Interaction of low energy (5–10 keV) argon atoms and ions with a Cu(100) surface; Ion fraction,ionization and neutralization

The ion fractions η⁺ of low energy (5–10 keV) argon particles scattered from a Cu(100) surface, are measured with a time of flight spectrometer. Neutral as well as charged projectiles are used. The scattering angle θ is 30°. The results for different angles of incidence ψ and crystal directions are reported. For scattering in the 〈100〉 direction, with a ψ-value of 15° and a primary energy E₀ of 5 and 10 keV, the ion fractions for the quasi single scattering peak, η⁺_QS, are 1.5 and 6.1% respectively. When E₀ is between 5 and 10 keV a reionization process with a constant reionization probability occurs during the violent interaction. This process, but also neutralization along the outgoing trajectory, determines η⁺_QS. With ions as projectiles, an energy difference of about 16 eV is observed between the quasi single scattering peaks in the spectra of all scattered particles and of ions only. The ion fraction for the quasi double scattering peak, η⁺_QD. depends largely upon E₀, indicating that the efficiency of the reionization process increases with E₀. A qualitative discussion of the data is given, using the reionization process and the interatomic neutralization processes along the trajectory of the scattered particles.     

On the energy spectra of secondary ions emitted from silicon and graphite single crystals

Secondary ion emission from silicon and graphite single crystals bombarded by argon ions with energies E ₀ varied from 1 to 10 keV at various angles of incidence α has been studied. The evolution of the energy spectra of C⁺ and Si⁺ secondary ions has been traced in which the positions of maxima (E _max) shift toward higher secondary-ion energies E ₁ with increasing polar emission angle θ (measured from the normal to the sample surface). The opposite trend has been observed for ions emitted from single crystals heated to several hundred degrees Centigrade; the E _max values initially remain unchanged and then shift toward lower energies E ₁ with increasing angle θ. It is established that the magnitude and position of a peak in the energy spectrum of secondary C⁺ ions is virtually independent of E ₀, angle α, and the surface relief of the sample (in the E ₀ and α intervals studied). Unusual oscillating energy distributions are discussed, which have been observed for secondary ions emitted from silicon (111) and layered graphite (0001) faces. Numerical simulations of secondary ion sputtering and charge exchange have been performed. A comparison of the measured and calculated data for graphite crystals has shown that C⁺ ions are formed as a result of charge exchange between secondary ions and bombarding Ar⁺ ions, which takes place both outside and inside the target. This substantially differs from the ion sputtering process in metals and must be taken into account when analyzing secondary ion emission mechanisms and in practical applications of secondary-ion mass spectrometry.     

Study of the angular and energy distributions of Na+ and K+ ions which have passed through thin copper films

The angular and energy distributions of alkaline Na⁺ and K⁺ ions which have passed through thin Cu films in different crystal states are studied. The ion energy E₀ is varied from 10 to 40 keV, and the incidence angle. ranges from 0° to 60°. The angular aperture of the detector is ～0.5°, which allows the form of the angular distribution of ions which have passed through the solid thin films as a function of the energy, the angle of primary-ion beam incidence, and the layer thickness to be studied in detail. It is shown that, in the range E₀ = 10.40 keV, the energy loss ΔE of those ions that have passed increases linearly as the energy of incident ions increases. The energy loss increases with increasing ion mass in the case of singly charged ions. The surface amorphization of single- and polycrystalline films leads to an increase (by 150–200 eV) in the energy loss caused by the diffuse propagation of ions and to loss-peak broadening. It is probable that surface amorphization is accompanied by an increase in the number of atoms experiencing multiple collisions with atoms of the film, which leads to an increase in the average energy loss by ions that have passed through films.     

Low energy (E0 < 10 keV) atom and ion scattering of neon from a Cu(100) surface; Ionization and neutralization

The ion fractions η⁺ of low energy (5–10 keV) neon particles scattered from a Cu(100) surface are measured with a time of flight spectrometer. These fractions are obtained for neutral as well as charged projectiles and for different crystal directions. The scattering angle θ was 30°. For a primary energy E₀ of 5 keV neutral projectiles have a value for η⁺ which is 30 times lower than for charged projectiles; these values are 0.15 and 4.5% respectively. For E₀ = 10 keV the values of η⁺ are about the same (~22%). Energy differences up to 22 eV, depending on E₀, are observed between the single scattering peaks in the ion spectra of charged and neutral projectiles but also between the single scattering peak in the spectra of all scattered particles and of ions, with ions as projectiles. A qualitative discussion of these data is given, involving charge transfer processes of noble gas particle and target atom. The data suggest that these neutralization processes can be described more adequately with interatomic neutralization processes along the trajectory than with Auger neutralization by conduction electrons.     

