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.     

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.     

Ion survival probabilities for 3 keV He+, Ne+, and Ar+ scattering from La and adsorbate covered La surfaces

TOF spectra of scattered neutrals and ions for 3 keV He⁺, Ne⁺, and Ar⁺ bombardment of La and adsorbate covered La surfaces show that the scattered ion fractions are 21.1% and 10.7% for Ar⁺ on clean and adsorbate covered La, respectively, and < 1% for all of the other systems. These results are consistent with a model in which Auger and resonant neutralization (AN and RN) transitions govern the ion survival probability.     

Vacancy-type defect distributions near argon sputtered Al(100) surface studied by variable-energy positrons and molecular dynamics simulations

A beam of variable-energy positrons, whose back-diffusion probability is measured as a function of positron implantation energy, is applied to studies of depth distribution of sputtering damage in aluminum. The defects are produced by argon ion bombardment of an Al(110) surface in ultra-high vacuum. We have varied the Ar⁺ energy, incident angle and dose, as well as sputtering and annealing temperatures. The extracted defect profiles have typically a narrow peak at the surface with a width of 10–20 A and a broader tail extending down to 50–100 Å. The shape of the defect profile varies only slightly with the sputtering energy and angle. Defect production at less than 1 keV Ar⁺ energies is typically 1–5 vacancies per incident ion. The defect profiles become fluence-independent at about 2 × 10¹⁶ Ar⁺ cm⁻². The defect density at the outer atomic layers saturates at high argon fluences to a few at%, depending on sputtering conditions. The sputtering temperature (below or above the vacancy migration stage at 250 K) has little effect on vacancy profiles. Defects anneal out gradually between 100 °C and 400 °C. Sputtering damage was also evaluated with the molecular dynamics technique. The shape and depth scale of the simulated collision cascades are in agreement with the experimentally extracted quantities.     

Preferential sputtering of TIC under keV Ar+ ion bombardment: Simultaneous sputtering-ISS measurement with He+ and Ar+ ions

The composition change of the outermost atom layer of TiC(110) under ion bombardment with 1.5–3 keV He⁺ and He⁺ + Ar⁺ ions has been measured by ion scattering spectroscopy with He⁺ ions at different sample temperatures. It has been found that the preferential sputtering of C atoms takes place for both the He⁺ and Ar⁺ ion bombardment, however the preferred sputtering is more pronounced for Ar⁺ ions than for He⁺ ions. The ion bombardment with He⁺ ions at elevated sample temperatures hardly results in any change in surface composition below ～800°C, while Ar⁺ ion bombardment results in C enrichment for elevated temperatures as reported so far.     

The measurement of energy spectra of neutral particles in low energy ion scattering

An apparatus is described for low energy (0.1–10 keV) ion scattering (LEIS) experiments. A time of flight (TOF) spectrometer is incorporated in the system to be able to measure the energy of particles in the neutral state after scattering. The energy resolution ΔE/E of the TOF spectrometer is discussed and found to be 0.5% (FWHM). This is sufficient for our scattering experiments. An electrostatic analyzer (ESA) is used to measure the energy of scattered ions [ΔE/E=0.5% (FWHM)]. Experiments show that in general the ion dose needed to obtain a TOF spectrum (2×10¹⁰ ions/cm²) is much smaller than the dose needed for an ESA-spectrum (6×10¹³ ions/cm²). The ion spectra measured with the TOF spectrometer, by subtracting the neutral yield from the total yield, as well as with the ESA are found to agree quite well. This provides a way to calibrate the TOF spectrometer. The determination of the ion fraction of scattered particles is discussed [10 keV⁴⁰Ar⁺ on Cu(100), scattering angle 30°]. It is shown that the TOF spectrometer is able to measure light recoil particles (e.g. hydrogen) from a heavy substrate. In the analysing system is, in addition to the TOF spectrometer, also incorporated a stripping cell to measure the energy of neutral scattered particles. An energy spectrum of neutral scattered particles measured with both methods is shown.     

