Synergism in sputtering of copper nanoclusters on graphite substrate at low energy Cu2 bombardment

Molecular dynamics simulation of Cu cluster sputtering by 50-200 eV/atom Cu₂ dimers and Cu single atoms has been performed. The clusters were located on a (0 0 0 1) graphite surface and consisted of 13-195 atoms. Synergy features were identified in the sputtering yield and energy distributions of sputtered particles calculated for the cases of cluster bombardment with Cu dimers and monomers at the same velocity. The reason for the nonlinear effects in surface cluster sputtering is the overlapping of collision cascades generated by each of the dimer atoms.     

Temporal development of sputtered atom distributions from Au(1 1 1) targets following bombardment with 100 keV/atom Au2 ions

Recently Bouneau et al. measured the angular and energy distributions of negative Au_n (n=2–7) ions emitted from gold targets following bombardment with swift gold cluster projectiles. They found that the energy distributions could be fitted with a spike-like model, and that the angular distributions were independent of the azimuthal emission angle and relatively strongly forward directed. We have used MD simulations to investigate the temporal development of energy and angular distributions of sputtered atoms from Au(1 1 1) targets following bombardment with 100 keV/atom Au₂ ions. Our results show that during the very early stages of the collision cascade the energy distribution of sputtered atoms is described well by the linear cascade model. Essentially all high energy sputtered atoms are emitted during this phase of the collision cascade. However, the energy distributions of atoms sputtered after 0.5 ps were typical of emission from a thermal spike and could be fitted well with a Sigmund–Claussen model. The polar angle distributions of sputtered atoms were strongly forward directed early in the collision cascade, but became less forward directed as the thermal spike developed.     

Low energy sputtering of eutectic Ag/Cu alloys

Experiments were carried out on the sputtering of a eutectic Ag/Cu (N_Ag/N_Cu = 1.5) alloy by normally incident 110 eV Ar⁺ ions. The collected sputtered flux was analyzed by Rutherford backscattering (RBS). Material sputtered normal to the surface at a fluence of 7 × 10¹⁹ Ar/cm² was stoichiometric (N_Ag/N_Cu ≈ 1.5), but became increasingly Cu rich at larger angles of ejection up to 75° at which N_Ag/N_Cu was about 1.09. The overall ejection was slightly Cu rich (N_Ag/N_Cu ≈ 1.3). RBS analysis of the sputtered alloy surfaces indicated they were Cu rich to a depth of about 1500 Å, with the greatest Cu content at about 450 Å depth (up to 56% Cu), the effect depending on the fluence of the bombarding Ar⁺ ions. Scanning electron micrographs of the sputtered alloy surfaces showed dense microtopographic formations.     

The influence of projectile charge state on ionization probabilities of sputtered atoms

The ionization probability of atoms sputtered from a clean polycrystalline metal surface was measured for different charge states of the projectile used to bombard the sample. More specifically, a polycrystalline indium surface was irradiated with Ar⁺ and Ar⁰ beams of energies between 5 and 15 keV, and In⁺ secondary ions and neutral In atoms emitted from the surface were detected under identical experimental conditions regarding the sampled emission angle and energy. The resulting energy integrated ionization probability of sputtered In atoms is consistently found to be smaller for neutral projectiles, the difference decreasing with decreasing impact energy. The observed trends agree with those measured for kinetic electron emission, indicating that secondary ion formation is at least partly governed by kinetic substrate excitation.     

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.     

Predicting the probability for fission gas resolution into uranium dioxide

Classical molecular dynamics simulations, using a set of previously established pair potentials, have been used to predict the minimum energy needed for krypton and xenon atoms to be resolved into uranium dioxide across a perfect (1 1 1) surface. The absolute minimum energy, E_min, is 53 eV for krypton and 56 eV for xenon atoms, significantly less than the 300 eV value often assumed in fuel modelling as the minimum energy required for gas resolution. The present values are, however, still sufficient to preclude thermal resolution at normal reactor temperatures. The discrepancies between the present and previous resolution energies are due to the significant variation in probabilities of absorption at different impact points on the crystal surface; we have mapped out the probability distribution for various impact sites across the crystal surface. The value of 300 eV corresponds to an 85% chance of resolution.     

