline surface was found to exhibit similar neutralization behaviour as the (1 1 1) single crystal surface. At higher energies, P⁺ shows a strong dependence on the angular orientation of the single crystal. The impact of these findings on quantitative surface composition analysis by LEIS is discussed.     

Cluster-induced sputtering of molecular targets

Using molecular-dynamics simulation, we study the cluster-induced sputtering of a diatomic (O₂) and a triatomic (H₂O) molecular target and compare it to the sputtering of an atomic target (Ar). In all three systems, sputtering occurs by the flow of gasified material out of the spike volume into the vacuum above it. Above a threshold, the sputter yield and also the number of dissociations and reactions increase linearly with the total impact energy. The number of reactions occurring is significantly higher than the number of surviving dissociations. The degrees of freedom of the sputtered molecules are not in thermal equilibrium with each other. While for the diatomic target, the internal energy amounts to only 10-20% of the translational energy, it is 40% for H₂O. The translational energy distributions of sputtered monomers are strongly reduced at high energies due to molecule dissociations.     

Comparison of secondary electron emission in helium ion microscope with gallium ion and electron microscopes

To evaluate secondary electron (SE) image characteristics in helium ion microscope, Si surfaces with a rod and step structures is scanned by 30 keV He and Ga ion beams and 1 keV electron beam. The topographic sensitivity of He ions is in principle higher than that for scanning electron microscope (SEM) because of the stronger dependency of SE yield versus incident angle for He ions. As shrinking to sub nm patterns, the pseudo-images constructed from line profile of SE intensity by the electron beam lose their sharpness, however, the images for the He and Ga ion beams keep clearness due to darkening the bottom corners of the pattern. Here, the sputter erosion for Ga ions must be considered. Furthermore, trajectories of emitted SEs are simulated for a rectangular Al surface scanned by the beams to study voltage contrast, where positive and negative voltages are applied to the small area of the sample. Both less high energy component in the energy distribution of SEs and dominant contribution of direct SE excitation by a projectile He ion keep a high voltage contrast down to a sub nm sized area positively biased against the zero-potential surroundings.     

Secondary ion emission from Cu(1 0 0) surfaces with atomic adsorbates (N, O, Cl, S and Br)

Several targets that consist of atomic species X (X = N, O, Cl, S, Br) adsorbed at hollow sites on the Cu(1 0 0) surface have been examined with low-fluence secondary ion mass spectrometry (SIMS). The positive and negative secondary ion (SI) abundance distributions, which show a range of characteristics, have been discussed with the aid of thermochemical data derived from ab initio calculations. In positive SIMS, CuX⁺ is never observed, while the only heteronuclear (mixed-atom) SI that is observed for all five systems is Cu₂X⁺. In negative SIMS, the dominant heteronuclear species for all systems is , except for N/Cu(1 0 0), which produces no , ions. Cu⁻ emission is observed only for O/Cu(1 0 0). By analogy with results from laser ablation studies of O/Cu targets, it is conjectured that Cu⁻ is a daughter product of the gas-phase dissociation of polyatomic Cu-O anion clusters.     

Charge exchange of medium energy H and He ions emerging from solid surfaces

Charge exchange of medium energy H and He ions emerging from clean solid surfaces is studied extensively using a toroidal electrostatic analyzer with an excellent energy resolution. The charge distributions of He ions scattered from sub-monolayers near a surface are non-equilibrated, resulting in a surface peak even for poly-crystal solids. By solving simultaneous rate equations numerically, we derive electron capture and loss cross sections for Ni and Au surfaces. Based on a free electron gas model, non-equilibrated He⁺ fractions dependent on emerging angle reveals uniform electronic surfaces for metals and corrugated surfaces for Si and graphite with covalent bonds. It is also found that equilibrium charge fractions of H⁺ are independent of surface materials (Z₂) and in contrast equilibrium He⁺ fractions depend pronouncedly on Z₂. The data obtained are compared with semi-empirical formulas.     