Mechanism of structural changes of Si(111) surfaces subjected to low-energy ion pulses during molecular-beam epitaxy

Reflected high-energy electron diffraction (RHEED) and detection of the intensity oscillations of the specular reflection have been used to investigate morphological changes in Si(111) associated with the two-dimensional layer-by-layer mechanism of silicon growth from a molecular beam under conditions of pulsed (0.25–1 s) bombardment with low-energy (80–150 eV) Kr ions in the interval of small total radiative fluxes (10¹¹–10¹² cm²²), for which the density of radiation-generated defects is small in comparison with the surface density of the atoms. After pulsed ion bombardment an increase in the intensity of the specular reflection is observed if the degree of filling of the monolayer satisfies 0.5<θ<1. No increase in the intensity occurs during the initial stages of filling of the monolayer. The maximum amplitude increment of the oscillations is reached at θ≈0.8. The magnitude of the amplitude increment of the RHEED oscillations increases with temperature up to 400°C and then falls. At temperatures above 500°C amplification of the reflection intensity essentially vanishes. Experiments on multiple ion bombardment of each growing layer showed that the magnitude of the amplitude increment of the oscillations decreased as a function of the number of deposited layers (the order of the RHEED oscillation). A mechanism for the observed phenomena is proposed, based on the concept of surface reconstruction by pulsed ion bombardment accompanied by formation of a (7×7) superstructure, which corresponds to a decrease of the activation energy of surface diffusion of the adatoms. Within the framework of the proposed mechanism the results of Monte Carlo modeling agree with the main experimental data. Zh. éksp. Teor. Fiz. 114, 2055–2064 (December 1998)     

Influence of argon ion bombardment on the formation of intermetallic compounds in the nickel-aluminum system

The formation of Ni _x Al _y intermetallic compounds in two-layer (Ni/Al) structures (nickel films deposited on aluminum substrates in vacuum) under bombardment by Ar⁺ ions has been studied experimentally. The method based on Rutherford backscattering of He⁺ ions is used to demonstrate that argon ion bombardment causes the formation of intermetallic compounds in the near-surface layer. The thickness of the intermetallic layer formed in the near-surface region substantially exceeds the projective ion path. The composition and thickness of the intermetallic layer depend mainly on the implantation dose and the substrate temperature, rather than on the ion current density. In the intermetallic layer, the content of nickel increases with increasing temperature. It has been established that, in the absence of bombardment, intermetallic phases are not observed at temperatures lower than T = 400°C and that, in the presence of bombardment, the Ni₃Al intermetallic layer arises at a temperature of 320°C.     

Sputter damage in Si surface by low energy Ar+ ion bombardment

The damage distributions in Si(1 0 0) surface after 1.0 and 0.5 keV Ar⁺ ion bombardment were studied using MEIS and Molecular dynamic (MD) simulation. The primary Ar⁺ ion beam direction was varied from surface normal to glancing angle. The MEIS results show that the damage thickness in 1.0 keV Ar ion bombardment is reduced from about 7.7 nm at surface normal incidence to 1.3 nm at the incident angle of 80°. However, the damage thickness in 0.5 keV Ar ion bombardment is reduced from 5.1 nm at surface normal incidence to 0.5 nm at the incident angle of 80°. The maximum atomic concentration of implanted Ar atoms after 1 keV ion bombardment is about 10.5 at% at the depth of 2.5 nm at surface normal incidence and about 2.0 at% at the depth of 1.2 nm at the incident angle of 80°. However, after 0.5 keV ion bombardments, it is 8.0 at% at the depth of 2.0 nm for surface normal incidence and the in-depth Ar distribution cannot be observable at the incident angle of 80°. MD simulation reproduced the damage distribution quantitatively.     

Polyethylene terephthalate (PET) bulk film analysis using C60, Au3, and Au primary ion beams

The damage characteristics of polyethylene terephthalate (PET) have been studied under bombardment by C₆₀⁺, Au₃⁺ and Au⁺ primary ions. The observed damage cross-sections for the three ion beams are not dramatically different. The secondary ion yields however were significantly enhanced by the polyatomic primary ions where the secondary ion yield of the [M + H]⁺ is on average 5× higher for C₆₀⁺ than Au₃⁺ and 8× higher for Au₃⁺ than Au⁺. Damage accumulates under Au⁺ and Au₃⁺ bombardment while C₆₀⁺ bombardment shows a lack of damage accumulation throughout the depth profile of the PET thick film up to an ion dose of ∼1 × 10¹⁵ ions cm⁻². These properties of C₆₀⁺ bombardment suggest that the primary ion will be a useful molecular depth profiling tool.     