Scattering of protons by hydrogen atoms at low energies: Phase shifts and differential cross sections

Phase shifts and differential cross sections for spin exchange (charge transfer) and total elastic scattering of protons by hydrogen atoms are presented for 36 and 38 values, respectively, of the collisional kinetic energy in the range 0.0001 to 10 eV (center of mass). The phase shifts are tabulated with a precision of six decimal digits. Each cross section is presented as a graph covering the complete angular range from 0 to π radians (in center-of-mass coordinates). The phase shifts were obtained via partial wave analysis within a modified Perturbed-Stationary-States theory by calculations based upon very accurate (nonrelativistic) internuclear potential energies for the 1Sσ_g and 2Pσ_u electronic states of H₂⁺. The cross sections demonstrate a transition from purely quantum behavior at very low energies (<0.1 eV) to semicllssical behavior at higher energies (>1 eV) in which protons scattered by spin exchange are angularly separated from those scattered without exchange. Thus the in-principle unobservable charge-transfer cross section becomes physically measurable at energies greater than about 1 eV.     

Sputtering of clusters from copper-gold alloys

Polycrystalline Cu, Cu₂₀Au₈₀, Cu₄₀Au₆₀, Cu₈₀Au₂₀ and Au samples were bombarded with 15 keV Ar⁺, and the resulting secondary neutral yield distribution was studied by non-resonant laser post-ionisation mass spectrometry. Neutral clusters containing up to 15 atoms were observed for the targets. The yield of neutral clusters, Cu_mAu_n−m, containing n atoms, Y_n, was found to follow a power in n, i.e. Y_n∝n^-δ, where the exponent δ varied from 5.2 to 10.1. For a fixed n, the cluster yields showed a variation with number of copper atoms, m, much greater than expected for a binomial distribution suggesting that the clusters are not formed randomly above the surface and a component of preformed cluster emission occurs. In addition, the cluster compositions from the sputtered alloys were indicative of sputtering from a copper rich surface.     

The energy distribution of sputtered particles at low bombarding energies

The transport equations for the ion sputtering of metal targets are solved in the P_L-approximation. After a Laplace transform in the logarithmic energy variable, analytical solutions for the flux at the surface can be obtained. These are numerically Laplace inverted for the case of equal masses of projectile and target atoms and hard sphere interaction; the case of a power law scattering cross section dσ(T) = CT^?1dT is covered in P₁-approximation, too. At high bombarding ion energies, the solution recovers the asymptot for the distribution in energy E of sputtered particles; at low bombarding energies, however, the solution displays — for normally incident ions and perpendicularly emitted target atoms — a steeper spectrum. This is in accordance with measurement. Boundary conditions for a semi-infinite medium as well as for an infinite medium are applied; these show only negligible influence on the solution. Furthermore, a solution by way of B_L-approximation is obtained, which confirms the above results.     

Repulsive potentials for low energy projectiles incident on copper surfaces

Interatomic potentials that are relevant for low energy (<2 keV) projectiles (X = He, Cl, Ar, Cu) incident on the Cu(1 0 0) and Cu(1 1 1) surfaces (represented by Cu₁₀ clusters), and on isolated Cu atoms, have been calculated from first principles using density functional theory. For energies above 10–20 eV, the diatomic X–Cu potentials provide acceptable approximations (typically within 1–2 eV) to the corresponding potentials for the surface environment.     

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.     

