Low-energy ion scattering and sputtering at grazing ion bombardment of clean and oxygen covered Ag(1 1 0) surface

The ion scattering and sputtering processes at low energy grazing N⁺ and Ne⁺ ion bombardment of clean and oxygen covered Ag(1 1 0) surface have been investigated by computer simulation in the binary collision approximation.

The spatial, angular and energy distributions of scattered, sputtered particles and desorbed molecules of oxygen as well as their yields versus the angle of incidence have been calculated. In these distributions the some characteristic peaks were observed and analysed. It was found that an adsorption layer plays a role of the additional surface barrier, i.e. it reflects leaving target atoms back to crystal. The azimuth angular dependencies of Ag sputtering yield and non-dissociative O₂ desorption yield at grazing incidence have been calculated. It was shown that these dependencies correlate the crystal orientation.     

Neutralization of keV Ne and Ar ions during grazing scattering from an Al(1 1 1) surface

Charge fractions after scattering of Ne⁺ ions, Ne⁰ atoms and Ar⁺ ions with keV energies under a grazing angle of incidence from an atomically clean and flat Al(1 1 1) surface are studied. For incoming Ne⁺ ions we observe defined ion fractions in the scattered beams, whereas for incident Ne⁰ atoms ion fractions are more than one order of magnitude smaller. This experimental result provides clear evidence for a survival of Ne⁺ ions over the whole scattering event. From the dependence of ion fractions on the perpendicular energy component we derive neutralization rates as function of distance from the surface. These rates compare well with recent theoretical calculations for the system He⁺–Al(1 1 1). For incident Ar⁺ ions no survival of ions is found and upper limits for the survival probability and lower limits for the neutralization rate are determined.     

Light emission from oxygen covered Al and Cu surfaces

Ion beam induced light emission is used to investigate the sputtering yield, S_O, of oxygen atoms on the surfaces of a polycrystalline copper and an Al(1 1 1) target. Under Ar⁺ and Ne⁺ ion bombardment of Al(1 1 1) and polycrystalline copper targets, spectral lines of Cu I and Al I emitting from sputtered excited atoms are measured as a function of the oxygen partial pressure, wavelength and beam energy. The light emission for two Al I lines (3082 and 3962 Å) and Cu I lines (3247 and 3274 Å) are proportional to the oxygen partial pressure (1×10⁻⁴ Torr). Above 2×10⁻⁴ Torr, the light intensities start to decrease which is consistent with other measurements. From saturated-oxygen covered target surfaces, light intensities of Al I and Cu I lines are measured as a function of time and oxygen partial pressures. The sputtering yields could be determined from the curves of spectral lines directly. For 10 and 20 keV Ar⁺ ions bombarding the copper surface, the oxygen sputtering yields are 0.34 and 0.22 (atoms/ion), respectively. The same copper target was bombarded by Ne⁺ ions at 5 and 10 keV, the oxygen sputtering yields are 0.87 and 0.59, respectively. For 10, 15, and 20 keV Ar⁺ bombarding an Al(1 1 1) target, the obtained sputtering yields are 0.44, 0.31, and 0.2 (atoms/ion), respectively.     

Ion beam enhanced etching of LiNbO3

Single crystals of z- and x-cut LiNbO₃ were irradiated at room temperature and 15 K using He⁺- and Ar⁺-ions with energies of 40 and 350 keV and ion fluences between 5 × 10¹² and 5 × 10¹⁶ cm⁻². The damage formation investigated with Rutherford backscattering spectrometry (RBS) channeling analysis depends on the irradiation temperature as well as the ion species. For instance, He⁺-irradiation of z-cut material at 300 K provokes complete amorphization at 2.0 dpa (displacements per target atom). In contrast, 0.4 dpa is sufficient to amorphize the LiNbO₃ in the case of Ar⁺-irradiation. Irradiation at 15 K reduces the number of displacements per atom necessary for amorphization. To study the etching behavior, 400 nm thick amorphous layers were generated via multiple irradiation with He⁺- and Ar⁺-ions of different energies and fluences. Etching was performed in a 3.6% hydrofluoric (HF) solution at 40 °C. Although the etching rate of the perfect crystal is negligible, that of the amorphized regions amounts to 80 nm min⁻¹. The influence of the ion species, the fluence, the irradiation temperature and subsequent thermal treatment on damage and etching of LiNbO₃ are discussed.     

