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.     

Desorption of gold nanoclusters (2-30 nm) under low excitation of their electronic subsystem by Ar ions (14 keV/nm)

Gold nanodispersed targets with islands-grains sized 2-30 nm were irradiated by Ar⁷⁺ ions with the energy of 45.5 MeV and (dE/dx)_e = 14.2 keV/nm in gold. The desorbed gold nanoclusters were studied by TEM method. For all the targets desorption of intact gold nanoclusters is observed. However, for inelastic stopping of monatomic Ar ions in gold of 14.2 keV/nm desorption of nanoclusters is observed only up to ∼25 nm. The yield of the desorbed nanoclusters considerably decreases from 3 to 0.02 cluster/ion with the increase of the mean size of the desorbed nanoclusters from 3 to 14.2 nm. The results are discussed.     

Desorption of nanoclusters from gold nanodispersed layers by 72 keV Au400 ions: Experiment and molecular dynamics simulation

The interaction of 72 keV Au₄₀₀ ions (with a diameter of approximately 2 nm) with nanodispersed gold targets has been studied. These interactions are dominated by elastic collisions. The gold nanodispersed target with 2-12 nm nanoislets was bombarded with a fluence of 1.7 × 10¹² ions/cm². The desorbed nanoclusters were collected on carbon foils supported by TEM-grids. Intact 29 nm gold nanoclusters were found on the collectors. The desorption yield (normalized to the total cross-section of the projectile-cluster interaction) was estimated to be 0.62 nanocluster/projectile. Preliminary estimates were made using molecular dynamic simulations for comparison with the experimental results.     

Monte Carlo study of ion-induced backward and forward secondary electron emission from thin Al foil

A direct Monte Carlo program has been developed to calculate the backward (γ_b) and forward (γ_f) electron emission yields from 20 nm thick Al foil for impact of C⁺, Al⁺, Ar⁺, Cu⁺ and Kr⁺ ions having energies in the range of 0.1-10 keV/amu. The program incorporates the excitation of target electrons by projectile ions, recoiling target atoms and fast primary electrons. 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. The calculated backward electron emission yield and the Meckbach factor R = γ_f/γ_b are compared with the available experimental data, and a good agreement is found. In addition, the effect of projectile energy and mass on the longitudinal and lateral distribution of the excitation points of the electrons emitted from front and back of Al target has been investigated.     

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.     

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.     

Sputtering of Langmuir-Blodgett multilayers by keV C60 projectiles as seen by computer simulations

Fundamental processes induced in a thick organic system composed of long, well-organized linear molecules by an impact of 5-20 keV C₆₀ are investigated. The organic system is represented by Langmuir-Blodgett multilayers formed from bariated molecules of arachidic acid. The thickness of the system varies between 2 and 16 nm. Coarse-grained molecular dynamics computer simulations are applied to investigate the energy transfer pathways and sputtering yields as a function of the kinetic energy of the projectile and the thickness of the organic overlayer.The results indicate that an impact of keV C₆₀ projectiles leads to significant ejection of organic material. The efficiency of desorption increases with the kinetic energy of the projectile for a given layer thickness. For a constant primary kinetic energy, the sputtering yield goes through a maximum and finally saturates as the LB layer becomes thicker. Such behaviour is caused by a competition between signal enhancement due to increasing number of organic molecules and signal decrease due to lowering of the amount of the primary energy being backreflected into the organic overlayer by the receding organic/metal interface as the layer is getting thicker. When the sample thickness becomes much larger than the penetration depth of the projectile, the sputtering yield is independent of thickness. The deposited energy is channelled by an open and ordered molecular structure, which leads to abnormally long projectile penetration and ion-induced damage.     

Study of density effect of large gas cluster impact by molecular dynamics simulations

Large gas cluster impacts cause unique surface modification effects because a large number of target atoms are moved simultaneously due to high-density particle collisions between cluster and surface atoms. Molecular dynamics (MD) simulations of large gas cluster impacts on solid targets were carried out in order to investigate the effect of high-density irradiation with a cluster ion beam from the viewpoint of crater formation and sputtering. An Ar cluster with the size of 2000 was accelerated with 20 keV (10 eV for each constituent atom) and irradiated on a Si(1 0 0) solid target consisting of 2 000 000 atoms. The radius of the Ar cluster was scaled by ranging from 2.3 nm (corresponding to the solid state of Ar) to 9.2 nm (64× lower density than solid state). When the Ar cluster was as dense as solid state, the incident cluster penetrated the target surface and generated crater-like damage. On the other hand, as the cluster radius increased and the irradiation particle density decreased, the depth of crater caused by cluster impact was reduced. MD results also revealed that crater depth was mainly dominated by the horizontal scaling rather than vertical scaling. A high sputtering yield of more than several tens of Si atoms per impact was observed with clusters of 4-20× lower volume density than solid state.     