Theory of He trapping, diffusion, and clustering in UO2

We have performed ab initio total energy calculations to investigate the behavior of helium and its diffusion properties in uranium dioxide (UO₂). Our investigations are based on the density functional theory within the generalized gradient approximation (GGA). The trapping behavior of He in UO₂ has been modeled with a supercell containing 96-atoms as well as uranium and oxygen vacancy trapping sites. The calculated incorporation energies show that for He a uranium vacancy is more stable than an oxygen vacancy or an octahedral interstitial site (OIS). Interstitial site hopping is found to be the rate-determining mechanism of the He diffusion process and the corresponding migration energy is computed as 2.79 eV at 0 K (with the spin-orbit coupling (SOC) included), and as 2.09 eV by using the thermally expanded lattice parameter of UO₂ at 1200 K, which is relatively close to the experimental value of 2.0 eV. The lattice expansion coefficient of He-induced swelling of UO₂ is calculated as 9 × 10⁻². For two He atoms, we have found that they form a dumbbell configuration if they are close enough to each other, and that the lattice expansion induced by a dumbbell is larger than by two distant interstitial He atoms. The clustering tendency of He has been studied for small clusters of up to six He atoms. We find that He strongly tends to cluster in the vicinity of an OIS, and that the collective action of the He atoms is sufficient to spontaneously create additional point defects around the He cluster in the UO₂ lattice.     

Electronic excitation in sputtered atoms and the oxygen effect

Bombardment of surfaces by ions gives rise to a variety of inelastic collision events leading to the ejection of excited atoms and ions. Such excited sputtered particles have been studied since more than 80 years through their optical emission, when they decay in front of the target to the electronic ground state, having lifetimes of 10⁻⁹ to 10⁻⁷ s, typically. Information on the energy distribution of such excited states can be obtained by two different techniques: light vs distance measurements (LvD) and by studying line profile broadening in light emission due to the Doppler effect. Only recently it has become possible to study in addition metastable excited atoms using laser induced fluorescence spectroscopy (LIF). Relative sputtering yields and energy distributions have been measured for such metastable states and two types can be distinguished. States with a very low excitation energy (0–0.3 eV), being sublevels of the electronic ground state, were found to have yields and energy distributions comparable to the electronic ground state, while metastable states at higher excitation energies (above 1 eV) seem to behave similar to short lived excited states, typically observed in secondary photon emission (BLE) with excitation energies in the range of 2–6 eV. This behaviour is also clearly visible with respect to oxygen surface coverage or increased near surface oxygen concentration where, similar to secondary ion emission, drastic changes in the yield by orders of magnitude have been found for excited atoms as well as for ions. In addition, under the same conditions a strong decrease in the sputtering yield of neutral ground state atoms has been observed for a number of metals. LIF results for highly excited metastable states are compared with recent results obtained by studying line profile broadening in light emission for Ca, Al and Cr targets. Different mechanisms that have been proposed to account for the observations will be discussed.     

Film growth by polyatomic C2H5 bombarding a diamond (1 0 0) surfaces: Molecular dynamics study

The deposition of polyatomic C₂H₅⁺ ions is studied using classical molecular dynamics simulations with a new improved Brenner potentials developed by Brenner. The simulation results show that when the incident energy is less than 65 eV, the deposition coefficient of H is larger than that of C atoms. When the incident energy is larger than 65 eV, the deposition of H is less than that of C atoms. With increasing incident energy, a transition from Csp3-rich to Csp2-rich in the grown films is found.     

RBS and ion channeling studies of Ag-doped YBa2Cu3O7−δ targets and films

The location of Ag in Ag-doped YBa₂Cu₃O_7−δ (YBCO) films and other high-T_c materials (such as Ag-doped BiSrCaCuO films and Ag-sheathed textured BiSrCaCuO wires) is a very important issue for improving high-T_c materials. In this work, laser ablated and DC magnetron sputtered YBCO films on (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃ were prepared from sintered Ag-YBCO composite targets (nominally containing 5 wt% Ag) and studied by Rutherford Backscattering Spectrometry (RBS) and ion channeling techniques using 2.0 MeV⁴He⁺ and ⁷Li⁺ beams. We have found that the Ag-YBCO targets contain about 3 wt% Ag and most of the retained Ag atoms form some small size Ag precipitates with a typical size smaller than a few microns. We have demonstrated that in very good single crystalline YBCO films, the percentage of retained Ag in substitutional sites can be estimated by ion channeling technique. For example, we have found that about 1.2 wt% Ag atoms remain in the laser ablated Ag-doped films prepared from the Ag-YBCO target and about two-thirds of the retained Ag atoms occupy substitutional sites. The sputtered films contain less retained Ag atoms since the deposition temperature is higher and deposition time is longer than those for laser ablated films.     