Surface spin polarization in Fe(1 1 0) and Ni(1 1 0)

The magnetism of Ni(1 1 0) and Fe(1 1 0) surfaces was investigated by electron capture spectroscopy. He⁺ and He²⁺ ions impinged on the Fe(1 1 0) and Ni(1 1 0) surfaces under grazing incidence, and the degree of polarization of the light emitted by the neutralized projectiles was analyzed. Our measurements show that in Ni(1 1 0) minority electrons have a higher density of states at the Fermi energy than majority electrons, opposed to the Fe(1 1 0) case. From a comparison of our measurements we estimate the ratio between captured minority and majority electrons in Ni(1 1 0) to be similar as the ratio between captured majority and minority electrons in Fe(1 1 0).     

Desorption of silver atoms from benzene-covered Ag(1 1 1) by energetic Ar bombardment

Experiments have been conducted to gain insight into the processes of desorption of neutral species from surfaces covered with organic molecules due to bombardment with keV particles. The system is comprised of benzene molecules adsorbed onto Ag(1 1 1) and bombarded with 8 keV Ar⁺ ions. Molecular dynamics (MD) simulations of the same system have been performed. Results show that the presence of the benzene alters the yield, the kinetic energy distributions, and the angular distributions of the silver atoms. These changes of the desorption characteristics are the result of collisions between the Ag atoms and the benzene molecules adsorbed to the surface. As more benzene is adsorbed to the surface, the changes to the Ag atom desorption characteristics become more pronounced. The simulations reproduce the modifications to the Ag atom energy and angle distributions.     

The influence of calcium ions on the development of acidity in corrosion product deposits on SIMFUEL, UO2

In order to clarify the influence of groundwater constituents on the formation of corrosion products and secondary phase deposits on corroding/dissolving nuclear fuel surfaces under waste disposal conditions we have investigated the influence of Ca²⁺, present as CaCl₂. The influence of calcium ions on the anodic dissolution of SIMFUEL (doped uranium dioxide) has been characterized over the potential range 0–500 mV (vs. SCE). Through the use of X-ray photoelectron spectroscopy (XPS) the surface composition over this potential range has been determined. Ca²⁺ was found not to influence the conversion of U^IVO₂ to , but to suppress the subsequent formation of a U^VI surface species which lead to the formation of a hydrated deposit, UO₃ · yH₂O. The adsorption of Ca²⁺ on the UO₂ surface is believed to inhibit fuel dissolution either via inhibiting the stabilization of the cation precursor (UO₂(OH)₂)_ads or by blocking the O²⁻ anion transfer reaction from the fuel surface.     

Irradiation-induced nanostructures in cadmium niobate pyrochlores

This paper reports the formation processes of crystalline Cd nanostructures on ion-cut surfaces of cadmium niobate pyrochlores (Cd₂Nb₂O₇). Irradiation with 3 MeV He⁺ ions has been performed at low temperatures (295 K) to induce material decomposition and aggregation of host atoms. The irradiation also leads to surface exfoliation due to rupture of gas (He and O₂) filled blisters. Nanoparticles and nanowires are observed on the ion-cut surfaces at low and higher doses, respectively. These structures are examined and characterized using a suite of experimental tools. Both the particles and wires are found to be single crystals that primarily consist of metallic Cd.     

Material dependence of total electron emission yields following slow highly charged ion impact

The total electron emission yields following the interaction of “Slow (2 keV/a.u.) Highly Charged Ions” (SHCI) (O³⁺⁷⁺, Xe¹²⁺⁵²⁺, Au⁵⁴⁺⁶⁹⁺) with different target surfaces (highly-oriented pyrolytic graphite (HOPG), Au and SiO2) have been measured. The emission yields increase with charge state, and is found to be highest for carbon, the HOPG target, and lowest for the SiO₂ target. An empirical formula for the electron emission is including recent results from investigations of plasmon excitation following SHCI impact are used to interpret the results.     

Neutralization rate for slow Ar ions in front of KCl(0 0 1)

Charge state distributions of reflected ions are measured when 5 keV Ar^q+(q = 0−2) ions are incident on a clean KCl(0 0 1) surface at grazing angle, θ_i. Although the charge state distribution does not depend on the incident charge state at larger θ_i, significant dependence of the charge state distribution on incident charge state is observed at smaller θ_i. The ionization of Ar⁰ is completely suppressed at θ_i < 20 mrad, while large neutralization probability is observed for Ar⁺ incidence. These features allow us to derive the position-dependent neutralization rate of Ar⁺ in front of KCl(0 0 1). The obtained neutralization rate decreases exponentially with distance from the surface as it is usually assumed.     