Energy dependence of the ionization probability of sputtered Cu and Ni

Despite its great sensitivity, the usefulness of secondary ion mass spectrometry (SIMS) for many applications has been limited by an inadequate understanding of the probability of sputtering an atom in an ionized state. To determine this ionization probability for clean Cu and Ni surfaces, I have measured the energy distribution of sputtered neutrals and ions by quadrupole mass filtering and retarding potential analysis using potential modulation differentiation. Analysis of sputtered neutrals was accomplished by electron impact ionization. Because the neutrals outnumber the ions by at least two orders of magnitude, the ratio of sputtered ions to neutrals is an accurate measure of the ionization probability. For energies below 20 eV the dependence of the ionization probability on energy goes as P(E) α Eⁿ, where n = 0.65 for clean Cu. The absorption of oxygen on the Cu surface increases the total ion yield while causing a reduction in the value of the exponent n. Similar results are found for nickel, where n = 0.54 for the clean surface.     

Features of the energy distribution of secondary particles upon the ion bombardment of graphite

The secondary emission of carbon atoms from the (0001) plane of graphite nanocrystallites bombarded with argon ions with energies of 1 and 10 keV and the incidence angle α = 45° is investigated. The unusual oscillating energy distributions of secondary C⁺ ions with main maxima E _max in the range of 40–60 eV and peaks corresponding to the energies E ₁ ≈ 20, 30, 70, 80, and 100 eV have been revealed. The C⁺ ion yield decreases, the energy spectrum increases, and the maximum E _max shifts to larger energies E ₁ with increasing emission angle (with respect to the normal to the surface). The secondary-ion emission from the (0001) face of graphite is numerically simulated with allowance for the charge exchange of secondary ions to obtain a qualitative explanation of the observed results.     

Ion survival probabilities for 3 keV Ar+ scattering from La,Yb, and chemisorbed H2, O2, and H2O on La surfaces

TOF spectra of scattered primary and surface recoiled neutrals and ions for 3 keV Ar⁺ bombardment of clean La and Yb and H₂, O₂, and H₂O saturated La surfaces are presented. The spectra are analyzed in terms of single (SS) and multiple (MS) scattering of the primary ions and surface recoiling (SR) of adsorbate atoms. Measurement of spectra of neutrals + ions and neutrals alone allows determination of scattered ion fractions Y. The Y values for the SS event are high for clean La (37%) and lower for adsorbate covered La (32% for H₂, 13% for O₂, and 8% for H₂O); Yb exhibits a similar behavior, i.e. 16% for clean Yb and 5% for O₂ + H₂O covered Yb. Photon emission accompanying the scattering collision has been observed from clean La and Yb and adsorbate covered La. A preferential inelastic energy loss of 15 ± 3 eV for the SS event has been observed for scattered neutrals as opposed to ions for La and H₂ saturated La at 135°. These results are interpreted within the models for Auger and resonant electronic charge exchange transitions during approach or departure of an ion with a surface and the electron promotions occuring during close atomic encounters where the electron shells are interpenetrating.     

Secondary ion emission from Si under nitrogen ion bombardment

The yield and energy distribution of positive secondary ions emitted from Si under N₂⁺ ion bombardment were measured. The obtained mass peaks correspond to three types of secondary ion species, that is, physically sputtered ions (Si⁺, Si₂⁺), chemically sputtered ions (SiN⁺ Si₂N⁺) and doubly charged ions (Si²⁺). The dependence of secondary ion emission on the primary ion energy was studied in a range of 2.0–20.0 keV. The yields of physically and chemically sputtered ions were almost independent of the primary ion energy. The yield of the doubly charged ion strongly depended on the primary ion energy. The energy distribution of secondary ions of the three types showed the same dependence on the primary ion energy. The most probable energy of the distribution increased with the primary ion energy. On the other hand, for the energy distribution curves of sputtered ions, the tail factors N in E^?N were constant and showed a m/e dependence.     

