Damage analysis of benzene induced by keV fullerene bombardment

Molecular dynamics computer simulations have been used to investigate the damage of a benzene crystal induced by 5 keV C₂₀, C₆₀, C₁₂₀ and C₁₈₀ fullerene bombardment. The sputtering yield, the mass distributions, and the depth distributions of ejected organic molecules are analyzed as a function of the size of the projectile. The results indicate that all impinging clusters lead to the creation of almost hemispherical craters, and the process of crater formation only slightly depends on the size of the fullerene projectile. The total sputtering yield as well as the efficiency of molecular fragmentation are the largest for 5 keV C₂₀, and decrease with the size of the projectile. Most of the molecules damaged by the projectile impact are ejected into the vacuum during cluster irradiation. Similar behavior does not occur during atomic bombardment where a large portion of fragmented benzene molecules remain inside the crystal after projectile impact. This “cleaning up” effect may explain why secondary ion mass spectrometry (SIMS) analysis of some organic samples with cluster projectiles can produce significantly less accumulated damage compared to analysis performed with atomic ion beams.     

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.     

High-speed processing with Cl2 cluster ion beam

Cluster ion beam processes can produce high rate sputtering with low damage compared with monomer ion beam processes. Cl₂ cluster ion beams with different size distributions were generated with controlling the ionization conditions. Size distributions were measured using the time-of-flight (TOF) method. Si substrates and SiO₂ films were irradiated with the Cl₂ cluster ions at acceleration energies of 10–30 keV and the etching ratio of Si/SiO₂ was investigated. The sputtering yield increased with acceleration energy and was a few thousand times higher than that of Ar monomer ions. The sputtering yield of Cl₂ cluster ions was about 4400 atoms/ion at 30 keV acceleration energy. The etching ratio of Si/SiO₂ was above eight at acceleration energies in the range 10–30 keV. Thus, SiO₂ can be used as a mask for irradiation with Cl₂ cluster ion beam, which is an advantage for semiconductor processing. In order to keep high sputtering yield and high etching ratio, the cluster size needs to be sufficiently large and size control is important.     

Study of crater formation and sputtering process with large gas cluster impact by molecular dynamics simulations

Molecular dynamics (MD) simulations of large argon clusters impacting on silicon solid targets were performed in order to study the transient process of crater formation and sputtering. The MD simulations demonstrate that the initial momentum of incident cluster is transferred to target surface atoms through multiple collision mechanism, where the initial momentum, which is along to the surface normal before impact, is deflected to lateral direction. This momentum transfer process was analyzed by the calculation of the velocity at the crater edge (the interface between cluster and target). In the case of Ar₁₀₀₀ cluster impact on Si(1 0 0) target at low energy per atom less than 40 eV/atom, the maximum value of lateral velocity of the crater edge increases in proportional to the velocity of incident cluster atoms. On the other hand, the crater edge velocity saturates over 40 eV/atom of incident energy per atom. In this case, the whole of constituent cluster atoms are implanted into the target and expand in both lateral and reflective directions at the subsurface region of the target. These MD simulations demonstrated that this collisional process result in the high yield sputtering of the target 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.     

Photon emission produced by particle-surface collisions

Visible, ultraviolet and infrared optical emission results from low-energy (20 eV–10 keV) particle-surface collisions. Several distinct kinds of collision induced optical radiation are discussed which provide fundamental information on particle-solid collision processes. Line radiation arises from excited states of sputtered surface constituents and backscattered beam particles. This radiation uniquely identifies the quantum state of sputtered or reflected particles, provides a method for identifying neutral atoms sputtered from the surface and serves as the basis for a sensitive surface analysis technique. Broadband radiation from the bulk of the solid is attributed to the transfer of projectile energy to the electrons in the solid. Continuum emission observed well in front of transition metal targets is believed to arise from excited atom clusters (diatomic, triatomic etc.) ejected from the solid in the sputtering process. Application of sputtered atom optical radiation for surface and depth profile analysis is demonstrated for the case of submonolayer quantities of chromium on silicon and aluminium implanted in SiO₂.     