Structural changes in anatase TiO2 thin films irradiated with high-energy heavy ions

In order to investigate possible structural changes due to high-density electronic excitation, anatase TiO₂ thin film specimens were irradiated with 230 MeV ¹³⁶Xe¹⁵⁺ ions and 200 MeV ¹⁹⁷Au¹³⁺ ions. X-ray diffraction (XRD) patterns were measured before and after irradiation. The intensity of the XRD peak assigned to the (0 0 4) planes of anatase TiO₂ decreases in an exponential manner as a function of ion-fluence. This result can be explained by the formation of the cylindrical damaged regions (i.e. ion tracks) with diameters of 9.6 and 16.3 nm for 230 MeV Xe and for 200 MeV Au ion irradiations, respectively. The difference in the track diameter between Xe ion irradiation and Au ion irradiation can be attributed to the difference in the electronic stopping power (and to the ion-velocity effect, if any). For 200 MeV Au ion irradiation, splitting of the (0 0 4) peak is observed. The original (0 0 4) TiO₂ peak remains in the same position, but the new peak shifts to higher angles as fluence increases.     

Oxygen ion source with plasma cathode

An ion source with a plasma cathode has been developed for long lifetime use in ion implanters. In this ion source, a plasma cathode replaces the conventional metallic filament used in a Freeman-type ion source. This ion source consists of two compartments, namely a plasma generator and an ion source chambers interconnected by a tapered narrow duct. The pressure difference between the two parts, maintained by differential pumping, prevents the feed gas from flowing into the plasma generator. With any combination of an argon plasma cathode and a feed gas of either fluoride (AsF₅, PF₅) or oxygen, the lifetime was found to be more than 90 h with an extraction voltage of 40 kV and a correspoding ion current density of 20 mA/cm², and a considerable amount of As⁺, P⁺, O⁺, and O₂⁺ ions were observed in mass spectra.     

Bubbles in SiC crystals formed by helium ion irradiation at high temperatures

Helium bubbles were found to be formed in SiC crystals by irradiation with He⁺ ions at 1000 to 1200° C. The size of bubbles increased with increasing irradiation temperatures.

The density of helium atoms in the bubbles was measured to be about 10²⁸ atoms/m³ by EELS measurement in combination with electron microscopic observation in the same selected areas, and the internal pressure of the bubbles was estimated therefrom to be on the order of 10⁸ Pa at room temperature.     

Color center annealing and ageing in electron and ion-irradiated yttria-stabilized zirconia

We have used X-band electron paramagnetic resonance (EPR) measurements at room-temperature (RT) to study the thermal annealing and RT ageing of color centers induced in yttria-stabilized zirconia (YSZ), i.e. ZrO₂:Y with 9.5 mol% Y₂O₃, by swift electron and ion-irradiations. YSZ single crystals with the 1 0 0 orientation were irradiated with 2.5 MeV electrons, and implanted with 100 MeV ¹³C ions. Electron and ion beams produce the same two color centers, namely an F⁺-type center (singly ionized oxygen vacancy) and the so-called T-center (Zr³⁺ in a trigonal oxygen local environment) which is also produced by X-ray irradiations. Isochronal annealing was performed in air up to 973 K. For both electron and ion irradiations, the defect densities are plotted versus temperature or time at various fluences. The influence of a thermal treatment at 1373 K of the YSZ single crystals under vacuum prior to the irradiations was also investigated. In these reduced samples, color centers are found to be more stable than in as-received samples. Two kinds of recovery processes are observed depending on fluence and heat treatment.     

Molecular dynamics simulation of fluorine ion etching of silicon

Formation of precursors and desorption of etching products by fluorine ion irradiation were studied using molecular dynamics (MD) simulation. When F atoms impact sequentially on a Si substrate, a mixed layer of F and Si atoms is formed on the surface. When the incident energy is below 30 eV, the fluorine coverage reaches steady state after 1.0×10¹⁶ atoms/cm² irradiation. The ratio of F to Si in the mixed layer is about 1:1. At an incident energy of 15 eV, the mixed layer at steady state consists of 4.5 ML of fluorine with a depth of 20 Å and the main etching products are SiF₃ and SiF₄. At 30 eV incident energy, the mixed layer at steady state is 6.5 ML with a depth of 40 Å and the main etching products are SiF₂ and SiF₃. When F atoms were irradiated onto a Si substrate heated at 1000 K, a significant reduction of F coverage was observed due to diffusion of F atoms.     