Energy distributions of atomic and molecular ions sputtered by C60 projectiles

In the process of investigating the interaction of fullerene projectiles with adsorbed organic layers, we measured the kinetic energy distributions (KEDs) of fragment and parent ions sputtered from an overlayer of polystyrene (PS) oligomers cast on silver under 15 keV C₆₀⁺ bombardment. These measurements have been conducted using our TRIFT™ spectrometer, recently equipped with the C₆₀⁺ source developed by Ionoptika, Ltd. For atomic ions, the intensity corresponding to the high energy tail decreases in the following order: C⁺(E^−0.4) > H⁺(E^−1.5) > Ag⁺(E^−3.5). In particular, the distribution of Ag⁺ is not broader than those of Ag₂⁺ and Ag₃⁺ clusters, in sharp contrast with 15 keV Ga⁺ bombardment. On the other hand, molecular ions (fragments and parent-like species) exhibit a significantly wider distribution using C₆₀⁺ instead of Ga⁺ as primary ions. For instance, the KED of Ag-cationized PS oligomers resembles that of Ag⁺ and Ag_n⁺ clusters. A specific feature of fullerene projectiles is that they induce the direct desorption of positively charged oligomers, without the need of a cationizing metal atom. The energy spectrum of these PS⁺ ions is significantly narrower then that of Ag-cationized oligomers. For characteristic fragments of PS, such as C₇H₇⁺ and C₁₅H₁₃⁺ and polycyclic fragments, such as C₉H₇⁺ and C₁₄H₁₀⁺, the high energy decay is steep (E⁻⁴ − E⁻⁸). In addition, reorganized ions generally show more pronounced high energy tails than characteristic ions, similar to the case of monoatomic ion bombardment. This observation is consistent with the higher excitation energy needed for their formation. Finally, the fraction of hydrocarbon ions formed in the gas phase via unimolecular dissociation of larger species is slightly larger with gallium than with fullerene projectiles.     

Effects of evolving surface morphology on yield during focused ion beam milling of carbon

We investigate evolving surface morphology during focused ion beam bombardment of C and determine its effects on sputter yield over a large range of ion dose (10¹⁷-10¹⁹ ions/cm²) and incidence angles (Θ = 0-80°). Carbon bombarded by 20 keV Ga⁺ either retains a smooth sputtered surface or develops one of two rough surface morphologies (sinusoidal ripples or steps/terraces) depending on the angle of ion incidence. For conditions that lead to smooth sputter-eroded surfaces there is no change in yield with ion dose after erosion of the solid commences. However, for all conditions that lead to surface roughening we observe coarsening of morphology with increased ion dose and a concomitant decrease in yield. A decrease in yield occurs as surface ripples increase wavelength and, for large Θ, as step/terrace morphologies evolve. The yield also decreases with dose as rippled surfaces transition to have steps and terraces at Θ = 75°. Similar trends of decreasing yield are found for H₂O-assisted focused ion beam milling. The effects of changing surface morphology on yield are explained by the varying incidence angles exposed to the high-energy beam.     

Computer simulation of atomic mixing during ion bombardment

The atomic mixing in the target under ion bombardment is assumed to result from cascades of atomic collision events. Computer simulations have been applied to collision cascades to estimate the depth resolution of surface analysis with an ion probe. The Monte Carlo method based on a single scattering model has been used mainly in the calculation under the assumptions of random collision process, no diffusion and no target saturation processes. High-energy collisions are characterized by a Lenz-Jensen or a Thomas-Fermi potential, while a Born-Mayer potential is used in the low energy region. The simulations have been performed for the bombardment of Ar ions withE ₀=5 keV and 10 keV at angles of incidence θ=0° and 60° on Si targets. The depth resolutions [the definition of which is explained by (15) in the text] are about 140Å for the Lenz-Jensen cross section and about 80Å for the Thomas-Fermi one for θ=0° atE ₀=5 keV, and decrease by 20–40% at θ=60° and increase by 70–90% forE ₀=10 keV.     

Influence of primary ion species on the secondary cluster ion emission process from SAMs of hexadecanethiol on gold