Characterization and ion-induced degradation of cross-linked poly(methyl methacrylate) studied using time of flight secondary ion mass spectrometry

In this study, a series of random copolymers of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) were prepared as surface-initiated polymer (SIP) films on silicon substrates using atom transfer radical polymerization. Positive and negative ion static time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to characterize SIP films with different MMA/EGDMA monomer ratios in an attempt to quantify their surface composition. However, matrix effects in the positive and negative ion modes led to preferential secondary ion generation from the EGDMA monomer and suppression of secondary ions characteristic of the MMA monomer, precluding accurate quantification using standard linear quantification methods. Ion-induced degradation of these films under 5 keV SF₅⁺ bombardment was also examined to determine the effect of cross-linking on the accumulation of ion-induced damage. Increasing incorporation of the EGDMA cross-linker in the SIP films decreased the sputter rate and increased the rate of damage accumulation under extended (>10¹⁴ ions/cm²) 5 keV SF₅⁺ bombardment. Comparison of the ion bombardment data with thermal degradation of cross-linked PMMA suggests that the presence of the cross-linker impedes degradation by depolymerization, resulting in ion-induced damage accumulation. The increased rate of ion-induced damage accumulation with increased cross-link density also suggests that polymers that can form cross-links during ion bombardment are less amenable to depth profiling using polyatomic primary ions.     

AES analysis of nitridation of Si(100) by 2–10 keV N+2 ion beams

Ion beam nitridation of Si(100) as a function of N⁺₂ ion energy in the range of 2–10 keV has been investigated by in-situ Auger electron spectroscopy (AES) analysis and Ar⁺ depth profiling. The AES measurements show that the nitride films formed by 4–10 keV N⁺₂ ion bombardment are relatively uniform and have a composition of near stoichiometric silicon nitride (Si₃N₄), but that formed by 2 keV N⁺₂ ion bombardment is N-rich on the film surface. Formation of the surface N-rich film by 2 keV N⁺₂ ion bombardment can be attributed to radiation-enhanced diffusion of interstitial N atoms and a lower self-sputtering yield. AES depth profile measurements indicate that the thicknesses of nitride films appear to increase with ion energy in the range from 2 to 10 keV and the rate of increase of film thickness is most rapid in the 4–10 keV range. The nitridation reaction process which differs from that of low-energy (< 1 keV) N⁺₂ ion bombardment is explained in terms of ion implantation, physical sputtering, chemical reaction and radiation-enhanced diffusion of interstitial N atoms.     

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.     

Velocity dependence of azimuthal anisotropies in ion scattering from rhodium {111}

The scattering of He⁺, Ne⁺ and Ar⁺ ions from Rh {111} is measured as a function of the azimuthal angle of the primary ion for an incident polar angle of 70° from the surface normal and an inplane collection angle of 60°. In this case anisotropy is defined as the ratio of the yield of ions scattered having the azimuth of 〈110〉 to the yield of those having the azimuth of 〈211〉. The yield ratio for all particle types correlates with particle velocity. The ratio is ～ 1 at low velocities, decreases to ～ 0.2 at 8 × 10⁶$\text{cm}\text{s}$ and then increases to a value of 1.4 at 25 × 10⁶$\text{cm}\text{s}$. Molecular dynamics calculations have been performed for Ne⁺ ion scattering from Rh{111} in order to understand the changes in anisotropy with particle velocity. Qualitative agreement with the experimental results is obtained without having to account for neutralization. A neutralization probability that depends on the collision time improves the agreement between the calculated and experimental yield ratios. A velocity dependent probability will not affect the ratio of yields in two different azimuthal directions.     

Two-dimensional observation of N2+ and N+ scattering patterns from Cu(001)

Low-energy (<1 keV) N₂⁺ and N⁺ ion scattering from the Cu(001) surface was directly observed by using a two-dimensional detection system. The two-dimensional pattern of the scattered ions changed when the primary ion energy was increased from 200 to 600 eV. The scattering peak shifted toward the [110] azimuth, to which the incident plane was not parallel, above 600 eV. The difference of ion-survival probabilities between N₂⁺ and N⁺ was discussed from the full width at half maximum of the angular distribution of scattered ions.     

Ion bombardment induced decomposition of polyimide (PIQ) studied by X-ray Photoelectron Spectroscopy (XPS) and Direct Recoil (DR) spectrometry

Angular resolved X-ray photoelectron spectroscopy (XPS) and time-of-flight direct recoil (DR) spectrometry are used to characterize the surface changes in polyimide iso-indroquinazolinedione (PIQ®: Hitachi Chem. Co.) induced by 4 keV Ar⁺ bombardment. Deconvolution of the XPS data along with a stoichiometry of CH_{2.2 ± 0.2} as determined from DR intensities indicate the presence of an uppermost hydrocarbon layer on the initial surface. Upon Ar⁺ bombardment the H, N, and O concentrations decrease and the surface layer carbon concentration increases to > 94 at %. This carbonaceous layer exhibits C1s chemical shifts and line shapes that are similar to those of an ion bombarded graphite surface, along with an enhanced electrical conductivity.     