Molecular dynamics simulations of argon cluster impacts on a nickel film surface

In this study we probe the surface phenomena that occur on nickel thin films after argon cluster impacts by performing several simulations using various energies. The simulations are carried out based on a molecular dynamics (MD) approach. The argon cluster consists of 353 atoms with energies ranging from 1 keV to 3.0 keV. The simulation results show that when the incident energy is 1 keV, the surface retains its smoothness after impact although a slight thermal effect appears near the surface beneath the impact area. Increasing the argon cluster energy to 2 keV causes the atoms in the film to shift slightly under impact and a small hillock appears on the film surface after impact. When the cluster energy increases to 3 keV, a hemispherical crater will appear on the film surface after impact. In addition, a shock wave is generated within the film due to the impact, which propagates toward to the substrate in a hemispherical shape. These shock wave related phenomena are difficult to probe experimentally on an atomic level however molecular dynamics simulations are a suitable tool for investigating the shock wave phenomena in thin film.     

Sputtering from spherical Au clusters by energetic atom bombardment

Using molecular-dynamics simulation, we study the effect of 100 keV Au atom bombardment of spherical Au clusters (radius R=40 Å), containing 15,784 atoms. Results range from projectile transmission with only few atoms sputtered to more or less complete cluster disintegration. During disintegration, besides major fragments of the original cluster, monatomics and a large number of clusters with sizes up to 100 atoms, and even beyond, are created. Angular and energy spectra of sputtered atoms show features of both collisional sputtering and evaporation: particle emission is isotropic with an additional contribution of preferential emission along [1 1 0] directions. Energy spectra show the high-energy E⁻² fall-off typical of linear-cascade sputtering plus an additional low-energy thermal component.     

Sputtering of GaAs under oblique Cs bombardment: A simulation study

Sputtering of GaAs under oblique 2–10 keV Cs ion bombardment is studied by means of computer simulation as applied to the experimental data by Verdeil et al. published recently. Special attention is given to the angular distribution of sputtered atoms in the steady-state limit and to the relevant concentrations of surface Ga and As atoms, S_Ga and S_As, respectively. The best-fit values of S_Ga and S_As found in simulations favor segregation of As. A very pronounced effect of resputtering of atoms deposited on a collector of sputtered matter is noted. For forecasting purposes, the sputtering of GaAs under oblique bombardment with 0.1–1 keV Cs ions is also shortly considered.     

Effect of impact angle and projectile size on sputtering efficiency of solid benzene investigated by molecular dynamics simulations

Molecular dynamics computer simulations have been used to investigate the effect of the cluster size on the sputtering yield dependence on the impact angle. Ar₃₆₆ and Ar₂₉₅₃ cluster projectiles with 14.75 keV of incident energy are directed at the surface of a solid benzene crystal described by a coarse-grained representation at angles between 0° and 70°. It is observed that the shape of the angular dependence of sputtering efficiency is strongly affected by the cluster size. For the Ar₃₆₆ cluster, the sputtering yield only slightly increases with the impact angle, has a broad maximum around 40°, and decreases at larger angles. For the Ar₂₉₅₃ cluster, the yield strongly increases with the impact angle, has a maximum around 45° followed by a steep decrease at larger angles. For both investigated cluster projectiles the primary energy is deposited so close to the surface so that the sputtering efficiency only weekly benefits from the shift of the deposited energy profile toward the surface which occurs at larger impact angles. In this study, molecular dynamics computer simulations are used to probe the effect of the impact angle on the efficiency of ejection molecules emitted from solid benzene by 14.75 keV Ar₃₆₆ and Ar₂₉₅₃ clusters.     

Fabrication of [110]-aligned Si quantum wires embedded in SiO2 by low-energy oxygen implantation

Si quantum wires (QWRs) embedded in SiO₂ are successfully fabricated by low-energy oxygen implantation on a V-groove patterned substrate. Si QWRs aligned to [1 1 0] appeared at the bottom-center of the V-groove. The [1 1 0] cross-section of the Si QWR is a hexagon encompassed by four Si {1 1 1} and two Si {0 0 1} lateral facets.     