Large conductivity enhancement in polycrystalline 12CaO · 7Al2O3 thin films induced by extrusion of clathrated O ions by hot Au implantation and ultraviolet light illumination

Large enhancement in electrical conductivity from <10⁻¹⁰ S cm⁻¹ to 4 × 10⁻² S cm⁻¹ was achieved in polycrystalline 12CaO · 7Al₂O₃ (p-C12A7) thin films by hot Au⁺ implantation at 600 °C and subsequent ultraviolet (UV) light illumination. Although the as-implanted films were transparent and insulating, the subsequent UV-light illumination induced persistent electronic conduction and coloration. A good correlation was found between the concentration of photo-induced F⁺-like centers (a cage trapping an electron) and calculated displacements per atom, indicating that the hot Au⁺ implantation extruded free O²⁻ ions from the cages in the p-C12A7 films by kick-out effects and left electrons in the cages. These results suggest that H⁻ ions are formed by the Au⁺ implantation through the decomposition of preexisting OH⁻ ions. Subsequent UV-light illumination produced F⁺-like centers via photoionization of the H⁻ ions, which leads to the electronic conduction and coloration.     

Kinetic electron emission yield induced by H and He ions versus stopping power for Al, Cu, Ag and Au

For H⁺ and He²⁺ ions impinging on Al, Cu, Ag and Au targets we measured simultaneously the yield, γ, of emitted electrons and the electronic energy loss, S_e, in the energy range 0.5 to 4.8 MeV. The targets were prepared under high-vacuum conditions before they were transferred to an ultra-high-vacuum chamber without breaking the vacuum. The targets were sputter cleaned and their composition was examined by Auger electron spectrometry. The values of γ were obtained by current integration and S_e was determined from the energy width of Rutherford backscattering spectra. For H⁺ ions impinging on Cu, Ag or Au and He²⁺ on Al and Cu, the expected proportionality between γ and S_e was found within the experimental errors of 2%. For H⁺ ions on Al and He²⁺ ions on Ag and Au targets, significant deviations were observed.     

High energy oxygen ion induced modifications in lead based perovskite thin films

The lead based ferroelectric PbZr_0.53Ti_0.47O₃ (PZT), (Pb_0.90La_0.10)TiO₃ (PLT10) and (Pb_0.80La_0.20)TiO₃ (PLT20) thin films, prepared by pulsed laser ablation technique, were studied for their response to the 70 MeV oxygen ion irradiation. The dielectric analysis, capacitance–voltage (C–V) and DC leakage current measurements were performed before and after the irradiation to high-energy oxygen ions. The irradiation produced considerable changes in the dielectric, C–V, leakage characteristics and induced some amount of amorphization. The PZT films showed partial recrystallization after a thermal annealing at 400 °C for 10 min. The phase transition temperature [T_c] of PLT20 increased from 115 °C to 120 °C. The DC conductivity measurements showed a shift in the onset of non-linear conduction region. The current density decreased by two orders of magnitude after irradiation. After annealing the irradiated films at a temperature of 400 °C for 10 min, the films partially regained the dielectric and electrical properties. The results are discussed in terms of the irradiation-induced amorphization, the pinning of the ferroelectric domains by trapped charges and the thermal annealing of the defects generated during the irradiation.     

Analysis of the desorption of clusters of intact amino acid valine molecules induced by energetic monoatomic and cluster ions

The experiments on the desorption of intact valine molecules and (nM + H)⁺ clusters are analyzed and a ln(Y/S_e) − 1/S_e scaling is found where Y, and S_e are the sputtering yield and the electronic stopping power, respectively. The scaling can be derived with the assumption of a thermal activation mechanism. In the plots the desorption is a uniform process without threshold value of S_e, having different activation energies U in various charge states. The desorption of (nM + H)⁺ clusters proceeds in n steps with varying Coulomb contributions. Irradiation with C₁₀ and C₆₀ ions leads to higher Y, however, the increment is reduced with the increase of S_e.     

Release of nitrogen from SiOxNy films during RBS measurement

We have found that nitrogen atoms are released very rapidly from ultrathin SiO_xN_y films (2.6 nm) during RBS measurement with 500 keV He⁺ ions. The release behavior strongly depends on the preparation technique of the SiO_xN_y films. There is no release from the film prepared by thermal nitridation of SiO₂, while 80% of the nitrogen atoms are released from the film prepared by plasma nitridation at a fluence of 1×10¹⁶ cm⁻². The release cross-section for plasma SiO_xN_y films is of the order of 10⁻¹⁶ cm². This large cross-section cannot be explained by a simple recoil mechanism. The nitrogen release is also observed under irradiation with 5–10 keV electrons though the cross-section is of the order of 10⁻¹⁹ cm². These findings suggest that the observed nitrogen release is an electronic excitation induced process.