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.     

Large-area and high-density silicon nanocone arrays by Ar sputtering at room temperature

The large-area, high-density of ∼1-2 × 10⁹/cm² silicon nanocone arrays by ion-irradiation with incident angle of 75° have been achieved by using carbon-cone-mask. The scanning electron microscopy (SEM) images show that the width of silicon nanocones is ∼150 nm and the height is ∼400 nm. The investigation of SEM shows that the formation of the silicon nanocones proceeds through three periods, carbon nanocones-nanocones with carbon on the top and silicon at the bottom-silicon nanocones.     

Collision cascade temperature

Interaction of a projectile with a solid has been considered in detail. It has been found that any collision cascade generated by a projectile can be characterized by the average kinetic energy of cascade atoms that represents an “instantaneous temperature” of the cascade during its very short lifetime (10⁻¹² s). We refer to this value as the “dynamic temperature” in order to emphasize the fact that cascade atoms are in a dynamic equilibrium and have a definite energy distribution. The dynamic temperature defines the electron distribution in the cascade area and, hence, the ionization probability of sputtered atoms. The energy distribution of cascade atoms and, as a consequence, the dynamic temperature can be found experimentally by measuring the energy distribution of sputtered atoms. The calculated dynamic temperature has been found to be in good agreement with the experimental data on ion formation in the case of cesium and oxygen ion sputtering of silicon. Based on the developed model we suggest an experimental technique for a radical improvement of the existing cascade sputtering models.     

Dependence of cluster ranges on target cohesive energy: Molecular-dynamics study of energetic Au402 cluster impacts

It has long been known that the stopping and ranges of atoms and clusters depends on the projectile-target atom mass ratio. Recently, Carroll et al. [S.J. Carroll, P.D. Nellist, R.E. Palmer, S. Hobday, R. Smith, Phys. Rev. Lett. 84 (2000) 2654] proposed that the stopping of clusters also depends on the cohesive energy of the target. We investigate this dependence using a series of molecular-dynamics simulations, in which we systematically change the target cohesive energy, while keeping all other parameters fixed. We focus on the specific case of Au₄₀₂ cluster impact on van-der-Waals bonded targets. As target, we employ Lennard-Jones materials based on the parameters of Ar, but for which we vary the cohesive energy artificially up to a factor of 20. We show that for small impact energies, E₀ ? 100 eV/atom, the range D depends on the target cohesive energy U, D ∝ U^−β. The exponent β increases with decreasing projectile energy and assumes values up to β = 0.25 for E₀ = 10 eV/atom. For higher impact energies, the cluster range becomes independent of the target cohesive energy. These results have their origin in the so-called ‘clearing-the way’ effect of the heavy Au₄₀₂ cluster; this effect is strongly reduced for E₀ ? 100 eV/atom when projectile fragmentation sets in, and the fragments are stopped independently of each other. These results are relevant for studies of cluster stopping and ranges in soft matter.     

Desorption of gold nanoclusters from gold nanodispersed targets by 200 keV Au5 polyatomic ions in the elastic stopping mode: Experiment and molecular-dynamics simulation

Au nanoislet targets (∅ 2-60 nm) were bombarded by 200 keV polyatomic ions (40 keV/atom), which deposit their energy mainly in the nuclear stopping mode: ∑(dE/dx)_n = 30 keV/nm and ∑(dE/dx)_e = 2 keV/nm. The matter desorbed in the form of nanoclusters was registered by TEM. The total transfer of matter was determined by neutron-activation analysis. The total yield of the ejected gold reached high values of up to 2.6 × 10⁴ atoms per Au₅ ion. The major part (2 × 10⁴ atoms per ion Au₅) of the emission is in the form of nanoclusters. The results are compared with the data of similar experiments with 1 MeV Au₅ (200 keV/atom) and other projectiles. The analysis of the experimental data and the comparison to molecular-dynamics simulation results of the desorption process show that the desorption of Au nanoislets is induced by their melting, build-up of pressure and thermal expansion.     

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%.     

Sputtering of cryogenic films of hydrogen by keV ions: Thickness dependence and surface morphology

The sputtering yield induced by keV hydrogen ions measured at CERN and at Risø National Laboratory for solid H₂ and D₂ at temperatures below 4.2 K decreases with increasing film thickness from about 100 × 10¹⁵ molecules/cm². For a film thickness comparable to or larger than the ion range the data from Risø show a slight increase, whereas the yield from CERN continues to decrease up to very large film thicknesses, i.e. one order of magnitude larger than the ion range. The different behavior of the yield is discussed in terms of the probable growth modes of the films. The films produced at the Risø setup are quench-condensed films, while those produced at CERN are supposed to grow with large hydrogen aggregates on top of a thin bottom layer.     