Internal energy distribution of sputtered sulfur molecules

Bombarding targets of CS₂ and sulfur with keV Ar⁺ ions induces among other species the sputtering of S₂ molecules. We measured the internal energy (vibration and rotation) of these sputtered molecules with a laser induced fluorescence technique. The results show a Boltzmann behaviour for both the vibrational and rotational distributions. A vibrational temperature T_vib = 1500 K and a rotational temperature T_rot = 300 K is obtained for both target materials. The results are compared with different ejection mechanisms, where a molecule on the surface receives one (single collision) or two (double collision) momentum transfers from the solid. Two classical models are able to explain part of the experimentally observed internal energy distribution: a Monte Carlo calculation of the double collision model, and a single collision model assuming a sudden momentum transfer to the molecule as a whole, which yields an analytical expression (via a relation between the internal and kinetic energy). If we assume that some additional rotational cooling, due to time dependent relaxation effects, occurs during the ejection from the surface, the experimental results can be reasonably interpreted within the proposed sputtering models.     

Erosion of tungsten-doped amorphous carbon films in oxygen plasma

Tungsten-doped amorphous carbon films with 0–9 at.% W concentration were produced by magnetron sputtering and eroded in oxygen plasmas applying different bias voltages and substrate temperatures. The partial C and W erosion rates were determined from the C and W areal density changes measured by Rutherford backscattering spectrometry (RBS). The initial C removal rate increases with increasing ion energy and temperature and decreases with increasing W concentration. For W-doped films the erosion rate decreases with increasing plasma exposure duration. At low bias voltages the erosion process stops after W accumulation at the surface, which protects the carbon underneath from further erosion. RBS and X-ray photoelectron spectroscopy suggest that the W-rich layer at the surface is carbon free and consists of porous WO₃. Biasing to 200 V leads to removal of W by physical sputtering and, therefore, inhibits the formation of the protecting W oxide layer and the C erosion proceeds.     

Self-organized formation of layered carbon–copper nanocomposite films by ion deposition

The quasi-simultaneous deposition of low energy-mass-selected C⁺ and metal⁺ ions leads to the formation of metal–carbon nanocomposites. In the case of C⁺ and Cu⁺ deposition, a homogeneous distribution of small copper clusters in an amorphous carbon matrix is expected. However, at a certain C⁺/Cu⁺ fluence ratio and energy range, alternately metal-rich and metal-deficient layers in an amorphous carbon matrix with periods in the nm range develop have been observed. The metal-rich layers consist of densely distributed crystalline Cu particles while the metal-deficient layers are amorphous and contain only few and small Cu clusters. The formation of multilayers can be described by an interplay of sputtering, surface segregation, ion induced diffusion, and the stability of small clusters against ion bombardment. This formation has been investigated for the a-C:Cu system with respect to the ion energy and the C⁺/Cu⁺ fluence ratio. The sputter coefficient S_M = r_f S_CCu + S_CuCu is the parameter to switch between layer growth (S_M < 1) and homogeneous cluster distribution (S_M > 1).     

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.     

MD simulation of atomic displacements in pure metals and metallic bilayers during low energy ion bombardment at 0 K