Single- and multiple-electron loss cross-sections for fast heavy ions colliding with neutrals: Semi-classical calculations

Extensive calculations of single, multiple and total electron-loss cross-sections of fast heavy ions in collisions with neutral atoms are performed in the semi-classical approximation using the DEPOSIT code based on the energy deposition model and statistical distributions for ionization probabilities. The results are presented for Ar¹⁺, Ar²⁺, Kr⁷⁺, Xe³⁺, Xe¹⁸⁺, Pb²⁵⁺ and U^q+ (q = 10, 28, 39, 62) ions colliding with H, N, Ne, Ar, Kr, Xe and U atoms at energies E > 1 MeV/u and compared with available experimental data and the n-particle classical-trajectory Monte Carlo (nCTMC) calculations. The results show that the present semi-classical model can be applied for estimation of multiple and total electron-loss cross-sections within accuracies of a factor of 2.From calculated data for the total electron-loss cross-sections σ_tot, their dependencies on relative velocity v, the first ionization potential I₁ of the projectile and the target atomic number Z_A are found and a semi-empirical formula for σ_tot is suggested. The velocity range, where the semi-classical approximation can be used, is discussed.     

Electrically active defects in BF2+ implanted and germanium preamorphized silicon

Ultra-shallow p⁺-n junctions have been formed using 15 keV/10¹⁵ cm⁻² BF₂⁺ implantation into both Ge⁺-preamorphized and crystalline 〈1 0 0〉 silicon substrates. Rapid thermal annealing (RTA) for 15 s at 950°C was used for dopant electrical activation and implantation damage gettering. The electrically active defects present in these samples were characterized using Deep Level Transient Spectroscopy (DLTS) and isothermal transient capacitance (ΔC(t, T)). Two electron traps were detected in the upper half of the band gap at, respectively, E_c - 0.20 eV and E_c - 0.45 eV. They are shown to be related to Ge⁺ implantation-induced damage. On the other hand, BF₂⁺ implantation along with RTA give rise to a depth distributed energy continuum which lies within the forbidden gap between E_c - 0.13 eV and E_c - 0.36 eV. From isothermal transient capacitance (ΔC(t, T)), reliable damage concentration profiles were derived. They revealed that preamorphization induces not only defects in the regrown silicon layer but also a relatively high concentration of electrically active defects as deep as 3.5 μm into the bulk.     

Alkali ion scattering from Ag(0 0 1) and Ag thin films at low and hyperthermal energies

We have investigated the scattering of K⁺ and Cs⁺ ions from a single crystal Ag(0 0 1) surface and from a Ag-Si(1 0 0) Schottky diode structure. For the K⁺ ions, incident energies of 25 eV to 1 keV were used to obtain energy-resolved spectra of scattered ions at θ_i = θ_f = 45°. These results are compared to the classical trajectory simulation safari and show features indicative of light atom-surface scattering where sequential binary collisions can describe the observed energy loss spectra. Energy-resolved spectra obtained for Cs⁺ ions at incident energies of 75 eV and 200 eV also show features consistent with binary collisions. However, for this heavy atom-surface scattering system, the dominant trajectory type involves at least two surface atoms, as large angular deflections are not classically allowed for any single scattering event. In addition, a significant deviation from the classical double-collision prediction is observed for incident energies around 100 eV, and molecular dynamics studies are proposed to investigate the role of collective lattice effects. Data are also presented for the scattering of K⁺ ions from a Schottky diode structure, which is a prototype device for the development of active targets to probe energy loss at a surface.