In order to investigate the secondary cluster ion emission process of organo-metallic compounds under keV ion bombardment, self-assembled monolayers (SAMs) of alkanethiols on gold are ideal model systems. In this experimental study, we focussed on the influence of the primary ion species on the emission processes of gold-alkanethiolate cluster ions from a hexadecanethiol SAM on gold. For this purpose, we carried out time-of-flight secondary ion mass spectrometry (TOF-SIMS) measurements using the following primary ion species and acceleration voltages: Ar⁺, Xe⁺, SF₅⁺ (10 kV), Bi⁺, Bi₃⁺(25 kV), Bi₃²⁺, Bi₅²⁺, Bi₇²⁺ (25 kV).It is well known that molecular ions M⁻ and gold-alkanethiolate cluster ions Au_xM_y⁻ with M = S-(CH₂)₁₅-CH₃, x − 3 ≤ y ≤ x + 1, x, y > 0, show intense peaks in negative mass spectra. We derived yields Y_SI exemplarily for the molecular ions M⁻ and the gold-hexadecanethiolate cluster ions Au_y+1M_y⁻ up to y = 8 and found an exponentially decreasing behaviour for increasing y-values for the cluster ions.In contrast to the well-known increase in secondary ion yield for molecular secondary ions when moving from lighter to heavier (e.g. Ar⁺ to Xe⁺) or from monoatomic to polyatomic (e.g. Xe⁺ to SF₅⁺) primary ions, we find a distinctly different behaviour for the secondary cluster ions. For polyatomic primary ions, there is a decrease in secondary ion yield for the gold-hexadecanethiolate clusters whereas the relative decrease of the secondary ion yield ξ_Y with increasing y remains almost constant for all investigated primary ions.     

Photoluminescence and optical properties of He ion bombarded ultra-high molecular weight polyethylene

Ion bombardment is a suitable tool to improve the physical and chemical properties of polymer surface. In this study UHMWPE samples were bombarded with 130 keV He ions to the fluences ranging from 1 × 10¹² to 1 × 10¹⁶ cm⁻². The untreated and ion beam modified samples were investigated by photoluminescence, and ultraviolet-visible (UV-vis) spectroscopy. Remarkable decrease in integrated luminescence intensity with increasing ion fluences was observed. The reduction in PL intensity with increase of ion fluence might be attributed to degradation of polymer surface and formation of defects. The effect of ion fluence on the optical properties of the bombarded surfaces was characterized. The values of the optical band gap E_g, and activation energy E_a were determined from the optical absorption. The width of the tail of the localized states in the band gap (E_a) was evaluated using the Urbach edge method. With increasing ion fluences a decrease in both the energy gap and the activation energy were observed. Increase in the numbers of carbon atoms (N) in a formed cluster with increasing the He ion fluence was observed.     

Secondary ion emission from polymer layers by atomic and molecular ion bombardment: Data evaluation based on linear-cascade sputtering theory

This paper constitutes an attempt to rationalise impact-energy dependent yields of molecular secondary ions emitted from polymer samples under bombardment with atomic and molecular primary ions. The evaluation was based upon a comparison with sputtering yields calculated from linear-cascade sputtering theory, including threshold effects. To explore general trends, sputtering yields for carbon, silicon and silver were calculated under impact of normally incident C, F, S, Ga, Xe, Au, SF₅, C_11, C₆₀ and Au₅. The yields of carbon, for example, bombarded with C₆₀ are larger than for Ga by factors of ∼5 and ∼10 at 10 and 100 keV, respectively. However, owing to the fact that the effective threshold energy for sputtering increases with the number of constituents of the projectile, the yields for molecular ion impact start to exceed the yields for atomic ions only at energies between 0.5 and 5 keV. The analysed experimental results relate to molecular ion emission from one monolayer (1 ML) and 9 ML films of polymethacrylate on silver bombarded with Xe and SF₅ ions at energies E between 0.5 and 10 keV. Comparison of (initial) secondary ion yields S⁺ (m/z 143) with calculated sputtering yields suggests that S⁺ constitutes the sum of two contributions. The first, labelled , prevails at low energies and appears to reflect molecule ejection due to the mean effect of nuclear energy deposition (“ordinary” linear-cascade sputtering). The second contribution, , dominates at E > 1.5 keV, increases with a high power of E, but does not correlate with the calculated sputtering yield. It is suggested that is a measure of those impact events which occasionally generate a very high energy density at the surface, thus providing optimum conditions for very efficient ejection of molecules that are located at the rim of the agitated area. The SF₅/Xe secondary ion yield ratios are distinctly different for the two contributions, only about 0.3 for but ∼4 (1 ML) and ∼20 (9 ML) for . The pronounced secondary ion “yield enhancement” frequently reported in the literature for molecular versus atomic ion bombardment appears to be due to an enlargement of the contribution, more so the higher the impact energy and the more massive the projectile. The total (integrated) secondary ion yields, estimated by making use of the reported damage cross sections, were found to be the same for SF₅ bombardment of the 1-ML and the 9-ML samples. This finding calls for more attention towards obtaining high secondary ion yields at minimum sample consumption.     