Molecular Dynamics (MD) simulations of 100 eV Ar ion bombardment of (1 0 0) Ni and Al crystals, of bilayer crystals consisting of an Al (or Ni) layer on a (1 0 0) Ni (or Al) substrate, as well as pseudo-isotope bilayer crystals have been performed at 0 K using tight-binding potentials. For these systems sputtering yields, energy deposition with depth, atomic relocations, production of ad-atoms, depth distributions of vacancies and interstitials per ion impact were studied for times up to 7 ps. We observed that both the mean square displacement of atoms and defect production (vacancies, interstitials and ad-atoms) are larger in pure Al than in pure Ni. In addition, we observed for the bilayer systems Al/Ni and Ni/Al a high number of the near surface atomic relocations; especially ion bombardment induced exchange processes between atoms of the 1st (Al or Ni) and of the 2nd (substrate) layer. Potential energy calculations indicate that such relocations between the 1st and the 2nd layer are in both bilayer crystals energetically favourable. Both Al/Ni and Ni/Al bilayers show considerable higher production of ad-atoms as the pure Al and Ni targets. Typically ad-atoms are from the first layer, but in the Ni/Al bilayer system we found a substantial amount of Al ad-atoms from the 2nd layer (first Al layer). They contribute more to the ad-atom number than 1st layer Ni atoms. The mean square displacement of atoms in Al/Ni and Ni/Al crystals increases considerably during the thermal stages of the cascade evolution while it is almost constant in the case of the pure Al and Ni. Finally we observed that the maximum kinetic energies of atoms in the cascade volume after 4 ps are lower in the Ni and Al/Ni crystals than in Al and Ni/Al crystals, reflecting the lower cohesive energy of Al as compared to Ni. Calculations with pseudo-isotope bilayer crystals were performed to elucidate the influence of mass or potential on the observed effects.     

Damage buildup and the molecular effect in Si bombarded with PFn cluster ions

We study the molecular effect (ME) in damage accumulation in Si bombarded at room temperature with atomic P and F and cluster PF_n (n = 2 and 4) ions with an energy of 2.1 keV/amu. Correct ion irradiation conditions for unambiguous studies of the ME are discussed. Rutherford backscattering/channeling spectrometry results show that the damage buildup behavior strongly depends on the cluster ion size, and the ME efficiency increases rapidly with increasing the number of atoms in cluster ions. Moreover, the ME efficiency decreases with increasing the defect generation rate, indicating that dynamic annealing processes, rather than nonlinear energy spikes, play a major role in the ME for these irradiation conditions.     

High energy Si ions bombardment effects on the properties of nano-layers of SiO2/SiO2 + Ag

We grew 50 periodic SiO₂/SiO₂ + Ag multi-layers by electron beam deposition technique. The co-deposited SiO₂ + Ag layers are 7.26 nm, SiO₂ buffer layers are 4 nm, and total thickness of film was determined as 563 nm. We measured the thickness of the layers using in situ thickness monitoring during deposition, and optical interferometry afterwards. The concentration and distribution of Ag in SiO₂ were determined using Rutherford backscattering spectrometry (RBS). In order to calculate the dimensionless figure of merit, ZT, the electrical conductivity, thermal conductivity and the Seebeck coefficient of the layered structure were measured at room temperature before and after bombardment with 5 MeV Si ions. The energy of the Si ions was chosen such that the ions are stopped deep inside the silicon substrate and only electronic energy due to ionization is deposited in the layered structure. Optical absorption (OA) spectra were taken in the range 200–900 nm to monitor the Ag nanocluster formation in the thin layers.     

Determination of the sticking coefficient of energetic hydrocarbon molecules by molecular dynamics

The sticking coefficient of hydrocarbon species is a key quantity that influences the growth process of amorphous hydrocarbon layers. To extend the very limited database for low impact energies, classical molecular dynamics simulations were performed, determining the sticking coefficients of CH_x (x = 0 … 4) with kinetic energies between 5 and 100 eV. Similar simulations are performed with hydrogen substituted by deuterium. Additionally, analytical formulas are presented that fit the data very well and can be used to interpolate the simulation results.     

Sputtering of condensed noble gases by keV heavy ions

Bombardment of condensed Kr and Xe by 2–8 keV noble gas ions results in very high sputtering yields. A considerable fraction (10–30%) of the sputtered particles consists of Van der Waals clusters, with Kr₂, Kr₃, Xe₂, XeKr, XeKr₂ and ArKr having been observed. The kinetic energy distributions of the sputtered monomer-species are in agreement with a collision cascade mechanism. However, at the low energy side an excess yield is observed. This is explained by a model which takes into account the large sputtering yields and the damage of the surface during the sputtering process. The energy distributions of the dimers and trimers are satisfactorily explained by a statistical model. It is concluded that the dimer and trimer species are sputtered during an early stage of the cascade.