Ion-induced electron emission monitoring of the structure and morphology evolution in HOPG

The temperature dependences of the ion-induced electron emission yield γ of highly-oriented pyrolytic graphite (HOPG) under high-fluence (10¹⁸-10¹⁹ ions/cm²) 30 keV Ar⁺ ion irradiation at ion incidence angles from θ = 0^o (normal incidence) to 80^o have been measured to trace both the structure and morphology changes in the basal oriented samples. The target temperature has been varied during continuous irradiation from T = −180 to 400 ^oC. The surface analysis has been performed by the RHEED and SEM techniques. The surface microgeometry was studied using laser goniophotometry (LGF). The dependences of γ(T) were found to be strongly non-monotonic and essentially different from the ones for Ar⁺ and N₂⁺ ion irradiation of the polygranular graphites. A sharp peak at irradiation temperature T_p ≈ 150 ^oC was found. A strong influence of electron transport anisotropy has been observed, and ion-induced microgeometry is discussed.     

The morphology and structure of one-dimensional carbon-carbon composite under high-fluence ion irradiation

The temperature dependences of the ion-induced electron emission yield γ(T), the crystal structure, and the morphology of a surface layer of the one-dimensional carbon fiber composite KUP-VM (1D) under high-fluence (10¹⁸-10¹⁹ ion/cm²) irradiation with 30 keV ions at normal incidence both perpendicular and parallel to the fiber directions have been studied. The target temperature has been varied during continuous irradiation from T = −180 to 400 °C. The surface analysis has been performed by the RHEED, SEM and RBS techniques. The surface microgeometry was studied using laser goniophotometry (LGP). It has been found that ion irradiation results in a loss of anisotropy of the surface layer structure because of amorphization at room temperature or recrystallization at a temperature higher than the ion-induced annealing temperature. The fiber morphology anisotropy remains under ion irradiation.     

The emission process of secondary ions from solids bombarded with large gas cluster ions

We investigated the effects of size and energy of large incident Ar cluster ions on the secondary ion emission of Si. The secondary ions were measured using a double deflection method and a time-of-flight (TOF) technique. The size of the incident Ar cluster ions was between a few hundreds and several tens of thousands of atoms, and the energy up to 60 keV. Under the incidence of keV energy atomic Ar ions, mainly atomic Si ions were detected, whereas Si cluster ions were rarely observed. On the other hand, under the incidence of large Ar cluster ions, the dominant secondary ions were  (2 ? n ? 11). It has become clear that the yield ratio of secondary Si cluster ions was determined by the velocity of the incident cluster ions, and this strong dependence of the yield ratio on incident velocity should be related to the mechanisms of secondary ion emission under large Ar cluster ion bombardment.     

Dynamics of cluster induced sputtering in gold

Impacts of 0.13-1.4 MeV Au₁₃ clusters onto Au(1 1 1) target are investigated in molecular dynamics simulations. The evolution of sputtered Au atoms and clusters are simulated up to 10 ns. The total sputtering yield, angular and velocity distributions of the sputtered material, as well as dimensions of impact induced craters are compared to recent experimental results. It is shown that the experimental observations can be explained by a flow of atoms from the craters. Secondary cluster ejection from crowns formed around the craters is found to be one of the main mechanisms of sputtering. The results are summed up in an empirical model.     

Temperature dependence of the chemical sputtering of amorphous hydrogenated carbon films by hydrogen

The temperature dependence of chemical erosion and chemical sputtering of amorphous hydrogenated carbon films due to exposure to hydrogen atoms (H⁰) alone and combined exposure to argon ions and H⁰ was measured in the temperature range from 110 to 950 K. The chemical erosion yield for H⁰ alone is below the detection limit for temperatures below about 340 K. It increases strongly with increasing temperature, goes through a maximum around 650–700 K and decreases again for higher temperatures. Combined exposure to Ar⁺ and H⁰ results in substantial chemical sputtering yields in the temperature range below 340 K. In this range the yield does not depend on temperature, but it increases with energy from about 1 (eroded carbon atoms per impinging Ar⁺ ion) to about 4 if the ion energy is increased from 50 to 800 eV. For temperatures above 340 K the measured erosion rates show the same temperature dependence as for the H⁰-only case, but they are higher than for H⁰-only. The difference between the Ar⁺ and H⁰ and the H⁰-only cases increases monotonically with increasing ion energy.