Absolute measurement of sputtered ion fractions using matrix isolation spectroscopy

Sputtering yields for neutrals and ions have been measured by collecting the sputtered species in a noble gas matrix and determining their amounts from optical absorption spectroscopy. The atomic ion fractions for Ti and Zr bombarded by O₂⁺ at 2 keV are 0.8 and 0.4, respectively, whereas TiO and ZrO are sputtered largely as neutrals. Neutral sputtering yields from Ar⁺ bombardment arc consistent with previous measurements. The experimental results are compared with various theoretical models for the sputtering process.     

Influence of massive projectile size and energy on secondary ion yields from organic surfaces

We investigated the influence of the projectile size and energy using Au_n^q+ clusters (5 < n < 400, 1 < q < 4) impacting on a glycine target with a 19q-34q keV energy range. We show that both CN⁻ fragment and Gly⁻ molecular ion yields are equivalent for projectiles with n > 9 and increase with the energy per projectile atoms. A maximum yield of 0.5 (50%) for both CN⁻ and Gly⁻ was obtained with the Au₄₀₀⁴⁺ projectile at 136 keV total energy. For Gly⁻, the yield enhancement is linear for Au_n when n > 5. Trends for the CN⁻ fragment are different. A nonlinear yield enhancement proportional to n³ is observed for Au_n when n < 9.     

Electron yield per ion charge-state correction for an ion collector with unsuppressed secondary electron emission

The electron yield per ion charge-state γ/q was measured for emission of electrons from clean polycrystalline gold induced due to impact of Ta ^q+ (11≤q≤41) ions with kinetic energy per chargeE _i/q from 15 keV/q to 150 keV/q. The dependence of γ on angle of incidence was analyzed with use of relation γ(ϑ)=γ₀ cos^−f ϑ. The fitting of experimental data gives a range of γ₀/q from 1 to 1.75 for Ta¹³⁺ and from 1.5 to 1.73 for Ta³⁹⁺. The dependence of γ₀/q onq andE _i is discussed with respect to measurement of ion currents emitted from laser-produced plasmas with an ion collector with unsuppressed secondary electron emission. This work was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, Office of Energy Research, U.S. Department of Energy, and by grant A1010819 from the Grant Agency of the Academy of Sciences of the Czech Republic.     

Comparison of detection efficiencies of negatively charged gold-alkanethiolate-, gold-sulfur- and gold-clusters in ToF-SIMS

In order to improve quantification of high mass ions, the influence of cluster composition on detection efficiencies has been studied using a TOF-SIMS IV with the extended capability of postaccelerating ions up to 20 keV. In this experimental study, we focus on the comparison of detection efficiencies for three types of negatively charged secondary cluster ions: gold-alkanethiolate-clusters (Au_xM_y), gold-sulfur-clusters (Au_xS_y) and gold-clusters (Au_x). The clusters were sputtered from self-assembled monolayers of hexadecanethiols on gold substrates using 10 keV Ar⁺ primary ions. The detection efficiencies were derived on the basis of a function for the secondary electron yield and a fourth-order approximated Poisson probability distribution for electron propagation and amplification within the microchannel plate.In addition to the well-known dependence of detection efficiencies on ion mass and energy, which has already been studied for positively charged ions, we were able to show a similar behaviour for the investigated negatively charged secondary ions. We have observed major variations among the three types of clusters at similar mass and energy as predicted in a theoretical approach. The observed differences are due to the different composition of the investigated clusters which has a major influence on the kinetic ion induced electron emission within the microchannel plate. For the first time it was possible to experimentally verify these predictions for detection efficiencies.     

Substrate effects on the analysis of biomolecular layers using Au, Au3 and C60 bombardments

Effects of platinum silicon, graphite and PET substrates on the secondary ion yield of sub-monolayer and multilayer samples of Cyclosporin A following 20 keV Au⁺, Au₃⁺and C₆₀⁺ impacts have been investigated. The obtained results of sub-monolayer samples show that platinum enhances the yield of the pseudo-molecular ion following Au⁺ and Au₃⁺ impacts due to the high density of the substrate that enables the energy of the primary ions to be deposited near the surface. C₆₀⁺ impacts on sub-monolayer samples are less effective, but there is an enhancement on PET substrates. Impacts of 20 keV Au⁺ and Au₃⁺ are not very efficient on multilayer samples. 20 keV C₆₀⁺ impacts enhance the yields significantly, especially for the relatively high molecular weight [M+H]⁺ ion.