Ellipsometric study of oxygen adsorption and the carbon monoxide-oxygen interaction on ordered and damaged Ag(111)

The adsorption of oxygen on Ag(111) has been studied by ellipsometry in conjunction with AES and LEED. The oxygen pressure varied between 10^?5 and 10^?3 Torr and the crystal temperature between room temperature and 250° C. Changes in the Auger spectrum and the LEED pattern upon oxygen adsorption are very small. Oxygen coverages were derived from the changes in the ellipsometric parameter Δ. At room temperature a maximum coverage is reached within a few minutes. Its value increases with the damage produced by the preceding argon ion bombardment. The sticking coefficient derived from the initial rate of Δ-change amounts to 3 × 10^?5 for well-annealed surfaces and 2.5 ? 5 × 10^?4 for damaged surfaces. After evacuation no desorption takes place. Other types of adsorption, associated with much larger changes in Δ, were observed upon bombardment with oxygen ions and with oxygen activated by a hot filament. The reaction of CO with adsorbed oxygen was studied ellipsometrically at room temperature in the CO pressure range 10^?7–10^?6 Torr. The initial reaction rate is proportional to the CO pressure. The reaction probability (number of oxygen atoms removed per incident CO molecule) is 0.36.     

ISS measurement of surface composition of AuCu alloys by simultaneous ion bombardments with Ar+ and He + ions

Surface composition of Au-Cu(43 at%) alloy under 1.5–5 keV argon ion bombardment has been investigated by ion scattering spectroscopy (ISS). In this experiment, we adopted a specific technique to use mixed He⁺ and Ar⁺ ions as primary beam in order to perform sputtering (Ar⁺) and ISS measurement (He⁺) simultaneously. The outermost atom layer of Au-Cu alloys under Ar⁺ ion bombardment is Au-rich leading to the conclusion that Ar⁺ ion bombardment of AuCu alloys causes the preferential sputtering of Cu atoms, resulting in a Au-rich outermost atom layer and a depletion layer of Au atoms beneath the outermost atom layer due to ion-beam-enhanced surface segregation. This result explains the experimental results obtained by AES as well.     

Ion bombardment-induced charge state effects CaO single crystals: F+ and F centers

The effects of heavy-and light-ion bombardment on defect formation in CaO have been investigated by UV-absorption spectroscopy and volume measurements. While 500 keV Ar or Ca implantation produces only F⁺ centers, 240 keVH produces both F⁺ and F centers at a F⁺ to F ratio of 5.6 to 1. On the other hand, when an argon implanted sample is subsequently bombarded with hydrogen, about 30% of the F⁺ centers anneal during 1 ×10¹⁴ H/cm²; at higher H fluences, new F⁺ and F centers are produced. An effect of energy partition between ionization and nuclear/atomic collision processes for the incident ions on the charge state of the resulting defect is thus clearly demonstrated.

The formation and annealing of these defects are accompanied by volume changes in the ion implanted surface layer which can be monitored in sltu with a cantilever beam technique. The measurements show volume expansion of the order of 1.5% following 10¹⁶ 500 keV Ar implantation; subsequent implantation of 10¹⁸ 240 keV H compacts the previously expanded material by 25 %. These results are in qualitative agreement with the optical data and seem to indicate that volume changes are associated with the formation and annealing of F⁺ centers.     

Structural and electrical analysis of S ion bombarded p-InP(1 0 0)

The chemical state of sulfur and surface structure on low-energy S⁺ ion-treated p-InP(1 0 0) surface have been investigated by high-resolution X-ray photoelectron spectroscopy (XPS) and low-energy electron diffraction (LEED). S⁺ ion energy over the range of 10-100 eV was used to study the effect of ion energy on surface damage and the process of sulfur passivation on p-InP(1 0 0) by S⁺ ion beam bombardment. It was found that sulfur species formed on the S⁺ ion-treated surface. The S⁺ ions with energy above 50 eV were more effective in formation of In-S species, which assisted the InP surface in reconstruction into an ordered (1 × 1) structure upon annealing. After taking into account physical damage due to the process of ion bombardment, we found that 50 eV was the optimal ion energy to form In-S species in the sulfur passivation of p-InP(1 0 0). The subsequent annealing process removed donor states that were introduced during the ion bombardment of p-InP(1 0 0). Results of theoretical simulations by Transport of Ions in Materials (TRIM) are in accordance with those of experiments.