Electron emission from tungsten induced by slow, fusion-relevant ions

Tungsten has recently been introduced as a new wall material for fusion, because it exhibits favourably low sputtering yields and a very low tritium retention as compared to the commonly used graphite wall and divertor tiles. We measure total electron emission yields due to impact of slow singly and multiply charged ions (deuterium, helium and carbon) on sputter-cleaned polycrystalline tungsten surfaces by using a current method in combination with a retarding grid. Results are presented in the eV to keV impact energy region as typical for fusion edge plasma conditions and discussed in terms of potential and kinetic electron emission.     

AODO: Secondary ion emission and surface modification

In order to study the sputtering of secondary ions from well characterized surfaces, we constructed a new UHV system named AODO. It consists of a detector chamber, a target preparation and analysis chamber, and a target transfer rod. We present the lay-out of this new instrument. The detector allows measuring the time-of-flight of emitted secondary ions and their position on a 2D imaging detector (XY-TOF imaging technique). The analysis chamber can be used to study surface modification by means of LEED (low energy electron diffraction). We show preliminary results of the evolution of the LEED patterns as a function of the projectile fluence during irradiation of HOPG (highly oriented pyrolytic graphite) with slow Xe¹⁴⁺ ions at ARIBE (the low energy, highly charged ion beam line of the French heavy ion accelerator GANIL).     

Monte Carlo study of ion-induced secondary electron emission from SiO2

Here we describe a recently developed direct Monte Carlo program to study kinetic electron emission from SiO₂ target. The program includes excitation of the target electrons (by projectile ions, recoiling target atoms and fast primary electrons), subsequent transport and escape of these electrons from the target surface. The program can be used to calculate the electron yields, distribution of electron excitation points in the target and other physical parameters of the emitted electrons. In order to demonstrate the capabilities of this program, we report a study on the kinetic electron emission from SiO₂ induced by fast (1-10 keV) rare gas ions. The calculated kinetic electron yield for various ion energies and masses is in good agreement with the predictions of most frequently applied theoretical model. In addition, the effects of projectile energy, mass and impact angle on the depth distribution of electron excitation points and average escape depth of the outgoing electrons were investigated. It is important to mention that the existing experimental techniques are not capable to measure these parameters.     

An attempt to solve Andersen’s puzzle in surface segregation during alloy sputtering

The paper addresses CuPt alloy sputtering by Ar ions and discusses the well-known experiment performed by Andersen et al. 25 years ago, but not yet properly explained. The atomistic (binary-encounter) simulation has been applied to extract the concentrations of surface Cu and Pt atoms from the experimental data. The results of simulations favor segregation of Cu at all bombarding energies studied experimentally (1.25-320 keV). It has been shown that some mysterious results of the experiment can be explained by a reconstruction of the surface undergoing sputtering. For forecasting purposes, the sputtering of CuPt alloy with 0.25-1 keV Ar ions is also considered.     

Segregation of atoms in NixPdy alloys during ion irradiation

Sputtering of Ni₅Pd and NiPd₅ alloys by 10 keV Ar ions has been studied using the binary-collision simulation. Special attention was given to the angular distributions of sputtered atoms at the steady-state conditions. The results of simulations were compared with the experimental data published recently. For both targets, the concentrations of Ni and Pd atoms in the top monolayer were extracted from the experimental data. The results of simulations favor segregation of Pd in Ni₅Pd and segregation of Ni in NiPd₅. The total concentration of surface vacancies was found to be about 10-30%.     

K X-ray emission induced by C and O ion impact on selected lanthanoids

Measurements of K-shell X-ray production cross sections by ¹²C⁴⁺ (beam energies between 12 MeV and 14 MeV), and ¹⁶O⁵⁺ ions (with energies between 12.5 MeV and 15 MeV) are presented. The target elements were selected lanthanoids (Ce, Gd, Dy, Ho and Er). The resulting measurements are evaluated through comparisons with the eECPSShsR-UA theory, the MECPSSR model and the adiabatic perturbation (also known as direct molecular orbital, MO) theory, using a scaling based on the reduced velocity parameter . Consideration is given to multiple ionization effects and electron capture contribution to K-shell ionization. An evaluation with previously published values is also given. It is shown that the behavior of the ratios of experimental to theoretical cross sections is different for both ions. The models do not seem to be accurate to predict the X-ray production cross sections for ¹²C⁴⁺ ions, while the MECPSSR theory predicts much better the experimental data for ¹⁶O⁵⁺ than the eECPSShsR-UA.